NIOSH Manual of Analytical Methods

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NMHM
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NIOSH
Manual of 4th
AnalyticalMethods Edition
MAY 3 0 1996
''S.OEPOS(TOfiypftOPERTV
U.S. DEPARTMENT OF HEALTH AND HUMAN SERVICES

Public Health Service
Centers for Disease Control and Prevention
National Institute for Occupational Safety and Health
CDC
CENTERS FOB DISEASE CONTROL
AND PREVENTION
s;/- •/
AN' 1/956j SUPP.COkk
FIRST SUPPLEMENT
to
NIOSH Manual of Analytical Methods (NMAM'™')
Fourth Edition
UNIVERSITY OF MINNESOTA
GOVERNMENT PUBLICATIONS LIBRARY
AUG 2 2 1997
U.S. DEPOSITORY PROPERTY

U.S.G.P.0.0-295
May 15, 1996
NIOSH Manual of Analytical Methods

TRANSMITTAL NOTICE
'This is the First Supplement to the NIOSH Manual of Analytical Methods (NMAM), 4th
edition (printed August 15, 1994). This supplement is dated May 15, 1996, and includes
15 methods, three new chapters, and updated Contents, Method Finder, and indexes, as
well as errata replacement pages.
INSTRUCTIONS FOR INSERTING FIRST SUPPLEMENT INTO YOUR MANUAL
Table of Contents
Remove Contents pages vi to xiii. Replace with new Contents.
Method Finder
Remove old pages MF-1 to MF-14. Replace with new MF-1 to MF-17.
Using NMAM (Blue pages)

Remove pp. 32 to 63. Replace with pp. 32 to 96.
Indexes (Yellow pages - end of 3rd volume)

Remove pp. A-1 1 through A-56. Replace with A-1 1 to A-59.
Methods
Insert methods alphabetically in NMAM.
Ammonia by IC, 6016

n-Butyl Mercaptan, 2525
Capsaicin and Dihydrocapsaicin, 5041
Carbon Monoxide, 6604
Chromium (VI) in Settled Dust Samples, 9101
Elemental Carbon (Diesel Exhaust), 5040
Glycols, 5523
Isocyanates, 5522
Lead in Air by Chemical Spot Test, 7700
Lead in Surface Wipe Samples, 9100 - Remove existing version, and replace.
Methyl Bromide, 2520
Methyl Ethyl Ketone, 2500 - Remove existing version, and replace.
Oil Mists, Mineral, 5026 - Remove existing version, and replace.
Terpenes, 1 552
Volatile Organic Compounds (Screening), 2549
Errata
Only the pages that contained errors are being replaced. In general, complete methods have
not been supplied, except where page content has changed because of additions or
deletions. Remove old pages and replace with corresponding pages.
NIOSH MANUAL OF ANALYTICAL METHODS
4th EDITION
Peter M. Eller, Ph.D., CIH

Editor
Mary Ellen Cassinelli

Associate Editor

Division of Physical Sciences and Engineering
Cincinnati, Ohio
August 1994
Mention of trade names or products in this publication does not constitute endorsement
by the National Institute for Occupational Safety and Health. Trade names are shown as
proper names but the trademark or registration symbols have been omitted for editorial
reasons.
A trademark application is pending for the designation "NMAM" for this manual.
This edition of NMAM was prepared as a project of the NIOSH Division of Physical
Sciences and Engineering (DPSE), Laurence J. Doemeny, Ph.D., Acting Director, with the
technical cooperation of the NIOSH Divisions of Biomedical and Behavioral Science
(DBBS), Respiratory Disease Studies (DRDS), Surveillance, Hazard Evaluations and Field
Studies (DSHEFS), Standards Development and Technology Transfer (DSDTT), and
Training and Manpower Development (DTMD); and the U.S. Department of Labor,
Occupational Safety and Health Analytical Laboratory.
Previous editions of NMAM are available from the National Technical Information Service
(NTIS), 5285 Port Royal Road, Springfield, VA 22161 (telephone 703/487-4650), with
the following stock numbers:
Second Edition
Volume 1 (April, 1977) Stock # PB 274-845
Volume 4 (August, 1978) Stock # PB 83-105439
Third Edition
Volumes 1 & 2 (February, 1984) Stock # PB 85-179018
First Supplement (May, 1985) Stock # PB 86-116266
Second Supplement (August, 1987) Stock # PB 88-204722
Third Supplement (May, 1989) Stock # PB 90-162470
Fourth Supplement (August, 1990) Stock # PB 91-152660
DHHS (NIOSH) Publication No. 94-113

FOREWORD
Adherence to exposure control limits has been an important strategy

in the prevention of occupational disease for almost 60 years. Methods of
monitoring exposure in the occupational environment are vital to this
prevention strategy. They produce the information needed to modify and
improve control systems so as to protect the worker from occupational health
hazards. These methods are also a necessary part of all standards that set
limits for environmental exposures to toxic substances.
The methods presented in this improved Fourth Edition are intended to be

accurate, clear, and concise. They incorporate the results of recent research
by NIOSH. Applicable methods are also incorporated into Criteria Documents
produced by NIOSH for recommending standards to the Occupational Safety
and Health Administration.
It is a pleasure to present this Manual for your use and welcome your
comments about it.
Linda Rosenstock, M.D., M.P.H.

Director, National Institute for
Occupational Safety and Health
Centers for Disease Control
and Prevention
ABSTRACT
One of the functions of the National Institute for Occupational Safety and Health (NIOSH) is
the development of sampling and analytical methods for monitoring occupational exposures
to toxic substances in air and biological samples. These methods are published in the NIOSH
Manual of Analytical Methods (NMAM), now in its fourth edition. The monitoring methods
cover the collection of aerosols, gases, and vapors in air with active samplers (filters, sorbent
tubes, impingers) followed by laboratory analysis, as well as with diffusive samplers and
direct-reading field instruments. Additions to the fourth edition are: method classification,
estimate of accuracy, RTECS numbers, and a method finder.
The purpose of method classification is to quickly identify the usefulness of the method;
therefore, methods in the NMAM, 4th ed., are classified into three evaluation categories: Full,
Partial, and Unrated.
An accuracy estimate, which indicates how closely the method compares to the NIOSH
±25% criterion for a valid method, has been added to the summary page of the method.
The methods are arranged in alphabetical order by method name. The Method Finder provides
a simple means of locating a method for a specific chemical. The Method Finder is a table in
which the names of common chemicals are listed alphabetically with the corresponding
method name and number, type of sampler, sampling rates and volumes, and analytical
technique.
Indices of chemical names and synonyms (alphabetical), Third and Fourth Edition method
numbers, and Second Edition method numbers are provided for cross reference.
The NMAM also includes chapters that discuss several topics of special interest. Notable
among these are quality assurance, strategies for sampling airborne substances, method
development and evaluation, and discussions of some portable direct-reading instrumentation.
The NIOSH Manual of Analytical Methods, 4th ed.. is available in electronic format through
private software vendors.
iv
ACKNOWLEDGMENTS
More than fifty people contributed to the publication of the 4th edition of NMAM. The authors
of individual methods and introductory chapters are indicated. These include NIOSH scientists
in the Division of Physical Sciences and Engineering; Division of Biomedical and Behavioral
Sciences; Division of Respiratory Disease Studies; Division of Surveillance, Hazard Evaluation,
and Field Studies; and Division of Training and Manpower Development; and personnel at
DataChem Laboratories, Salt Lake City, Utah.
The revision was accomplished under the direction of Laurence J. Doemeny, Ph.D., Acting
Director, Division of Physical Sciences and Engineering, NIOSH.
Special thanks for manuscript preparation are due to Grace A. Fannin and Deanna L. Elfers.
CONTENTS
PAGE
FOREWORD iii
ABSTRACT iv
ACKNOWLEDGMENTS v
METHOD FINDER MF-1
INTRODUCTION
A. Purpose and Scope 1
B. How to Use NMAM 1
C. Quality Assurance by D. L. Smith, CIH, and M. L. Bolyard, CIH 6
D. Considerations for Sampling Airborne Substances by Charles S. McCammon, Ph.D 16
E. Development and Evaluation of Methods by Eugene R. Kennedy, Ph.D, Thomas J. Fishbach,
Ruiguang Song, Ph.D, Peter M. Eller, Ph.D, Stanley A. Shulman, Ph.D, and R. DeLon Hull, Ph.D.. . . 32
F. Application of Biological Monitoring Methods by Alexander W. Teass, Ph.D,
Raymond E. Biagini, Ph.D, D. Gayle DeBord, Ph.D, and R. DeLon Hull, Ph.D 48
G. Aerosol Photometers for Respirable Dust Measurements by Paul A. Baron, Ph.D 62
H. Portable Electrochemical Sensor Methods by W. J. Woodfin 69
I. Portable Gas Chromatography by Judd C. Posner, Ph.D 74
J. Sampling and Characterization of Bioaerosols by Paul A. Jensen, Ph.D., and Millie P. Schafer, Ph.D. 80
METHODS
METHOD
METHOD NAME NUMBER
ACETALDEHYDE by GC 2538
ACETALDEHYDE by HPLC 3507
ACETIC ACID 1 603
ACETIC ANHYDRIDE 3506
ACETONE CYANOHYDRIN 2506
ACETONITRILE 1 606
ACIDS, INORGANIC 7903
Hydrobromic acid Hydrofluoric acid Phosphoric acid
Hydrochloric acid Nitric acid Sulfuric acid
ACROLEIN 2501
ACRYLONITRILE 1 604
ALCOHOLS I (desorption in 99:1 CS2:2-butanol) 1400
tert-Butyl alcohol Isopropyl alcohol Ethanol
ALCOHOLS II (desorption in 99:1 CS2:2-propanol) 1401
n-Butyl alcohol Isobutyl alcohol
sec-Butyl alcohol n-Propyl alcohol
ALCOHOLS III (desorption in 95:5 CS2:2-propanol) 1402
Allyl alcohol Isoamyl alcohol Methyl isobutyl carbinol
Cyclohexanoi Diacetone alcohol
ALCOHOLS IV (desorption in 95:5 CH2CI2:methanol) 1403
2-Butoxyethanol 2-Ethoxyethanol 2-Methoxyethanol
ALDEHYDES, SCREENING 2539
ALDRIN and LINDANE 5502
ALKALINE DUSTS 7401
ALLYL CHLORIDE 1 000
ALLYL GLYCIDYL ETHER 2545
ALUMINUM 7013
5/15/96 vi NIOSH Manual of Analytical Methods

AMINES, ALIPHATIC 2010
Diethylamine Dimethylamine
AMINES, AROMATIC 2002
Aniline /V,/V-Dimethyl-p-toluidine 2,4-Xylidine
/V,/V-Dimethylaniline o-Toluidine
AMINOETHANOL COMPOUNDS I 2007
2-Aminoethanol 2-Diethylaminoethanol
2-Dibutylaminoethanol
AMINOETHANOL COMPOUNDS II 3509
Monoethanolamine (MEA) Diethanolamine (DEA)
Triethanolamine (TEA)
AMMONIA 601 5
AMMONIA by IC 601 6
ANISIDINE 2514
ARSENIC (hydride AAS) 7900
ARSENIC, ORGANO- 5022
P-Aminophenylarsonic acid Methylarsonic acid
Dimethylarsenic acid
ARSENIC TRIOXIDE (GFAAS) 7901
ARSINE 6001
ASBESTOS (bulk) by PLM 9002
ASBESTOS, CHRYSOTILE by XRD 9000
ASBESTOS and other FIBERS by PCM 7400
ASBESTOS FIBERS by TEM 7402
ASPARTAME 5031
AZELAIC ACID 501 9
BARIUM, soluble compounds 7056

BENZENE by portable GC 3700
BENZIDINE and 3,3'-DICHLOROBENZIDINE 5509
BENZIDINE in urine (GC) 8306
BENZOYL PEROXIDE 5009
BERYLLIUM 7102
BORON CARBIDE 7506
BROMOXYNIL and BROMOXYNIL OCTANOATE 5010
1 ,3-BUTADIENE 1 024
n-BUTYLAMINE 201 2
n-BUTYL GLYCIDYL ETHER 1616
n-BUTYL MERCAPTAN 2525
CADMIUM by FAAS 7048

CALCIUM 7020
CAPSAICIN and DIHYDROCAPSAICIN 5041
CARBARYL 5006
CARBON BLACK 5000
CARBON DIOXIDE 6603
CARBON DISULFIDE 1 600
CARBON MONOXIDE 6604
CHLORDANE 5510
CHLORINATED CAMPHENE 5039
CHLORINATED DIPHENYL OXIDE 5025
CHLORINATED TERPHENYL 5014
CHLORINE AND BROMINE 601 1
CHLOROACETALDEHYDE 201 5
CHLOROACETIC ACID 2008
p-CHLOROPHENOL 2014
3-CHLOROPRENE 1 002
5/1 5/96 vii NIOSH Manual of Analytical Methods

CHROMIUM by FAAS 7024
CHROMIUM, HEXAVALENT, by VIS 7600
CHROMIUM, HEXAVALENT, by 1C 7604
CHROMIUM, HEXAVALENT, in settled dust samples 9101
COBALT 7027
COPPER (dust and fume) 7029
CRESOLS and PHENOL 2546
CROTONALDEHYDE 351 6
CYANIDES (aerosol and gas) by ISE 7904
CYANURIC ACID 5030
1 ,3-CYCLOPENTADIENE 2523
2,4-D and 2,4,5-T 5001

DEMETON 5514
DIAZOMETHANE 251 5
DIBORANE 6006
DIBUTYL PHOSPHATE 501 7
DIBUTYL PHTHALATE and DK2-ETHYLHEXYL) PHTHALATE 5020
DICHLORODIFLUOROMETHANE, 1 ,2-DICHLOROTETRAFLUOROETHANE,
and CHLORODIFLUOROMETHANE 1018
DICHLOROETHYL ETHER 1004
DICHLOROFLUOROMETHANE 2516
1,1-DICHLORO-1-NITROETHANE 1601
DIFLUORODIBROMOMETHANE 1012
DIMETHYLACETAMIDE and DIMETHYLFORMAMIDE 2004
1 ,1-DIMETHYLHYDRAZINE 351 5
DIMETHYL SULFATE 2524
DIOXANE 1 602
DIPHENYL 2530
DYES, BENZIDINE, o-DIANISIDINE, and o-TOLIDINE 5013
ELEMENTAL CARBON (DIESEL EXHAUST) 5040

ELEMENTS in blood or tissue 8005
Antimony Lanthanum Silver
Cadmium Lead Strontium
Chromium Manganese Tin
Cobalt Molybdenum Titanium
Copper Nickel Zinc
Iron Platinum
ELEMENTS by ICP 7300

Aluminum Iron Platinum Tungsten
Arsenic Lead Selenium Vanadium
Beryllium Lithium Sodium Yttrium
Calcium Magnesium Silver Zinc
Cadmium Manganese Tellurium Zirconium
Chromium Molybdenum Tin
Cobalt Nickel Titanium
Copper Phosphorus Thallium
ENDRIN 5519
EPICHLOROHYDRIN 1010
EPN 5012
ESTERS I 1 450
n-Amyl acetate Ethyl acrylate
sec-Amyl acetate Isoamyl acetate
n-Butyl acetate Isobutyl acetate
5/1 5/96 viii NIOSH Manual of Analytical Methods

sec-Butyl acetate Methyl isoamyl acetate
t-Butyl acetate n-Propyl acetate
2-Ethoxyethyl acetate
ETHYL ACETATE 1 457
ETHYL BROMIDE 1011
ETHYL CHLORIDE 251 9
ETHYL ETHER 1610
ETHYL FORMATE 1 452
ETHYLENE CHLOROHYDRIN 251 3
ETHYLENEDIAMINE, DIETHYLENETRIAMINE, & TRIETHYLENETETRAMINE 2540
ETHYLENE DIBROMIDE 1008
ETHYLENE OXIDE 1614
ETHYLENE OXIDE (portable GO 3702
ETHYLENE THIOUREA 501 1
ETHYLENIMINE 3514
FLUORIDE in urine 8308

FLUORIDES by lC 7906
FLUORIDES by ISE 7902
FLUOROTRICHLOROMETHANE 1006
FORMALDEHYDE [2-(hydroxymethyl)piperidine] by GC 2541
FORMALDEHYDE (chromotropic acid) by VIS 3500
FORMALDEHYDE ON DUST 5700
FORMIC ACID by IC 201 1
FURFURAL 2529
FURFURYL ALCOHOL 2505
GLUTARALDEHYDE by HPLC/UV 2532

GLYCIDOL 1 608
GLYCOLS 5523
Ethylene glycol 1 ,3-butylene glycol Triethylene glycol
Propylene glycol Diethylene glycol Tetraethylene glycol
HEXACHLOROBUTADIENE 2543
HEXACHLORO-1,3-CYCLOPENTADIENE 2518
HIPPURIC ACID in urine (VIS) 8300
HIPPURIC and METHYL HIPPURIC ACIDS in urine (HPLC) 8301
HYDRAZINE 3503
HYDROCARBONS, BP 36 - 1 26 <>C 1 500
Benzene n-Heptane n-Octane
Cyclohexane n-Hexane n-Pentane
Cyclohexene Methylcyclohexane Toluene
HYDROCARBONS, AROMATIC 1 501
Benzene a-Methylstyrene Vinyltoluene
p-tert-Butyltoluene Naphthalene Xylene
Cumene Styrene
Ethylbenzene Toluene
HYDROCARBONS, HALOGENATED 1003
Benzyl chloride o-Dichlorobenzene Hexachloroethane
Bromoform p-Dichlorobenzene Methylchloroform
Carbon tetrachloride 1,1-Dichloroethane 1,1,2-Trichloroethane
Chloroform 1,2-Dichloroethylene 1,2,3-Trichloropropane
Chlorobenzene Ethylene dichloride Tetrachloroethylene
Chlorobromomethane
HYDROGEN CYANIDE 601 0
HYDROGEN SULFIDE by IC 601 3
HYDROQUINONE 5004
5/15/96 ix NIOSH Manual of Analytical Methods

IODINE 6005
ISOCYANATES, MONOMERIC 5521
2,4-TDI 2,6-TDI MDI HDI
ISOCYANATES (Fluorescence Detection) 5522
2,4-TDI 2,6-TDI MDI HDI
ISOPHORONE 2508
ISOPROPYL ACETATE 1 454
ISOPROPYL ETHER 1618
ISOPROPYL GLYCIDYL ETHER 1 620
KEPONE 5508
KETONES I (desorption in CS2) 1 300
Acetone 2-Hexanone
Cyclohexanone Methyl isobutyl ketone
Diisobutyl ketone 2-Pentanone
KETONES II (desorption in 99:1 CS2:methanol) 1301
Camphor 5-Methyl-3-heptanone
Ethyl butyl ketone Methyl-(n-amyl)-ketone
Mesityl oxide
LEAD in air by chemical spot test 7700

LEAD in blood and urine 8003
LEAD in surface wipe samples 9100
LEAD by FAAS 7082
LEAD by GFAAS 71 05
LEAD SULFIDE 7505
MALEIC ANHYDRIDE 3512

MBOCA in urine 8302
MERCAPTANS, Methyl-, Ethyl-, n-Butyl- 2542
MERCURY 6009
METALS in urine (ICP) 831 0
Aluminum Lead Silver
Barium Manganese Strontium
Cadmium Molybdenum Tin
Chromium Nickel Titanium
Copper Platinum Zinc
Iron
METHANOL 2000
METHYL ACETATE 1 458
METHYL ACRYLATE 1 459
METHYL BROMIDE 2520
METHYLAL 1611
METHYL CELLOSOLVE ACETATE 1451
METHYL CHLORIDE 1 001
METHYLCYCLOHEXANOL 1404
METHYLCYCLOHEXANONE 2521
METHYLENE CHLORIDE 1005
4,4'-METHYLENEDIANILINE (MDA) 5029
METHYL ETHYL KETONE 2500
METHYL ETHYL KETONE, ETHANOL and TOLUENE in blood 8002
METHYL ETHYL KETONE PEROXIDE 3508
METHYL IODIDE 1014
METHYL METHACRYLATE 2537
METHYL tert-BUTYL ETHER (MTBE) 1615
MONOMETHYLANILINE 351 1
MONOMETHYLHYDRAZINE 3510
5/15/96 x NIOSH Manual of Analytical Methods

NAPHTHAS 1 550
Coal tar naphtha Mineral spirits Petroleum naphtha Stoddard solvent
Kerosene Petroleum ether Rubber solvent
NAPHTHYLAMINES 5518
NICKEL CARBONYL 6007
NICOTINE 2544
NITRIC OXIDE and NITROGEN DIOXIDE 6014
p-NITROANILINE 5033
NITROBENZENES 2005
4-Chloronitrobenzene Nitrobenzene Nitrotoluene
NITROETHANE 2526
NITROGLYCERIN/EGDN 2507
NITROMETHANE 2527
2-NITROPROPANE 2528
NITROSAMINES 2522
/V-nitrosodimethylamine /V-nitrosomorpholine
/V-nitrosodiethylamine /V-nitrosopiperidine
/V-nitrosodipropylamine A/-nitrosopyrrolidine
A/-nitrosodibutylamine
NITROUS OXIDE (field-readable) 6600
1-OCTANETHIOL 2510
OIL MIST, MINERAL 5026
ORGANOPHOSPHORUS PESTICIDES 5600
Azinphos methyl Chlorpyrifos Diazinon Dicrotophos
Disulfoton Ethion Ethoprop Fenamiphos
Fonofos Malathion Methamidophos Methyl parathion
Mevinphos (E) Mevinphos (E&Z) Monocrotophos (E) Monocrotophos (Z)
Parathion Phorate Ronnel Sulprophos
Terbufos
ORGANOTIN COMPOUNDS 5504
Dibutyltin A/s(isooctyl mercaptoacetate) Tetrabutyltin
Tributyltin chloride Tricyclohexyltin hydroxide
OXYGEN (field-readable) 6601
PARAQUAT 5003
PARTICULATES NOT OTHERWISE REGULATED, RESPIRABLE 0600
PARTICULATES NOT OTHERWISE REGULATED, TOTAL 0500
PENTACHLOROETHANE 2517
PENTACHLOROPHENOL 5512
PENTACHLOROPHENOL in blood 8001
PENTACHLOROPHENOL in urine 8303
PENTAMIDINE ISETHIONATE 5032
PHENOL and p-CRESOL in urine 8305
PHENYL ETHER 1617
PHENYL ETHER-DIPHENYL MIX 201 3
PHENYL GLYCIDYL ETHER 1619
PHENYLHYDRAZINE 3518
PHOSPHINE 6002
PHOSPHORUS 7905
PHOSPHORUS TRICHLORIDE 6402
POLYCHLOROBENZENES 5517
POLYCHLOROBIPHENYLS 5503
POLYCHLOROBIPHENYLS in serum 8004
POLYNUCLEAR AROMATIC HYDROCARBONS (HPLC) 5506
Acenaphthene Benzo[ghi]perylene Fluorene
Acenaphthylene Benzo[a]pyrene lndeno[1,2,3-cd]pyrene
5/1 5/96 xi NIOSH Manual of Analytical Methods

Anthracene Benzo[e]pyrene Naphthalene
Benz[a]anthracene Chrysene Phenanthrene
Benzo[b]fluoranthene Dibenz[a,h]anthracene Pyrene
Benzo[k]fluoranthene Fluoranthene
POLYNUCLEAR AROMATIC HYDROCARBONS (GC) 5515
Acenaphthene Benzo[ghi]perylene Fluorene
Acenaphthylene Benzo[a]pyrene lndeno[1,2,3-cd]pyrene
Anthracene Benzo[e]pyrene Naphthalene
Benz[a]anthracene Chrysene Phenanthrene
Benzo[b]fluoranthene Dibenz[a,h]anthracene Pyrene
Benzol k I fluoranthrni: Fluoranthene
PROPYLENE DICHLORIDE 1013
PROPYLENE OXIDE 1612
PYRETHRUM 5008
PYRIDINE 1613
RIBAVIRIN 5027
ROTENONE 5007
SILICA, AMORPHOUS 7501

SILICA in coal mine dust by IR 7603
SILICA, CRYSTALLINE, Respirable, by XRD 7500
SILICA, CRYSTALLINE by VIS 7601
SILICA, CRYSTALLINE by IR 7602
STIBINE 6008
STRYCHNINE 501 6
SULFUR DIOXIDE 6004
SULFUR HEXAFLUORIDE by portable GC 6602
SULFURYL FLUORIDE 601 2
SUPER ABSORBENT POLYMER 5035
TERPENES 1 552
Limonene, d-, I- a-pinene 3-pinene 3-carene
o-TERPHENYL 5021
1,1,2,2-TETRABROMOETHANE 2003
1,1,1,2-TETRACHLORO-2,2-DIFLUOROETHANEand
1,1,2,2-TETRACHLORO-1,2-DIFLUOROETHANE 1016
1,1,2,2-TETRACHLOROETHANE 1019
TETRAETHYL LEAD 2533
TETRAETHYL PYROPHOSPHATE (TEPP) 2504
TETRAHYDROFURAN 1609
TETRAMETHYL LEAD 2534
TETRAMETHYL THIOUREA 3505
TETRANITROMETHANE 3513
THIRAM 5005
TOLUENE (passive) 4000
2,4- & 2,6-TOLUENEDIAMINE (TDA) 5516
TOLUENE-2,4-DIISOCYANATE (TDI) 2535
TRIBUTYL PHOSPHATE 5034
TRICHLOROETHYLENE 1022
TRICHLOROETHYLENE (portable GC) 3701
1,1,2-TRICHLORO-1,2,2-TRIFLUOROETHANE 1020
TRIFLUOROBROMOMETHANE 1017
TRIMELLITIC ANHYDRIDE 5036
2,4,7-TRINITROFLUOREN-9-ONE 5018
TRIORTHOCRESYL PHOSPHATE 5037
TRIPHENYL PHOSPHATE 5038
5/15/96 xii NIOSH Manual of Analytical Methods

TUNGSTEN (soluble and insoluble) 7074
TURPENTINE 1551
VALERALDEHYDE 2536
VANADIUM OXIDES 7504
VINYL ACETATE 1 453
VINYL BROMIDE 1 009
VINYL CHLORIDE 1 007
VINYLIDENE CHLORIDE 1015
VOLATILE ORGANIC COMPOUNDS (SCREENING) 2549
WARFARIN 5002
ZINC 7030
ZINC OXIDE 7502
III. APPENDIXES
A. Unit Equivalents A-1

B. Air Concentration Calculations for Comparison to OSHA Standards A-2
IV. Glossary of Abbreviations, Definitions and Symbols A-3
V. Indexes
A. Third and Fourth Edition Method Numbers A-1 1
B. First and Second Edition Method Numbers A-1 5
C. Names and Synonyms A-29
5/15/96 xiii NIOSH Manual of Analytical Methods

METHOD FINDER (Key on page MF-17)
Meth. Eval Flow Rate Min. Max. Analytical

Chemical No. Method Name (L/min) Vol. Vol. Technique Sampler
(L) (L)
Acenaphthene 5506; POLYNUCLEAH AROMATIC P 2.0 200 1000 HPLC-FL/UV; PTFE & XAD-2
5515 HYDROCARBONS GC-FIO
Acenapbthylene 5506; POLYNUCLEAR AROMATIC P 2.0 200 1000 HPLC-FL/UV; PTFE »V XAD-2
5515 HYDROCARBONS GC-FID
Acetaldehyde 2538 ACETALDEHYDE U 0.01-0.05 1 12 GC-FID XAD-2/HMP
Acetaldehyde 2539 ALDEHYDES, SCREENING P 0.01-0.05 5 5 GC-FID/MS XAD2/HMP
Acetaldehyde 3507 ACETALDEHYDE F 0.1-0.5 6 60 HPLC-UV BuB
Acetic acid 1603 ACETIC ACID F 0.01-0.1 20 300 GC-FID CCT
Acetic anhydride 3506 ACETIC ANHYDRIDE F 0.2-1.0 25 100 VIS BuB
Acetone 1300 KETONES 1 F 0.01-0.2 0.5 3 GC-FID CCT
Acetone 2549 VOLATILE ORGANIC CPDS (Screening) P 0.01-0.05 1 6 TD/GC-MS TD
Acetone cynnohydrin 2506 ACETONE CYANOHYDRIN P 0.2 0.3 12 GC-NPD PorQS
Acetonltrile 1606 ACETONITRILE P 0.01-0.2 3 25 GC-FID CCT
Acetylene dlchlorlde 1003 HYDROCARBONS, HALOGENATED P 0.01-0.2 0.2 5 GC-HD CCT
Acetylene tetrabromide 2003 1,1.2,2-TETRABROMOETHANE P 0.2-1.0 50 100 GC-FID SG
Acetylene tetrachloride 1019 1 .1 ,2,2-TETRACHLOROETHANE P 0.01-0.2 3.0 30 GC-FID PCT
Acids, inorganic 7903 ACIDS, INORGANIC F 0.2-0.5 3.0 100 IC SG (washed)
Acrolein 2501 ACROLEIN P 0.01-0.1 1.5 48 GC-NPD XAD-2/HMP
Acrolein 2539 ALDEHYDES, SCREENING P D.01-O.O5 5 5 GC-FID/MS XAD-2WMP
Acrylonitrilft 1604 ACRYLONITRILE F 0.01-0.2 3.5 20 GC-FID CCT
Aldehydes, screening 2539 ALDEHYDES, SCREENING P 0.01-0.05 5 5 GC-FID/MS XAD-2
Aldrin 5502 ALDRIN & LINDANE F 0.2-1.0 18 240 GC-ECN GFF & BuB
Alkaline dusts 7401 ALKALINE DUSTS F 1 -4 70 1000 Titration PTFE
Allyl alcohol 1402 ALCOHOLS III P 0.01-0.2 1 10 GC-FID CCT
Allyl chloride 1000 ALLYL CHLORIDE F 0.01-1.0 16 100 GC-FID CCT
Allyl glycidyl ether 2545 ALLYL GLYCIDYL ETHER F 0.01-0.2 1.5 8 GC-FID Tenax
Allyl trichloride 1003 HYDROCARBONS, HALOGENATED P 0.01-0.2 2 60 GC-FID CCT
Alumina 0500 PARTICULATES N.O.R. F 1 -2 7 133 Gray PVC, tared
Aluminum 7300 ELEMENTS by ICP P 1 -4 5 100 ICP-AES MCEF
Aluminum 7013 ALUMINUM & CPDS, as Al P 1-3 10 400 FAAS MCEF
Amines, aliphatic 2010 AMINES, ALIPHATIC P 0.01-1.0 3 30 GC-FID SG
Amines, aromatic 2002 AMINES, AROMATIC F 0.2-1.0 30 150 GC-FID SG
Aminobenzene 2002 AMINES, AROMATIC F 0.2-1.0 30 150 GC-FID SG
2-Aminoathanol 2007 AMINOETHANOL COMPOUNDS 1 P 0.01-0.2 4 24 GC-FID SG
2-Aminoethanol 3509 AMINOETHANOL COMPOUNDS II P 0.5-1.0 5 300 IC IMP
Q-Aminophenylarsonic acid 5022 ARSENIC, ORGANO- F 1 -3 50 1000 IC-HYAAS PTFE
2-Aminotoluene 2002 AMINES, AROMATIC F 0.02-1.0 10 150 GC-FID SG
Ammonia 6015 AMMONIA by VIS P 0.1-0.2 0.1 90 VIS-Auto SG » H,SO,
Ammonia 6016 AMMONIA by IC f 0.1 -O.5 0.1 96 IC SG + H,SO..
5/15/96 MF-1 NIOSH Manual of Analytical Methods

Meth. Eval Flow Rate Mill Max. Analytical
Ch«mlcsl No. Method Name (L/min) Vol. Vol. Technique Sampler
(LI (U
n- and sec-Amyl acetate 1450 ESTERS I P 0.01-0.2 1 10 GC-FID CCT
Amyl acetate 2549 VOLATILE ORGANIC CPDS (Screening) P 0.01-0.05 1 6 TD/GC-MS TD
Aniline 2002 AMINES, AROMATIC F 0.02-0.2 5 30 GC-FID SG
Anlsldhna 2514 ANISIDINE F 0.5-1.0 24 320 HPLC-UV XAD-2
Anthracene 5506; POLYNUCLEAR AROMATIC P 2.0 200 1000 HPLC-FUUV; PTFE & XAD-2
p-Anunllte acid 5022 ARSENIC, organo- F 1-3 50 1000 IC-HYAAS PTFE
Arsenic 7800 ARSENIC & compounds, as As P 1-3 30 1000 FAAS MCEF
Arsenic 7300 ELEMENTS by ICP P 1 -4 5 2000 ICP-AES MCEF
Arsenic trioxlde 7901 ARSENIC TRIOXIDE, as As F 1 -3 30 1000 GFAAS MCEF
Arsine 6001 ARSINE F 0.01-0.2 0.1 10 GFAAS CCT
Asbestos 7400 ASBESTOS FIBERS by PCM F 0.5-16 400 Var PCM MCEF-open
Asbestos 7402 ASBESTOS FIBERS by TEM P 0.5-16 400 Var TEM MCEF-open
Asbestos 9000 ASBESTOS, CHRYSOTILE by XRD F NA NA NA XRD bulk
Asbestos 9002 ASBESTOS (bulk) by PLU P NA NA NA PLM bulk
Aspartame 5031 ASPARTAME P 1-3 70 1200 HPLC-UV PTFE
Azelalc acid 5019 AZELAIC ACID P 1 -3 200 1000 GC-FID PVC
Azinphos methyl 6600 ORGANOPHOSPHORUS PESTICIDES F 0.2-1.0 12 240 GC-FPD OVS-2
BMP 5506;
5515
POLYNUCLEAR AROMATIC
HYDROCARBONS
P 2.0 200 1000 HPLC-FUUV;
GC-FID
PTFE & XAD-2
Barium 7056 BARIUM, SOLUBLE COMPOUNDS F 1-4 5O 2000 FAAS MCEF
Benuldehyde 2549 VOLATILE ORGANIC CPUS (Screening) P 0.01-0.05 1 6 TD/GC-MS TD
Beni(a)anthr»CBne 5506; POLYNUCLEAR AROMATIC P 2.0 200 1000 HPLC-FUUV; PTFE & XAD-2
Benzene 2549 VOLATILE ORGANIC CPDS (Screening) P 0.01-0.05 1 6 TD/GC-MS TD
Benzene 1700 BENZENE by portable GC P >0.02 NA 80% GC air bag

vol
Benzene 1501 HYDROCARBONS, AROMATIC P 0.01-0.2 5 30 GC-FID CCT
Benzene 1500 HYDROCARBONS, BP 36-126'C F 0.01-0.2 2 30 GC-FID CCT
Benzidine Dyes 5013 DYES P 1 -3 150 500 HPLC-UV PTFE
Benzldine 5509 BENZIDINE and 3,3'-DICHLORO- F 0.2 20 100 HPLC-UV GFF

BENZIDINE
Benzo(a}pyn>ne 5506; POLYNUCLEAR AROMATIC P 2.0 200 1000 HPLC-FUUV; PTFE & XAD-2
8enzo(b)nuoranthene 5606; POLYNUCLEAR AROMATIC P 2.0 200 1000 HPLC-FUUV; PTFE & XAD-2
Benzo(e)pynin« 5506; POLYNUCLEAR AROMATIC P 2.0 200 1000 HPLC-FUUV; PTFE & XAD-2
5515 HYDROCARBONS GC-ID
B«nzo(k)fluoranthen» 5508; POLYNUCLEAR AROMATIC P 2.0 200 1000 HPLC-FUUV; PTFE S. XAD-2
Benzo(ghi)perylene 5506; POLYNUCLEAR AROMATIC P 2.0 200 1000 HPLC-FUUV; PTFE & XAD-2
Benzoyl peroxide 6009 BENZOYL PEROXIDE F 1 -3 40 400 HPLC-UV MCEF
Benzyl chloride 1003 HYDROCARBONS, HALOGENATED P 0.01-0.2 6 50 GC-FID CCT
Beryllium 7300 ELEMENTS bv ICP P 1 -4 1250 2000 ICP-AES MCEF

Meth. Eval Flow Rate Mill Max. Analytical
Chemical No. Method Name (I mini Vol. Vol. Technique Sampler
(L) (L)
BeryIIium & compound* 7102 BERYLLIUM and cpds, as Bo F 1-4 25 1000 HGAAS MCEF
Biphenyl 2510 DIPHENYL F 0.01-0.5 15 30 GC-FID Tenax GC
Boron carbide. 7506 BORON CARBIDE P 1.7 or 2.2 100 1000 XRD CYC & PVC
Boron oxide 0500 PARTICULATES N.O.R. F 1.5-2.0 25 133 Grav PVC
Bromine 6011 CHLORINE and BROMINE F 0.3-1.0 8 360 IC AgF
Bromoform 1003 HYDROCARBONS, HALOGENATED P 0.01-0.2 4 70 GC-FID CCT
Bromotrifluoromethane 1017 TRIFLUOROBROMOMETHANE P 0.01-0.05 0.3 1.0 GC-FID 2CCT
BromoxynII 5010 BROMOXYNIL and B'OCTANOATE P 1 -3 2 400 HPLC-UV PTFE
Bromoxynil octanoate 5010 BROMOXYNIL and B'OCTANOATE P 1-3 90 400 HPLC-UV PTFE
1,3-Butadiene 1024 1,3-BUTADIENE F 0.01-0.5 5 26 GC-FID CCT
2-Butanone 2500 METHYL ETHYL KETONE F 0.01-0.2 1 12 GC-FID Carbon beads
2-Butanone 2549 VOLATILE ORGANIC CPDS (Screening) P 0.01-0.05 1 6 TD/GC-MS TD
2-Butoxyethyanol 2549 VOLATILE ORGANIC CPDS (Screening) P 0.01-0.05 1 6 TD/GC-MS TD
2-Butoxyethanol 1403 ALCOHOLS IV P 0.01-0.05 2 10 GC-FID CCT
n-, sec-, 4 (-Butyl acetate 1450 ESTERS I P 0.01-0.2 1 10 GC-FID CCT
Butyl acetate 2549 VOLATILE ORGANIC CPDS (Screening) P 0.01-0.05 1 6 TD/GC-MS TD
Butyl alcohol 2549 VOLATILE ORGANIC CPDS (Screening) P 0.01-0.05 1 6 TD/GC-MS TD
(ert-Butyj alcohol 1400 ALCOHOLS I P 0.01-0.2 1 10 GC-FID CCT
n- & sac-Butyl alcohol 1401 ALCOHOLS II F 0.01-0.2 2 10 GC-FID CCT
n-Butyjamine 2012 n-BUTYLAMINE F 0.01-1.0 2 100 GC-FID SG * H2S04
Butyl ceilosolve 2549 VOLATILE ORGANIC CPDS (Screening) P 0.01-0.05 1 j 6 TD/GC-MS TD
Butyl ceIIosolve 1403 ALCOHOLS IV P 0.01-0.05 1 10 GC-FID CCT
1,3-Butylene glygol 5523 GLYCOLS P 0.5-2 5 60 GC-FID OVS-7
Butyl glycldyl ether 1616 BUTYL GLYCIDYL ETHER P 0.01-0.2 15 30 GC-FID CCT
n-Bulyl marcaptan 2525 n-BUTYL MERCAPTAN F 0.01-0.05 1 4 GC-FPD Chrom104
n-Butyl marcaptan 2542 MERCAPTANS P 0.1-0.2 10 150 GC-FPD GFF/HgAc
D-fert-ButyJtojuwe 1501 HYDROCARBONS, AROMATIC P 0.01-0.2 1 29 GC-FID CCT
ButyraldehydB 2539 ALDEHYDES, SCREENING P 0.05 5 5 GC-FID/MS XAD-2/HMP
Cadmium 7300 ELEMENTS by ICP P 1-4 13 2000 ICP-AES MCEF
Cadmium & compounds 7048 CADMIUM and cpds, as Cd F 1-3 25 1500 FAAS MCEF
Calcium 7300 ELEMENTS by ICP P 1 -4 5 200 ICP-AES MCEF
Calcium & compounds 7020 CALCIUM and cpds as Ca F 1 -3 20 400 FAAS MCEF
Camphor 1301 KETONES II F 0.01-0.2 1 25 GC-FID CCT
Capsalcln 5041 CAPSAICIN and DIHYDROCAPSAION P 1 -3 5 1000 HPLC-FL GFF
Carbaryl (Sevin) 5006 CARBARYL F 1 -3 20 400 VIS GFF
Cyrtiftoj 2549 VOLATILE ORGANIC CPDS (Screening) P 0.01-0.05 1 6 TD/GC-MS TD
Carbon black 5000 CARBON BLACK F 1 -2 30 570 Gray PVC
Carbon, elemental 5040 ELEMENTAL CARBON (DIESEL P 1 -4 106 4300 EGATTOA OFF
EXHAUST)

Meth. Eval Flow Rate Mm. Max. Analytical
IU (L)
Carbon dioxide 6603 CARBON DIOXIDE F 0.02-0.1 NA 80% GC-TCD air bag
Vol
Carbon dlaulfide 1600 CARBON DISULFIDE F 0.01-0.2 2 25 GC-FPD CCT & dry
tube
Carbon monoxide •804 CARBON MONOXIDE F NA NA NA Senaor Port inetr
1003 HYDROCARBONS, HALOGENATED P 0.01-0.2 3 150 GC-FID CCT
delta-3-C«ren« 1552 TERPENES P 0.01-0.02 2 30 GC-FID CCT
Chlordane 5510 CHLORDANE F 0.5-1.0 10 200 GC-ECD MCEF&

Chrom 102
Chlorinated carn£hene 5039 CHLORINATED CAMPHENE P 0.2-1 2 30 GC-ECD MCEF
Chlorinated dlphenyl oxide 5025 CHLORINATED DIPHENYL OXIDE P 0.5-1.5 8 200 GC-ECN MCEF
Chlorinated terphenyl 5014 CHLORINATED TERPHENYL P 1 -3 100 1500 GC-ECD GFF
Chlorine 6011 CHLORINE and BROMINE F 0.3-1.0 2 90 IC AgF
ChloroaceUldahyda 2015 CHLOROACETALDEHYDE F 0.05-0.2 3 16 GC-ECD SG
Chloroacetlc acid 2008 CHLOROACETIC ACID F 0.05-0.2 1 100 rc SG
Chlorobanzene 1003 HYDROCARBONS, HALOGENATED P 0.01-0.2 1.5 40 GC-FID CCT
ChlorobromomeUiane 1003 HYDROCARBONS, HALOGENATED P 0-01-0.2 0.5 8 GC-FID CCT
Chlorodlfluoromethane 1018 DICHLORODIFLUOROMETHANE F 0.01-0.05 1 4 GC-FID 2CCT (Ig+am)
Chlorodlphenyl
54% Cl) K (42% & 5503 POLYCHLOROBIPHENYLS P 0.05-0.2 1 50 GC-ECD GFF & Florisil
2-Chloroethanol 2513 ETHYLENE CHLOROHYDRIN P 0.01-0.2 2 35 GC-FID PCT
Chloroform 1003 HYDROCARBONS, HALOGENATED P 0.01-0.2 1 50 GC-FID CCT
4-Chloronltrobenzene 2005 NITROBENZENES F 0.01-1.0 1 150 GC-FID SG
p-Chforophenol 2014 p-CHLOROPHENOL F 0.054.2 1.5 40 HPLC-UV SG
Chloroprwie 1002 B-CHLOROPRENE F 0.01-0.1 1.5 8 GC-FID CCT
Chtenoyrifo. 5600 ORGANOPHOSPHORUS PESTICIDES F 0.2-1.0 12 240 GC-FPD OVS-2
Chromic acid 7600 CHROMIUM, HEXAVALENT F 1 -4 8 400 VIS PVC
Chromic acid 7604 CHROMIUM, HEXAVALENT F 1 -4 100 1000 IC PVC
Chromium 7024 CHROMIUM and cpds, aa Cr F 1 -3 10 1000 FAAS MCEF
Chromium 7300 ELEMENTS by ICP P 1 -4 5 1000 ICP-AES MCEF
Chromium, hexavalent 7600 CHROMIUM, HEXAVALENT F 1-4 8 400 VIS PVC
Chromium, hexavalent 7604 CHROMIUM, HEXAVALENT F 1 -4 100 1000 IC PVC
Chromium, hexavalent 9101 CHROMIUM, HEXAVALENT in aettld NA NA NA NA Spot Teat atrip

dual
Chrysem 5506; POLYNUCLEAR AROMATIC H/C P 2.0 200 1000 HPLC-FL/UV; PTFE & XAD-2
5515 GC-FID
Coal tar naphtha 1550 NAPHTHAS F 0.01-0.2 1.3 20 GC-FID CCT
Coal tar pitch volatilea OSHA COAL TAR PITCH VOLA T(LES 1.5-2.0 480 960 Gray & HPLC- GFF
58 UV
Cobalt 7300 ELEMENTS by ICP P 1 -4 25 2000 ICP-AES MCEF
Cobalt & compounda 7027 COBALT and cpds, as Co F 1 -3 30 1500 FAAS MCEF
Copper 7300 ELEMENTS by ICP P 1-4 5 1000 ICP-AES MCEF
Copper (dual & fume) 7029 COPPER (duet & fumea) F 1 -3 50 1500 FAAS MCEF

Math. Eval Flow Rate W'n Max. Analytical
Chemical No. Mathod Name (L/min) Vol. Vol. Technique Sampler
(U (L)
Crasol 2549 VOLATILE ORGANIC CPDS (Screening) P 0.01-0.05 1 6 TD/GC-MS TD
Cresol, all IsornerB 2546 CRESOLS and PHENOL P 0.01-0.1 1 24 GC-FID XAD-7
Crotonaldehyde 2539 ALDEHYDES, SCREENING P 0.01-0.05 5 5 GC-FID/MS XAD-2/HMP
Crotonaldehyde 3516 CROTONALDEHYDE F 0.1-0.2 1 49 DPP BuB
Cryolluorane 1018 DICHLORODIFLUOROME.THANE, 1.2- F 0.01-0.05 1 4 GC-FID 2CCT

DICHLOROTETRAFLUORO-ETHANE, &
CHLORODIFLUOROMETHANE
Cumene 1501 HYDROCARBONS, AROMATIC P 0.01-0.2 1 30 GC-FID CCT
Cyanldet 7904 CYANIDES, aerosol and gas F 0.5-1.0 10 180 ISE MCEF & BuB
Cyanides 6010 HYDROGEN CYANIDE F 0.05-0.2 0.6 90 VIS soda lima
Cyanurfc acid 5030 CYANURIC ACID P 1 -3 10 1000 HPLC-UV PVC
Cyclohexane 1500 HYDROCARBONS, BP 36-126'C F 0.01-0.2 2.5 5 GC-FID CCT
Cyclohaxanol 1402 ALCOHOLS III P 0.01-0.2 1 10 CG-FID CCT
Cyclohaxanona 2549 VOLATILE ORGANIC CPDS (Screening) P 0.01-0.05 1 6 TD/GC-MS TD
Cyclohexanone 1300 KETONES I F 0.01-0.2 1 10 CG-FID CCT
Cyclohexene 1500 HYDROCARBONS, BP 36-126'C F 0.01-0.2 5 7 CG-FID CCT
1,3-Cyclopentadiene 2523 1,3-CYCLOPENTAUIENE F 0.01-0.05 1 5 GC-FID Chrom104/

maleic anh.
2,4-0 5001 2,4-D and 2.4,5 -T F 1-3 15 200 HPLC-UV GFF
o-Decan« 2548 VOLATILE ORGANIC CPOS (Scraaning) P 0.01-0.05 1 6 TD/GC-MS TD
Demoton 6514 DEMETON F 0.2-1.0 30 500 GC-FPO MCEF &XAD-2
Dlacatona alcohol 1402 ALCOHOLS III P 0.01-0.2 1 10 GC-FID CCT
o-Dianlsidine 5013 DYES P 1 -3 150 500 HPLC-UV PTFE
Dlatomacaoua earth 7501 SILICA, AMORPHOUS P 1 -3 50 400 XRD PVC/CYC
Diazinon 5600 ORGANOPHOSPHORUS PESTICIDES F 0.2-1 12 240 GC-FPD OVS-2
Dlaiomettiane 2515 DIAZOMETHANE P 0.2 6 30 GC-FID XAD-2

(coated)
Dibenz(«,h) anthr»c«n« 5508; POLYNUCLEAR AROMATIC P 2.0 200 1000 HPLC-FUUV; PTFE 4 XAD-2
Diborane 6006 DIBORANE F 0.5-1.0 60 260 PES PTFE & CCT

w/oxidizer
DibromodifluoromiJthana 1012 DIFLUOROOIBROMOM ETHANE P 0.01-0.2 2.5 10 GC-FID 2 CCT
2-pibutylaminoethanol 2007 AMINOETHANOL COMPOUNDS P 0.01-0.2 4 24 GC-FID SG
Dibutyl phosphate 5017 DIBUTYL PHOSPHATE P 1-3 50 250 GC-FPD PTFE
Dibutyl phthalata 5020 DIBUTYL PHTHALATE & F 1-3 6 200 GC-FID MCEF
DI(2-ETHYLHEXYL) PHTHALATE P
Dihuiyltin bla(laoocty) 5504 ORGANOTIN COMPOUNDS F 1-1.5 50 500 HPLC/GFAAS GFF + XAD-2
marcaptoacetata)
o-, g-Djchlorobanzene 2549 VOLATILE ORGANIC CPDS (Screening) P 0.01-0.05 1 6 TD/GC-MS TD
o-Diehlorobenzene 1003 HYDROCARBONS, HALOGENATED P 0.01-0.2 1 60 GC-FID CCT
p-Dlchlorobenzana 1003 HYDROCARBONS, HALOGENATED P 0.01-0.2 1 10 GC-FID CCT
S.r-Dlchlorobanzlcflna 5509 BENZIDINE and F 0.2 20 100 HPLC-UV GFF

3.3'-DICHLOROBENZlDINE
5/15/96 NIOSH Manual of Analytical Methods

Chemical No. Method Name U/min) Vol. Vol. Technique Sampler
(L) ID
Dichlorodifluorom«thane 1018 DICHLORODIFLUOROMETHANE, 1,2- F 0.01-0.05 1 < GC-FID 2CCT

DICHLOROTETRAFLUORO-ETHANE t, (Ig + «n)
1.1-Dichloroethane 1003 HYDROCARBONS, HALOGENATED P 0.01-0.2 0.5 15 GC-FID CCT
1,2-Dichloroethane 1003 HYDROCARBONS, HALOGENATED P 0.01-0.2 0.8 BO GC-FID CCT
Dlchloroothyl other 1004 DICHLOROETHYL ETHER F 0.01-1.0 2 15 GC-FID CCT
1,2-Dlchloroethylene 1003 HYDROCARBONS, HALOGENATED P 0.01-0.2 0.2 5 GC-FID CCT
Dichlorofluoromethane 2516 DICHLOROFLUOROMETHANE F 0.01-0.05 0.25 3 GC-FID 2CCT(lg)
Dichloromethane 2549 VOLATILE ORGANIC CPDS (Screening) P 0.01-0.05 1 6 TD/GC-MS TD
1,1-Dichloro-1-nitroethane 1601 1 ,1 -DICHLORO-1 -NITROETH ANE F 0.01-1.0 1.5 15 GC-FID PCT
1,2-Dlchlaropropan« 1013 PROPYLENE DICHLORJDE F 0.01-0.2 0.1 3.5 GC-ECN PCT
1,2-DichlorotBtra- 1018 DICHLORODIFLUOROMETHANE, 1,2- F 0.01-0.05 1 4 GC-FID 2 CCT

nuoroethane DICHLOROTETRAFLUORO-ETHANE & (lg + *m)
Dicrotophos 5600 ORGANOPHOSPHORUS PESTICIDES F 0.2-1 12 240 GC-FPO OVS-2
Diethanolamlne 3509 AMINOETHANOL COMPOUNDS II P 0.5-1.0 5 300 IC IMP
Diethylarnine 2010 AMINES, ALIPHATIC P 0.01-1.0 3 30 GC-FID SG
2-Diethylaminoethanol 2007 AMINOETHANOL COMPOUNDS I P 0.01-0.2 4 24 GC-FID SG
Diesel exhaust 5040 ELEMENTAL CARBON (DIESEL P 1 -4 106 4300 EGA/TOA OFF
EXHAUST)
Dlethylene glycol 5523 GLYCOLS P 0.5-2 5 60 GC-FID OVS-7
Dlethylene glycol ether 2549 VOLATILE ORGANIC CPDS (Screening) P 0.01-0.05 1 e TD/GC-MS TD
Diethylenetriamine 2540 ETHYLENEDIAMINE, U 0.01-0.1 1 2° HF1.C.UV XAD-2

DIETHYLENETRIAMINE, & w/10% NITC
TRIETHYLENETETRAMINE
DH2-aihylhexyl) phthalate 5020 DIBUTYL PHTHALATE and F 1-3 10 200 GC-FID MCEF
DI(2-ETHYLHEXYL) PHTHALATE P
Difluorodibromomethane 1012 DIFLUORODIBROMOMETHANE P 0.01-0.2 2.5 10 GC-FID 2CCT
Difluorodichloromethane 1018 DICHLORODIFLUOROMETHANE, 1,2- F 0.01-0.05 1 4 GC-FID 2 CCT

DICHLOROTETRAFLUORO-ETHANE &
Dihydrocapsaicin 5041 CAPSAICIN and DIHYDROCAPSAICIN P 1 -3 7 1000 HPLC-FL GFF
Dilsobutyl ketone 1300 KETONES I F 0.01-0.2 1 10 GC-FID CCT
Dimethylacetamide 2004 DIMETHYLACETAMIDE and F 0.01-1.0 15 80 GC-FID SG

DIMETHYLFORMAMIDE
Dimethylamine 2010 AMINES, ALIPHATIC P 0.01-1.0 3 30 GC-FID SG
Ai.N-Dlmeth • aniline 2002 AMINES, AROMATIC P 0.02-1.0 3 30 GC-FID SG
Dimethylarsinlc acid 5022 ARSENIC, ORGANO- F 1-3 60 1000 IC-HYAAS PTFE
Dimethylformamlde 2004 DIMETHYLACETAMIDE 1 F 0.01-1.0 16 80 GC-FID SG

DIMETHYLFORMAMIDE
1 ,1 - Dimethy Ihydr azine 3515 1,1-DIMETHYLHYDRAZINE P 0.2-1.0 2 100 VIS BuB(.1 MHCI)
N,/V-Dimethyl-p-toluidine 2002 AMINES, AROMATIC P 0.02-1.0 20 100 GC-FID SG
Dimethyl sulfate 2524 DIMETHYL SULFATE P 0.01-0.2 0.25 12 GC-ECN PorP
Dloxane 1602 DIOXANE F 0.01-0.2 0.5 15 GC-FID CCT
Diphanvl 2530 DIPHENYL F 0.01-0.5 15 30 GC-FID Tensx GC

Meth. Eval Flow Rate Mln. Max. Analytical
(L) (LI
Disulfoton 5400 ORGANOPHOSPHORUS PESTICIDES F 0.2-1 12 240 GC-FPD OVS-2
Dyes- benzidine-, a- 5013 DYES, BENZIDINE-, o- TOLIDINE-, P 1 -3 150 500 HPLC-UV PTFE
toIIdine-, o-dianieldlne- o- DIANISIDINE
Elements 7300 ELEMENTS by ICP P 1-4 Var Va ICP-AES MCEF
Endrin 5519 ENDRIN F 0.5-1.0 12 4OO GC-ECD MCEF 4

Chrom 102
Epichlorohydrin 1010 EPICHLOROHYDRIN F 0.01-0.2 2 30 GC-FID CCT
EPN 5012 EPN F 1 -2 15 700 GC-FPD GFF
1,2-Epoxypropane 1612 PROPYLENE OXIDE P 0.01-0.2 0.5 5 GC-FID CCT
Elhanol 2549 VOLATILE ORGANIC CPDS (Screening) P 0.01-0.05 1 6 TD/GC-MS TD
Ethanol 1400 ALCOHOLS I P 0.01-0.05 0.1 1 GC-FID CCT
Ethanolamine 2007 AMINOETHANOL COMPOUNDS I P 0.01-0.2 4 24 GC-FID SG
Ethlon; Ethoprop 5600 ORGANOPHOSPHORUS PESTICIDES F 0.2-1 12 240 GC-FPD OVS-2
2-Ethoxyethanol 1403 ALCOHOLS IV P 0.01-0.05 1 6 GC-FID CCT
2-Ethoxyethyl acetate 1450 ESTERS I P 0.01-0.2 1 10 GC-FID CCT
Ethyl acetate 2549 VOLATILE ORGANIC CPDS (Screening) P 0.01-0.05 1 6 TD/GC-MS TD
Ethyl acetate 1457 ETHYL ACETATE F 0.01-0.2 0.1 10 GC-FID CCT
Ethyl acrylate 1450 ESTERS I P 0.01-0.2 1 10 GC-FID CCT
Ethyl amyl ketone 1301 KETONES II F 0.01-0.2 1 25 GC-FID CCT
Ethylbenzene 1501 HYDROCARBONS, AROMATIC P 0.01-0.2 1 24 GC-FID CCT
Ethyl bromide 1011 ETHYL BROMIDE P 0.01-0.2 0.5 4 GC-FID CCT
Ethyl butyl ketone 1301 KETONES II F 0.01-0.2 1 25 GC-FID CCT
Ethyl chloride 2519 ETHYL CHLORIDE F 0.02-0.05 0.3 3 GC-FID 2CCT(lg))
Ethylene chlorohydrin 2513 ETHYLENE CHLOROHYDRIN P 0.01-0.2 2 35 GC-FID PCT
Ethylenedlamlne 2540 ETHYLENEDIAMINE. U 0.01-0.1 1 20 HPLC-UV XAD-2

Ethylene djbromide 1006 ETHYLENE DIBROMIDE P 0.02-0.2 0.1 25 GC-ECD CCT
Ethylene dlchloride 1003 HYDROCARBONS, HALOGENATED P 0.01-0.2 1 50 GC-FID CCT
Ethylene glycol 5523 GLYCOLS P 0.5-2 5 60 GC-FID OVS-7
Ethylene glycol dinitrate 2507 NITROGLYCERIN & ETHYLENE F 0.2-1.0 3 100 GC-ECD Tenax GC
GLYCOL DINITRATE
Ethylene oxide 1614 ETHYLENE OXIDE F 0.05-0.15 1 24 GC-ECD PCTw/HBr
Ethylene oxide 3702 ETHYLENE OXIDE by portable GC F >0.02 NA 80% GC-PID air bag
vol
Ethylene thiourea 5011 ETHYLENE THIOUREA P 1 -3 200 800 VIS PVC or MCEF
Ethylonimlna 3514 ETHYLENIMINE F 0.2 1 40 HPLC-UV BUB

EOtylether 1610 ETHYL ETHER P 0.01-0.2 0.25 3 GC-FID CCT
Ethyl formate 1452 ETHYL FORMATE P 0.01-0.2 0.3 10 GC-FID CCT
Ethyl mercaptan 2542 HERCAPTANS P 0.1-0.2 10 150 GC-FPD GFF/HgAc
Fenamiphos 5600 ORGANOPHOSPHORUS PESTICIDES F 0.2-1 12 240 GC-FPD OVS-2
Fibrous glass 7400 ASBESTOS & other FIBERS bv PCM F 0.5-16 400 var PCM MCEF

Meth. Eval Flow Rate Mil. Max. Analytical
(L) (L)
Fluoranthene 5506; POLYNUCLEAR AROMATIC P 2.0 200 1000 HPLC-FUUV; PTFE & XAD-2
Fluorene 5506; POLYNUCLEAR AROMATIC P 2.0 200 1000 HPLC-FUUV; PTFE & XAD-2
851 5 HYDROCARBONS GC-FID
Fluorides 7902 FLUORIDES, aerosol & gas P 1-2 12 800 ISE MCEF & pad
w/ Na2CO3
:
FLUORIDES bV IC p 1-2 •j. 800 IC MCEF & pad
;;.. .;''. . .. : ; sol w/ Na,CO,
120-
inso
I
Fluorotrlchloromethane 1006 FLUOROTRICHLOROMETHANE F 0.01-0.05 0.3 7 GC-FID CCT(lg)
Fonofos 5600 ORGANOPHOSPHORUS PESTICIDES f 0.2-1.0 12 240 GC-FPD OVS-2
FOT7rHJd»hyde_ .:...'...:.: ;::.:..' ZW1 FORMALDEHYDE P 0.01-0,1 1 M OC-FID XAD-2/HMP
Formaldehyde 3500 FORMALDEHYDE F 0.2-1.0 1 100 VIS PTFE & 2 IMP
Formaldehyde 2539 ALDEHYDES, SCREENING P 0.01-0.05 5 5 GC-FID/MS XAD-2/HMP
Formaldehyde 5700 FORMALDEHYDE on dust F 2 240 1050 HPLC-UV IOM/PVC
Formic acid 2011 FORMIC ACID P 0.05-0.2 1 24 IC PTFE&

SG (washed)
Furfural 2529 FURFURAL F 0.014.05 1 12 GC-FID XAD-2/HMP
Furfural 2539 ALDEHYDES, SCREENING P 0.05 5 5 GC-FID/MS XAD-2/HMP
Furfuryl alcohol 2505 FURFURYL ALCOHOL F 0.014.05 3 25 GC-FID PorQ
Glutaraldehyde 2532_ GLUTARALDEHYDE P 0.01 -0.08 4 39 HPLC-UV SG/DNPH
Glycerin mist 0500 PARTICULATES N.O.R. F 1 -2 7 133 Grav PVC
Glycldol 1608 GLYCIDOL F 0.01-1.0 5 100 GC-FID CCT
Glycols 6523 GLYCOLS P 0.5-2 5 60 GC-FID OVS-7
Hoptanal 253V ALDEHYDES. SCREENING P 0.01-0.05 5 5 GC-FID/MS XAD-2/HMP
n-Heptane 2549 VOLATILE ORGANIC CPDS (Screening) P 0.01-0.05 1 6 TD/GC-MS TO
n-Hegtane 1500 HYDROCARBONS, BP 36-126'C F 0.01-0.2 4 4 GC-FID CCT
Hsxachlorobutadiene 2543 HEXACHLOROBUTADIENE F 0.05-0.2 1 100 GC-ECD XAD-2
Hexachloro-1,3- 2518 HEXACHLORO 1 3 F 0.01-0.2 0.25 90 GC-ECD 2PorT

cyclopantadlene CYCLOPENTADIENE
Hexachloroethane 1003 HYDROCARBONS, HALOGENATED P 0.01-0.2 3 70 GC-FID CCT
Hexametriylene- 5522 ISOCYANATES P 1 -2 15 360 HPLC-FL IMP

dlisocyanate
Hexamethylene- 5521 ISOCYANATES. MONOMERIC u 1.0 5 500 HPLC-ECHD IMP

dIIsocyanata
Hexanal 2539 ALDEHYDES, SCREENING p 0.01-0.05 5 5 GC-FID/MS XAD-2/HMP
Hexanal 2549 VOLATILE ORGANIC CPDS (Screening) p 0.01-0.05 1 6 TD/GC-MS TO
n-Hexane 2549 VOLATILE ORGANIC CPDS (Screening) p 0.01 -0.05 1 6 TD/GC-MS TD
n-Hexane 1600 HYDROCARBONS, BP 36-126'C F 0.01-0.2 4 4 GC-FID CCT
2-Hexanone 1300 KETONESt F 0.01-1.8 1 10 GC-FID CCT
Hydrazlne 3503 HYDRAZINE F 0.2-1.0 7 100 VIS BuB
Hvdroaen bromide 7903 ACIDS. INORGANIC F 0.2-0.5 3 100 IC SG
5/15/96 MF 8 NIOSH Manual of Analytical Methods

Meth. Eval Flow Rate Win. Max. Analytical
Chemical No. Method Name IL/min) Vol. Vol. Technique Sampler
(LI (L)
Hydrogen chloride 7903 ACIDS, INORGANIC F 0.2-0.5 3 100 IC SG
Hydrogen cyanide 6010 HYDROGEN CYANIDE F 0.05-0.2 2 90 VIS soda lime
Hydrogen cyanide 7904 CYANIDES, AEROSOL & GAS F O.5-1.0 7 100 ISE MCEF
Hydrogen flourfde 7903 ACIDS, INORGANIC F 0.2-0.6 3 100 IC SG
Hydrogen flouride 7902 FLUORIDES, AEROSOL & GAS P 1-2 12 800 lSE MCEF & pad
w/Na2CO,
Hydrogen flouride 7906 FLUORIDES by IC P 1-2 1 800 IC MCEF & pad

w/NajCOj
Hydrogen sulflde 6013 HYDROGEN SULFIDE F 0.1-1.5 1.2 40 IC PTFE&

CCT(lg)
Hydroquinone 5004 HYDROQUINONE F 1 -4 30 180 HPLC-UV MCEF
lnd»no [1,2,3-cd] pyrane 5506; POLYNUCLEAR AROMATIC P 2.0 200 1000 HPLC-FL/UV; PTFE «. XAD-2
Iodine 6005 IODINE F 0.5-1.0 15 225 IC CCT w/alkali
Iron 7300 ELEMENTS by ICP P 1-4 6 100 ICP-AES MCEF
Isoamyl acetate 1450 ESTERS I P 0.01-0.2 1 10 GC-FID CCT
Isoamyl alcohol 1402 ALCOHOLS III P 0.01-0.2 1 10 GC-FID CCT
Isobutyl acetate 1450 ESTERSI P 0.01-0.2 1 10 GC-FID CCT
Isobutyl alcohol 1401 ALCOHOLS II F 0.01-0.2 2 10 GC-FID CCT
Isobutyraldehyde 2539 ALDEHYDES, SCREENING P 0.01-0.05 5 5 GC-FID/MS XAD-2/HMP
Isocyanates 5521 ISOCYANATES, MONOMERIC u 1.0 5 500 HPLC-ECHD IMP
Isocyanates 5522 ISOCYANATES P 1 -2 15 360 HPLC-FL IMP
Isophorone 2508 ISOPHORONE F 0.01-1.0 2 25 GC-FID PCT
Isopropyj acetate 1454 ISOPROPYL ACETATE P 0.02-0.2 0.1 8 GC-FID CCT
Isopropyl alcohol 2649 VOLATILE ORGANIC CPDS (Screening) P 0.01-0.05 1 6 TD/GC-MS TD
Isopropyl alcohol 1400 ALCOHOLS 1 P 0.01-0.2 0.2 3 GC-FID CCT
Isopropyl ether 1618 ISOPROPYL ETHER F 0.01-0.06 0.1 3 GC-FID CCT
Isopropyl glycldyl ether 1620 ISOPROPYL GLYCIDYL ETHER P 0.01-0.2 1 30 GC-FID CCT
Isovaleraldehyde 2539 ALDEHYDES, SCREENING P 0.01-0.05 5 6 GC-FID/MS XAD-2/HMP
Kepone 5508 KEPONE P 0.5-1.0 50 600 GC-ECD MCEF & IMP
Kerosene 1550 NAPHTHAS F 0.01-0.2 1.3 20 GC-FID CCT
Lead 7082 LEAD by FAAS F 1-4 200 1600 FAAS MCEF
Lead 7105 LEAD by GFAAS P 1-4 1 1500 GFAAS MCEF
Lead 7300 ELEMENTS by ICP P 1-4 1250 2000 ICPjAES MCEF
Lead 7700 LEAD In Air by Chemical Spot Test P 2 10 240 Spot MCEF
Lead 9100 LEAD tn Surface Wipe Samples NA NA NA NA AAS; ICP Wipes
Lead sulfide 7505 LEAD SULFIDE P 1.7 or 2.2 600 1000 XRD CYC & PVC
Llmonene 1552 TERPENES P 0.01-0.2 2 30 GC-FID CCT
Limonene 2549 VOLATILE ORGANIC CPDS (Screening) P 0.01-0.06 1 6 TD/GC-MS TD
Lindane 5502 ALDRIN and LINDANE F 0.2-1.0 18 240 GC-ECN GFF*8uB

Lithium 7300 ELEMENTS bv ICP P 1-4 100 2000 ICP-AES MCEF
MF-9 NIOSH Manual of Analytical Methods

Chemical No. Method Name (L.'inin) Vol. Vol. Technique Sampler
(L) (L)
Lithium hydroxide 7401 ALKALINE OUSTS F 1-4 70 1000 Titration PTFE
Magnesium 7300 ELEMENTS by ICP p 1 -4 5 67 ICP-AES MCEF
Malathion 5600 ORGANOPHOSPHORUS PESTICIDES F 0.2-1 12 60 GC-FPD OVS-2
Maleic Anhydride 3512 MALEIC ANHYDRIDE F 0.2-1.5 40 500 HPLC-UV BuB
Manganese 7300 ELEMENTS by ICP P 1-4 5 200 ICP-AES MCEF
MBK 1300 KETONES I F 0.01-0.2 1 10 GC-FID CCT
MEM (4,41-melhyl«ne- 5521 ISOCYANATES, MONOMERIC U 1.0 6 500 HPLC-ECHD IMP

bisphenyl Isocyanate)
'DI (4,4'-methylene- 5522 ISOCYANATES P 1-2 15 360 HPLC-FL IMP

blsphenyl Isocyanate)
Mercury 6009 MERCURY P 0.15-0.26 2 100 AAS-cold vap Hopcalite
Mercaptans 2542 MERCAPTANS P 0.1-0.2 10 150 GC-FPD GFF/HgAc
Mesltyl oxide 1301 KETONES II F 0.01-0.2 1 25 GC-FID CCT
Metals in air 7300 ELEMENTS by ICP P 1 -4 var 2000 ICP-AES MCEF
Methamidophos 5600 ORGANOPHOSPHORUS PESTICIDES F 0.2-1 12 240 GC-FPD OVS-2
Methanol 2549 VOLATILE ORGANIC CPDS (Screening) P 0.01-0.06 1 6 TD/GC-MS TD
Methanol 2000 METHANOL F 0.02-0.2 1 5 GC-FID SO
2-Methoxyethyl acetate 1451 METHYL CELLOSOLVE ACETATE F 0.01-0.2 0.2 20 GC-FID CCT
2-Methoxyethanol 1403 ALCOHOLS IV P 0.01-0.06 6 50 GC-FID CCT
Methyl acetate 1458 METHYL ACETATE F 0.01-0.2 0.2 10 GC-FID CCT
Methyl acrylate 1459 METHYL ACRYLATE P 0.01-0.2 1 5 GC-FID CCT
Methylal 1611 METHYLAL F 0.01-0.2 1 3 GC-FID CCT
MethyHn-amyl)-ketone 1301 KETONES II F 0.01-0.2 1 25 GC-FID CCT
Methylarsonic acid 6022 ARSENIC, ORGANO- F 1 -3 SO 10O0 IC-HYAAS PTFE
Methyl bromido 2520 METHYL BROMIDE F 0.01-0.1 1 5 GC-AED PCT(2) + dry

tube
Methyl ceIIosolve 1403 ALCOHOLS IV P 0.01-0.05 6 50 GC-FID CCT
Methyl ceIIosolve acetate 1451 METHYL CELLOSOLVE ACETATE F 0.01-0.2 0.2 20 GC-FID CCT
Methyl chloride 1001 METHYL CHLORIDE F 0.01-0.1 0.4 3 GC-FID 2 CCT (Ig+sm)
Methyl chloroform 1003 HYDROCARBONS, HALOGENATED P 0.01-0.2 0.1 8 GC-FID CCT
Methyl Chloroform 2549 VOLATILE ORGANIC CPDS (Screening) P 0.01-0.05 1 6 TD/GC-MS TD
Methyl cyanide 1606 ACETONITRILE P 0.01-0.2 3 25 GC-FID CCT
Methyl cyclohexane 1500 HYDROCARBONS, BP 36-126'C F 0.01-0.2 4 4 GC-FID CCT
Methylcyclohexanol 1404 METHYLCYCLOHEXANOL F 0.01-0.2 1 15 GC-FID CCT
Methylcyclohexanone 2521 METHYLCYCLOHEXANONE F 0.01-0.05 1 6 GC-FID PorQ
Methylene chloride 2549 VOLATILE ORGANIC CPDS (Screening) P 0.01-0.05 1 6 TD/GC-MS TD
Methylene chloride 1005 METHYLENE CHLORIDE F 0.01-0.2 0.5 2.5 GC-FID 2 CCT
M'-MethylenedianlIIne 5029 4,4'-METHYLENEDIANILINE P 1 -2 10 1000 HPLC-UV GFF/H2SO4
4,4-Methylene diphenyl 5522 ISOCYANATES P 1 -2 15 160 HPLC-FL IMP

diisocyanate
Methyl ethyl ketone 2549 VOLATILE ORGANIC CPDS (Screeninal P 0.01-0.05 1 6 TD/GC-MS TD

(LI in
Methyl ethyl ketone 2500 METHYL ETHYL KETONE F 0.01-0.2 0.25 12 GC-FID Carbon beads
Methyl ethyl ketone 3508 METHYL ETHYL KETONE PEROXIDE P 05-0.2 52 620 VIS IMP
peroxide
5-Methyl-3-heptanone 1301 KETONES II F 0.01-0.2 1 25 GC-FID CCT
Methyl Iodide 1014 METHYL IODIDE P 0.01-1.0 15 50 GC-FID CCT
Methyl isoamyl acetate 1450 ESTERS I P 0.01-0.2 1 10 GC-FID CCT
Methyl Isobutyl carbinol 1402 ALCOHOLS III P 0.01-0.2 1 10 GC-FID CCT
Methyl Isobutyl ketone 2549 VOLATILE ORGANIC CPDS (Screening) P 0.01-0.05 1 6 TD/GC-MS TD
Methyl isobutyl ketone 1300 KETONES I F 0.01-0.2 1 10 GC-FID CCT
Methyl mercaptan 2542 MERCAPTANS P 0.1-0.2 10 150 GC-FPD GFF/HgAc
Methyl methacrylatt 2537 METHYL METHACRYLATE F 0.01-0.05 1 8 GC-FID XAD-2
Methyl panrthlon MOO ORGANOPHOSPHORUS PESTICIDES F 0.2-1 12 240 GC-FPD OVS-2
Methyl phenol 2549 VOLATILE ORGANIC CPDS (Screening) P 0.01-0.05 1 6 TD/GC-MS TD
a-Methyl styrene 1501 HYDROCARBONS, AROMATIC P 0.01-0.2 1 30 GC-FID CCT
Methyl tert-butyl ether 1615 METHYL tert-BUTYL ETHER P 0.1-0.2 2 96 GC-FID 2CCT(lg)
Mevinphos 5600 ORGANOPHOSPHORUS PESTICIDES F 0.2-1.0 12 240 GC-FPD OVS-2
Mineral spirits 1550 NAPHTHAS F 0.01-0.2 1.3 20 GC-FID CCT
Molybdenum 7300 ELEMENTS by ICP P 1 -4 5 67 ICP-AES MCEF
Monocrotophos 5600 ORGANOPHOSPHORUS PESTICIDES F 0.2-1 12 240 GC-FPD OVS-2
Monomethylaniline 3511 MONOMETHYLANILINE P 0.2-1.0 11 100 GC-FID BuB/H2SO.
Monomethylhydrazine 3510 MONOMETHYLHYDRAZINE F 0.5-1.5 3 20 VIS BuB/HCI
Naphtha (coal tar) 1550 NAPHTHAS F 0.01-0.2 1.3 20 GC-FID CCT
Naphthalene 1501 HYDROCARBONS, AROMATIC P 0.01-1.0 100 200 GC-FID CCT
Naphthalene 5506 POLYNUCLEAR AROMATIC H/C P 2.0 200 1000 HPLC-UV; PTFE & XAD-2
GC-FID
Naphthylamines 5518 NAPHTHYLAMINES P 0.2-0.8 30 100 GC-FID GFF & SG
Nickel 7300 ELEMENTS by ICP P 1 -4 25 1000 ICP-AES MCEF
Nickel carbonyl 6007 NICKEL CARBONYL P 0.05-0.2 7 80 GFAAS CCT (low Nl)
Nicotine 2544 NICOTINE P 1.0 60 400 GC-NPD XAD-2
Nitric acid 7903 ACIDS, INORGANIC F 0.2-0.5 3 100 IC SG (washed)
Nitric oxide 6014 NITRIC OXIDE & F 0.025 1.5 6 VIS MSwfTEA&
NITROGEN DIOXIDE oxldizer
p-Nitroaniline 5033 p-NITROANILINE F 1 -3 16 350 HPLC-UV MCEF
Nitrobenzene 2005 NITROBENZENES F 0.01-1 10 150 GC-FID SG
p-Nitrochlorobenzene 2005 NITROBENZENES F 0.01-1 1 150 GC-FID SG
Nitroethane 2526 NITROETHANE F 0.01-0.05 1.5 3 GC-FID 2XAD-2
Nitrogen dioxide 6014 NITRIC OXIDE * F 0.025-0.2 1.5 6 VIS MS wrTEA

NITROGEN DIOXIDE
Nitroglycerin 2507 NITROGLYCERIN & ETHYLENE F 0.2-1.0 3 100 GC-ECD Tenax-GC

GLYCOL DINITRATE
Nitrornethane 2527 NITROM ETHANE F 0.01-0.05 1.2 3 GC-FPD ChromlOe
NIOSH Manual of Analytical Methods

Ch.mical No. Method Name (L/minl Vol. Vol. Technique Sampler
(LI (LI
2-Nitropropane 2528 2-NITROPROPANE F 0.01-0.05 0.1 2 GC-FID Chrom 106
Nltrosamines 2522 NITROSAMINES P 0.2-2.0 15 1000 GC-TEA Thermosorb/N
Nltrotoluene 2005 NITROBENZENES F 0.01-0.2 1 30 GC-FID SG
Nitrous oxid. 6600 NITROUS OXIDE F NA NA 80% IR air bag

Vol
Nuisance dusts 0500 PARTICULATES N.O.R. F 1-2 7 133 GRAV PVC
n-Oct«n« 2549 VOLATILE ORGANIC CPDS (Screening) P 0.01-0.05 1 6 TD/GC-MS TD
n-Octana 1500 HYDROCARBONS. BP 36-126'C F 0.01-0.2 4 4 GC-FID CCT
Octanwthylcyclotstn- ZS49 VOLATlLE ORGANIC CPDS (Screening) P 0.01-0.05 1 6 TD/GC-MS TD

sltoxane
1-OcUnethlol 2510 1-OCTANETHIOL F 0.01-0.2 1 15 GC-FPD Tenax GC
Oil mist (mineral) 5026 OIL MIST, MINERAL F 1 -3 20 500 IR PVC or MCE
Orgsnophosphorus 5600 ORGANOPHOSPHORUS PESTICIDES F 0.2-1 12 240 GC-FPD OVS-2

Pesticides
Oxygen 6601 OXYGEN F NA 1 NA Sensor portable
Paraqust 5003 PARAQUAT F 1-4 40 1000 HPLC-UV PTFE
Parathlon 5600 ORGANOPHOSPHORUS PESTICIDES F 0.2-1.0 12 240 GC-FPD OVS-2
ParHculates N.O.R. 0600 PARTICULATES, N.O.R, HESP. F 1.7 or 2.2 20 400 Grav. CYC & PVC
Pentachlorobenzene 5517 POLYCHLOROBEN2ENES F 0.01-0.2 3 12 GC-ECD PTFE & XAD-2
Pentachloroethane 2517 PENTACHLOROETHANE F 0.01-0.2 1 10 GC-ECD PorR
Pentachlorophenol 5512 PENTACHLOROPHENOL F 0.5-1.0 48 480 HPLC-UV MCEF&BuB
PenUmldins 5032 PENTAMIDINE ISETHIONATE P 1 -2 50 1500 HPLC/FL PVC/opaque
n-Pentane 2549 VOLATILE ORGANIC CPDS (Screening) P 0.01-0.05 1 6 TD/GC-MS TD
n-Pent«ne 1500 HYDROCARBONS, BP 36-1 26'C F 0.01-0.05 2 2 GC-FID CCT
2-PenUnone 1300 KETONESI F 0.01-2.0 1 10 GC-F1D CCT
Perchloroethylene 254• VOLATILE ORGANIC CPDS (Screening) P 0.01-0.05 1 6 TD/GC-MS TD
Petroleum ether/naphtha 1550 NAPHTHAS F 0.01-0.2 1.3 20 GC-FID CCT
Phsnol 2549 VOLATILE ORGANIC CPDS (Screening) P 0.01-0.05 1 6 TD/GC-MS TD
Phenol 2546 CRESOLS and PHENOL P 0.01-0.1 1 24 GC-FID XAD-7
Phenyl ether 1617 PHENYL ETHER P 0.01-0.2 1 50 GC-FID CCT
Phenyl ether-diphenyl 2013 PHENYL ETHER-DIPHENYL MIXTURE P 0.01-0.2 1 40 GC-FID SG

mixture
Phenyl glyddyt ether 1619 PHENYL GLYCIDYL ETHER P 0.01-1 80 150 GC-FID CCT
Phenylhydrazlne 3518 PHENYLHYDRAZINE F 0.2-1.0 25 120 VIS BuB/HCI
Phorate WOO ORGANOPHOSPHORUS PESTICIDES F 0.2-1 12 240 GC-FPD OVS-2
Phosdrln (mevinphos) 5600 ORGANOPHOSPHORUS PESTICIDES F 0.2-1 12 480 GC-FPD OVS-2
Phosphine 6002 PHOSPHINE F 0.01-0.2 1 16 VIS SG/Hg(CN)2
Phosphoric acid 7903 ACIDS, INORGANIC F 0.2-0.5 3 100 IC SG (washed)
Phosphorus 7300 ELEMENTS by ICP P 1 -4 50 2000 ICP-AES MCEF
Phosphorus 7905 PHOSPHORUS F 0.01-0.2 5 100 GC-FPD Tenax GC
Phosohorus trichloride 6402 PHOSPHORUS TRICHLORIDE P 0.05-0.2 11 100 VIS BuB/H,O

(L) Ill
Pinane 1562 TERRENES P 0.01-0.2 2 30 GC-FID CCT
Ptnene 2549 VOLATILE ORGANIC CPDS (Screening) P 0.01-0.05 1 6 TD/GC-MS TD
PJatinum 7300 ELEMENTS by ICP P 1-4 13 2000 ICP-AES MCEF
PAH 5506 POLYNUCLEAR AROMATIC H/C P 2.0 200 1000 HPLC-FL/UV PTFE & XAD-2
Polyacrylate 5035 SUPER ABSORBENT POLYMER P 1 -2 50 1500 ICPorAAS PVC
Polychloroblphenyl 5503 POLYCHLOROBIPHENYLS P 0.05-0.2 1 50 GC-ECD GFF & Florisil

(42% & 54% Cl)
PoUMlum hydroxide 7401 ALKALINE DUSTS F 1 -4 70 1000 Miration PTFE
ProplonaldehydB 2539 ALDEHYDES, SCREENING P 0.01-0.05 5 5 GC-FID/MS XAD-2/HMP
n-Propyl acetate 1450 ESTERS! P 0.01-0.2 1 10 GC-FID CCT
n-Propyl alcohol 1401 ALCOHOLS II F 0.01-0.2 1 10 GC-FID CCT
Propylene dichlorlde 1013 PROPYLENE DICHLORIDE F 0.01-0.2 0.1 3.5 GC-ECN PCT
Propylene glycol 5523 GLYCOLS P 0.5-2 5 60 GC-FID OVS-7
Propylene oxide 1612 PROPYLENE OXIDE P 0.01-0.2 0.5 5 GC-FID CCT
Pyrene 5506 POLYNUCLEAR AROMATIC P 2.0 200 1000 HPLC-FLAJV; PTFE & XAD-2
HYDROCARBONS GC-FID
Pyrethmm 5008 PYRETHUM F 1-4 20 400 HPLC-UV GFF
Pyridine 1613 PYRlDINE F 0.01-1.0 18 150 QC-FID CCT
Ribavirin 5027 RIBAVIRIN U 1 -4 5 1000 HPLC-UV GFF
Ronrwl 5600 ORGANOPHOSPHORUS PESTICIDES F 0.2-1 12 60 GC-FPD OVS-2
Rotenone 5007 ROTENONE F 1-4 8 400 HPLC-UV PTFE
Rubber solvent 1550 NAPHTHAS F 0.01-0.2 1.3 20 GC-FID CCT
Selenium 7300 ELEMENTS by ICP P 1 -4 5 2000 ICP-AES MCEF
Silica, amorphous 7501 SILICA, AMORPHOUS P 1.7 or 2.2 50 400 XRD PVC (total) or
PVC & CYC
Silica In coal mine dust 7603 SILICA In coal mine dust U 1.7 or 2.2 300 1000 IR CYC & PVC
Silica, crystalline 7601 SILICA, CRYSTALLINE P 1.7 or 2.2 400 800 VIS CYC & MCE or
PVC
Silica, crystalline 7602 SILICA, CRYSTALLINE (IR) P 1.7 or 2.2 400 800 IR CYC & MCE or
PVC
Silica, crystalline, 7500 SILICA. CRYSTALLINE, RESP. F 1.7 or 2.2 400 1000 XRD CYC I PVC
respjrable
Silver 7300 ELEMENTS by ICP P 1-4 :•:- : 250 2000 ICP-AES MCEF
Sodium hexafluoro- 7902 FLUORIDES, aerosol & gas P 1-2 12 800 ISE MCEF & pad
aluminate w/Na2CO3
Sodium hexafluoro- 7906 FLUORIDES by IC P 1-2 120 800 IC MCEF & pad
alumlnate w/Na2CO,
Sodium hydroxide 7401 ALKALINE DUSTS F 1 -4 70 1000 Titiation PTFE
Stlbine 6008 STIBINE F 0.01-0.2 4 50 VIS SG w/HgCI;
Stoddard solvent 1550 NAPHTHAS F 0.01-0.2 1.3 20 GC-FID CCT
Strychnine 5016 STRYCHNINE F 1-3 70 1000 HPLC-UV GFF
Stvrene 1501 HYDROCARBONS. AROMATIC P 0.01-1.0 1 14 GC-FID CCT

(U (L)
Sulfur dioxide 6004 SULFUR DIOXIDE P 0.5-1.5 4 200 1C HCEFi

padw/Na2CO,
Sulfur hexafluoride 6602 SULFUR HEXAFLUORIDE F 0.01-0.05 NA 80% GC-ECD air bag
Vol
Sulfuric acid 7903 ACIDS, INORGANIC F 0.2-0.5 3 100 IC SG (washed)
Sulfuryl fluoride 6012 SULFURYL FLUORIDE F 0.05-0.1 1.3 10 IC CCT(lg)
Sulprofos 5600 OR6ANOPHOSPHORUS PESTICIDES F 0.2-1 12 240 GC-FPD OVS-2
Super absorbent polymer 5035 SUPER ABSORBENT POLYMER P 1-3 50 1500 ICPorAAS PVC
2,4,5-T 5001 2,4-D and 2,4,6-T F 1-3 15 200 HPLC-UV GFF
Tellurium 7300 ELEMENTS by ICP P 1 -4 25 2000 ICP-AES MCEF
Terbufo* 6600 ORGANOPHOSPHORUS PESTICIDES F 0.2*1 12 240 GC-FID OVS-2
Terpenes 1552 TERPENES P 0.01-2 2 30 GC-FID CCT
o-Terphenyl 5021 0-TERPHENYL P 1 -3 2 30 GC-FID PTFE
1,1,2,2-Tetrabromoethane 2003 1,1,2,2-TETRABROMOETHANE P 0.2-1.0 50 100 GC-FID SG
Tetrabutyltin 5504 ORGANOTIN COMPOUNDS F 1-1.5 50 500 HPLC/HGAAS GFF & XAD-2
1,2,4,5-Tetrachlorobenzene 5517 POLYCHLOROBENZENES F 0.01-0.2 3 12 GC-ECD PTFE & XAD-2
1,1,2,2-Tetrachloro- 1016 1,1,2,2-TETRACHLORO-«- P 0.01-0.035 0.5 2 GC-FID CCT

2,2-difIuoroethan« DIFLUOROETHANE 1 1,1,2,2-
TETRAC HLORO- 1 , 2-DI F L UORO-
ETHANE
1,1,1,2-Tetrachloro- 1016 1,1,2^-TETRACHLORO-2,2- P 0.01-0.035 0.5 2 GC-FID CCT

1,2-dHluoroethane DIFLUOROETHANE & 1,1.2,2-
TETRACHLORO-1,2-DIFLUORO-
ETHANE
1,1,2,2-Tetrachloroethane 1019 1,1,2,2-TETRACHLOROETHANE P 0.01-0.2 3 30 GC-FID PCT
Tetrachloroethylene 1003 HYDROCARBONS, HALOGENATED P 0.01-0.2 0.2 40 GC-FID CCT
Tetraathylene glycol 5523 GLYCOLS P 0.5-2 5 60 GC-FID OVS-7
Tetraethyl lead 2533 TETRAETHYL LEAD (as Pb) F 0.01-1.0 30 200 GC-PID XAD-2
Tetraethyl pyrophosphate 2504 TETRAETHYL PYROPHOSPHATE F 0.01-0.2 20 48 GC-FPD 2Chrom102
Tetrahydrofuran 1609 TETRAHYDROFURAN P 0.01-0.2 1 1 GC-FID CCT
Tetramethyl lead 2534 TETRAMETHYL LEAD (as Pb) F 0.01-0.2 15 100 GC-PID XAD-2
Tetrarnethyl thiourea 3505 TETRAMETHYL THIOUREA P 0.2-1.0 50 250 VIS IMP/H,0
TefranMromethane 3513 TETRANITROMETHANE F 0.5-1.0 20 250 GC-FID IMP/EtAc
Thallium 7300 ELEMENTS by ICP P 1-4 25 2000 ICP-AES MCEF
Thiram 5005 THIRAM F 1 -4 10 400 HPLC-UV PTFE
Tin, organic compds as Sn 5504 ORGANOTIN CPDS. (as Sn) F 1-1.5 50 500 HPLC/GFAAS GFF & XAD-2
Titanium 7300 ELEMENTS by ICP P 1 -4 6 100 ICP-AES MCEF
o-Tolldine 5013 DYES P 1-3 150 500 HPLC-UV PTFE
Toluene 2549 VOLATILE ORGANlC CPDS (Screening) P 0.01-0.05 1 6 TD/GC-MS TD
Toluene 4000 TOLUENE F NA (« (8h) GC-FID passive

rrfnj
Toluene 1500 HYDROCARBONS, BP 36-126'C F 0.01-0.2 2 8 GC-FID CCT
Toluene 1501 HYDROCARBONS. AROMATIC P 0.01-0.2 1 8 GC-FID CCT

(L) (L)
2,4 & 2,6-Toluenediamine 5516 2,4- & 2,6-TOLUENEDIAMINE P 1.0 30 500 HPLC-UV IMP
Toluene-2,4-diisocyanate 2535 TOLUENE-2.4-DIISOCYANATE F 0.2-1.0 2 170 HPLC-UV GW coated
Toluene-2,4-dl)socyanate 5521 ISOCYANATES, MONOMERIC U 1.0 5 500 HPLC-ECHD IMP
Toluene-2,4-dilsocyanate 5522 ISOCYANATES . P 1-2 16 360 HPLC-FL lMP
Toluene-2,6-dllsocyanate 5522 ISOCYANATES P 1-2 16 360 HPUC-FL lMP
Toluene-2,6-diisocyariate 6521 ISOCYANATES, MONOMERIC U 1.0 5 MO HPLC-ECHD IMP
o-Toluidine 2002 AMINES, AROMATIC F 0.02-1.0 10 150 GC-FID SO
Tribromomethane 1003 HYDROCARBONS, HALOGENATED P 0.01-0.2 4 70 GC-FID CCT
Tributyl phosphate 5034 TRlBUTYL PHOSPHATE P 1 -3 2 100 GC-FPD MCEF
Tributyltin chloride 5504 ORGANOTIN COMPOUNDS F 1-1.5 50 500 HPLC/GFAAS GFF & XAD-2
1 ,2,4-Trichlorobenzene 5517 POLYCHLOROBENZENES F 0.01-0.2 3 12 GC-ECD PTFE & XAD-2
1,1,2-Trtchloroethane 1003 HYDROCARBONS, HALOGENATED P 0.01-0.2 2 60 GC-FID CCT
1,1.1-Trtchloroethane 1003 HYDROCARBONS, HALOGENATED P 0.01-0.2 0.1 8 GC-FID CCT
1,1,1-Trichloroethane 2549 VOLATILE ORGANIC CPDS (Screening) P 0.01-0.05 1 6 TD/GC-MS TD
Trichloroethylene 1022 TRICHLOROETHYLENE P 0.01-0.2 1 30 GC-FID CCT
Trichloroothylene 3701 TRICHLOROETHYLENE by portable GC F >0.02 NA 80% GC air bag

Vol
Trichlorofluoromethane 1008 FLUOROTRICHLOROMETHANE F 0.01-0.05 0.3 7 GC-FID CCT
Trichloromethane 1003 HYDROCARBONS, HALOGENATED P 0.01-0.2 1 50 GC-FID CCT
1 ,2,3-Trich loropropane 1003 HYDROCARBONS, HALOGENATED P 0.01-0.2 0.6 60 GC-FID CCT
Trichcylohexyltin 5504 ORGANOTlN COMPOUNDS F 1-1.5 50 500 HPLC-GFAAS GFF & XAD-2
hydroxide
1.1,2-Trtehloro 1,2,2- 1020 1,1.2-TRICHLORO-1,2,2- P 0.01-0.06 0.1 3 GC-FID CCT

trifluoroethane TRIFLUOROETHANE
1,1,2-Trtchloro 1,2.2- 25*9 VOLATILE ORGANIC CPDS (Screening) P 0.01-0.05 1 6 TD/GC-MS TD

trtfluoroathane
Trielhanolamine 3509 AMINOETHANOL COMPOUNDS II P 0.5-1.0 5 300 IC lMP
Triethylene glycol 5523 GLYCOLS P 0.5-2 5 60 GC-FID OVS-7
Triethylenetetramine 2540 ETHYLENEDIAMINE, U 0.01-0.1 1 20 HPLC-UV XAD-2

Trifluorobromomethane 1017 TRIFLUOROBROMOMETHANE P 0.01-0.05 0.1 1 GC-FID 2 CCT (Ig+sm)
Trtmellitlc anhydride 5036 TRIMELLITIC ANHYDRIDE P 1.5-2 400 1000 GC-FID PVC
2,4,7-Trimtrofli40ren-9-one 5018 2,4,7-TRINITRO-FtUOREN-e-ONE P 1-3 100 500 HPLC-UV PTFE
Triorthocresyl phosphate 5037 TRIORTHOCRESYL PHOSPHATE P 1-3 2 100 GC-FPD MCEF
Triphenyl phosphate 5038 TRIPHENYL PHOSPHATE P 1-3 10 400 GC-FPD MCEF
Tungsten, 7074 TUNGSTEN (soluble/Insoluble) F 1-4 200 1000 FAAS MCEF

soluble/insoluble
Turpentine 1551 TURPENTINE F 0.01-0.2 1 10 GC-FID CCT
Turpentine 2549 VOLATILE ORGANIC CPDS (Screening) P 0.01-0.05 1 6 TD/GC-MS TD
Valeraldehyde 2536 VALERALDEHYDE F 0.01-0.04 0.5 10 GC-FID XAD-2/HMP
Valeraldehvde 2539 ALDEHYDES. SCREENING P 0.01-0.05 5 5 GC-FID/MS XAD-2/HMP
MF-15 NIOSH Manual of Analytical Methods

Meth. Eval Flow Rate Mln. Max. Analytical
(LI (LI
V*n*dIum 7300 ELEMENTS by ICP P 1-4 6 2000 ICP-AES MCEF
Vanadjum oxldes 7604 VANADIUM OXIDES P 1.7 or 2.2 200 1000 XRD CYC & PVC
Vinyl acetate 1X53 VINYL ACETATE U 0.1-0.2 0.76 24 GC-FID MS (carbon)
Vinytbetuene 1601 HYDROCARBONS, AROMATIC P .01-1 1 14 GC-FID CCT
Vinyl bromide 1009 VINYL BROMIDE F 0.01-0.2 2 10 GC-FID CCT (Ifl)
Vinyl chloride 1007 VINYL CHLORIDE F 0.06 0.7 6 GC-FID 2 CCT
VlnyIIdene chloride 1016 VINYLIDENE CHLORIDE F 0.01-0.2 2.6 7 GC-FID CCT
Vinyl toluene 1601 HYDROCARBONS, AROMATIC P 0.01-0.2 1 24 GC-FID CCT
VM&P naphtha 1660 NAPHTHAS F 0.01-0.2 1.3 20 GC-FID CCT
voc» 2549 VOLATILE ORGANIC CPD3 (3OT«ning| P 0.01-0.05 1 1 TD/OC-M3 TO
Warfarin 5002 WARFARIN P 1 -4 200 1000 HPLC-UV PTFE
Xylen« 2549 VOLATILE ORGANIC CPDS (Screening) P 0.01-0.06 1 6 TD/GC-MS TO
Xylene 1601 HYDROCARBONS, AROMATIC P 0.01-0.2 2 23 GC-FID CCT
2,4-XyIIdlna 2002 AMINES, AROMATIC F 0.02-0.2 3 20 GC-FID SG
Yttrium 7300 ELEMENTS by ICP P 1 -4 6 1000 ICP-AES MCEF
Zinc and compounds 7030 ZINC and compounds, as Zn P 1 -3 2 400 FAAS MCEF
Zinc 7300 ELEMENTS by ICP P 1 -4 6 200 ICP-AES MCEF
Zinc oxide 7602 ZINC OXIDE F 1 -3 10 400 XRO PVC
Zirconium 7300 ELEMENTS by ICP P 1-4 6 200 ICP-AES MCEF

METHOD FINDER KEY TO ABBREVIATIONS
Sampling Media/Devices
Ag F Silver membrane filter
BuB Bubbler
CCT Coconut shell charcoal tube
Chrom Chromosorb
CYC Cyclone
DNPH Dinitrophenylhydrazine HCI
Dry Drying tube
GFF Glass fiber filter
GW Glass wool
HMP 2-(Hydroxymethyl)piperidine
IMP Impinger
IOM Inspirable dust sampler
MCEF Mixed cellulose ester filter
MS Molecular sieve
NITC 1-naphthylisothiocyanate
OVS-2 OSHA versatile sampler (quartz filter/XAD-2)
OVS-7 OSHA versatile sampler ( glass fiber filter/XAD-7)
Pad Cellulose backup pad
PCT Petroleum charcoal tube
Por Poropak
PTFE Polytetrafluoroethylene (Teflon) filter
PVC Polyvinyl chloride filter
OFF Quartz fiber filter
SG Silica gel
TD Thermal desorption tube
TEA Triethanolamine
Analytical Techniques
AAS Atomic absorption spectrophotometry
AMP Amperometric detector
CD Conductivity detector
DPP Differential Pulse Polargraphy
ECD Electron capture detector
ECHO Electrochemical detector
ECN Electrolytic conductivity detector
EGA Evolved gas analysis
FAAS Flame AAS
FID Flame ionization detector
FL Fluorescence detector
FPD Flame photometric detector
GC Gas chromatography
Grav Gravimetric (filter weight)
GFAAS Graphite furnace AAS
HPLC High performance liquid chromatography
HYAAS Hydride generation AAS
IC Ion chromatography
ICP-AES Inductively coupled plasma-atomic emission spectroscopy
IR Infrared spoectrophotometry
ISE Ion specific electrode
MS Mass spectrometry
NPD Nitrogen phosphorus detector
PCM Phase contrast microscopy
PES Plasma emission spectrometry
PID Photoionization detector
PLM Polarized light microscopy
SEM Scanning electron microscopy
Spot Spot test
TCD Thermal conductivity detector
TEM Transmission electron microscopy
TOA Thermal optical analyzer
UV Ultraviolet
VIS Visible absorption spectrophotometry
XRD X-ray diffraction
XRF X-ray fluorescence
Evaluation
F Full evaluation
P Partial evaluation
U Unrated
NA Not applicable
Var Variable

INTRODUCTION
A. PURPOSE AND SCOPE
The NIOSH Manual of Analytical Methods (NMAM) is a collection of air and

biological analytical methods which NIOSH has evaluated. NMAM will be updated
as methods are developed, evaluated or revised by NIOSH. NMAM is available in
looseleaf hard copy form, without binders, from the U.S. Government Printing
Office, Washington, DC 20402 (telephone 202/783-3238), and in electronic form
from various software companies that have entered into publishing agreements with
NIOSH as of the time of this printing:
WindowChem Canadian Centre for Occupational Health

420-F Executive Court North and Safety (CCOHS)
Suite 7-288 250 Main Street East
Fairfield, CA 94585 Hamilton, Ontario, Canada L8N 1H6
Telephone: 800/536-0404 Telephone: 800/668-4284 or
FAX: 707/864-2815 905/570-8094
FAX: 905/572-2206
The present edition of NMAM replaces previous editions (see page ii for ordering
information if previous editions are needed for historical purposes). A few methods
from the second edition have not been included in the present edition because of
infrequent use at NIOSH (see pp. A-15 through A-28).
These methods are intended to promote accuracy, sensitivity and specificity in

industrial hygiene analyses. The scientific literature contains equally accurate
methods for many of the substances. There will be situations where users of these
methods will need to modify them (e.g., to accommodate interfering compounds
from the workplace, to take advantage of special capabilities of the laboratory, or to
make possible the analysis of a single sample for several contaminants). When
method modifications are made, quality control data showing the reliability of the
modified method should be obtained. For example:
• The volume of air sampled on solid sorbents should be reduced in cases

of high vapor concentration or high humidity and, in some cases, may be
increased above VMAX if such concentrations are relatively low.
• The automation of sample work-up and measurement procedures usually

requires some modification of the nonautomated procedure.
• Chromatographic conditions, including choice of column and detector,

can be modified to eliminate interferences during measurement.
B. HOW TO USE NMAM
The methods are arranged alphabetically by method name, and some method names
may refer to a group of related substances. It is possible for you to rearrange the
methods in order of method number if you find this arrangement more convenient.
1. METHOD FINDER
The easiest and fastest way to locate a method is to refer to the Method Finder inside
the front cover of the Manual. The Method Finder is an alphabetical listing of common
chemical names and their associated methods with information on Compound, Method
Number, Method Name, Sampling Rate, Minimum Volume, Maximum Volume,
Analytical Technique, and Sampler for quick reference.
2. METHOD NUMBERING SYSTEM
Substances having the same sampler, sample preparation and measurement technique
may be grouped together in one method (note that this numbering system is unchanged
from the Third Edition):
Method # Substances
0001-0899 General air samples
0900-0999 Bioaerosols
1000-1999 Organic gases on charcoal
2000-3499 Organic gases on other solid sorbents
3500-3999 Organic gases on other samplers (e.g., liquids, direct-reading)
4000-4999 Organic gases on diffusive samplers
5000-5999 Organic aerosols
6000-6999 Inorganic gases
7000-7999 Inorganic aerosols
8000-8999 Biological samples
9000-9999 Bulk samples
3. INDEXES
There are three indexes in the back of the Manual which can be used in locating
methods:
a. Fourth Edition Methods - An index of current NIOSH methods in order of

Method number (pp. A-1 1 through A-14). [NOTE: The fourth edition uses
the same numbering system as the third edition. This Index also lists the
disposition of all third edition methods.]
b. First and Second Edition Method Numbers - An index of the first and second
edition "P&CAM" and "S" methods, from which many of the current
methods were derived. This index shows the disposition of all of these
methods, whether or not they were revised into current methods (pp. A-1 5
through A-28).
c. Names and Synonyms - An alphabetical listing of all chemical names and

synonyms used in the current methods, including Chemical Abstracts
Service numbers ("yellow pages", pp. A-29 through A-45).
8/15/94 2 NIOSH Manual of Analytical Methods

4. METHOD FORMAT
The methods consist of three major parts:
a. Front page The first page of each method concisely summarizes sampling and
measurement parameters, and gives estimates of limit of detection, working range,
overall and measurement precision, and interferences. References to other
methods are given. New to the fourth edition are: Method Classification, NIOSH
Registry of Toxic Effects of Chemical Substances (RTECS) number, and an estimate
of Accuracy at the OSHA PEL. (See Figure 1.)
b. Instructions The second page of each method begins with lists of required
REAGENTS and EQUIPMENT. Please note that these reflect the conditions under
which the methods were evaluated, and that there may be some latitude for
variation. Commercial versions of the samplers may differ slightly from the
methods. The user of the methods is responsible for assuring accuracy of the
results (e.g., to determine that breakthrough and recovery are acceptable for each
lot of samplers used). Typical tolerances are:
• Glass tubing used to contain solid sorbents: inside diameter is usually

not critical within the range 4 to 6 mm; length should be sufficient to
contain the specified mass of sorbent.
• Contents of sorbent tubes: mass of sorbent within ±10% of

specification; separators of either glass wool or cleaned polyurethane
foam unless otherwise indicated; sorbent mesh size of 20/40 unless
sampling efficiency dictates otherwise. Filled sorbent tubes should be
sealed to protect from contamination.
The SPECIAL PRECAUTIONS section gives safe practices to be observed during

sampling and measurement. Next come the step-by-step instructions for
SAMPLING, SAMPLE PREPARATION, CALIBRATION AND QUALITY CONTROL,
MEASUREMENT, and CALCULATIONS. Any lengthy instructions for sampler
preparation or standardization of stock solutions appear in appendixes to the
method. Nomenclature is consistent with the Glossary of Abbreviations,
Definitions and Symbols (page A-3).
[NOTE: Additional general information relating to sampling and measurement

is contained in the chapters on quality assurance and sampling (pp. 6
through 16 and 17 through 32 of these "Blue Pages").]
c. Supporting information Laboratory and field data relating to the method are
summarized in the EVALUATION OF METHOD section and on the summary page,
along with pertinent references.
8/1 5/94 3 NIOSH Manual of Analytical Methods

NAME OF SUBSTANCE METHOD #
FORMULA Molecular Weight Chemical Abstracts Service # RTECS #
Method numbers are the same as those in the 3rd edition. Evaluation (Full, Partial, Unrated) is assigned as described
on p. 5 of the "blue pages". Issue date reflects current version (August 15, 1993) and previous 3rd edition versions,
if any.
OSHA : These exposure limit values are PROPERTIES: Boiling/melting points, equilibrium
NIOSH: those in effect at the time of vapor pressure, and density help
ACGIH: printing of the method. determine the sample aerosol/vapor
composition.
SYNONYMS: Common synonyms for the substance, including Chemical Abstracts Service (CAS) numbers; these are all
listed alphabetically in the Index of Names and Synonyms ("yellow pages" in this Manual).
SAMPLING MEASUREMENT
SAMPLER: Brief description of sampling EQUIPMENT TECHNIQUE: The measurement technique used
FLOW RATE: Acceptable sampling range, t /iuin ANALYTE: The chemical species actually
measured
VOL-MIN: Minimum sample volume (L); corresponds
to Limit of Quantitation (LOQ) at OSHA PEL A summary of the measurement
EQUIPMENT, SAMPLE PREPARATION,
-MAX: Maximum sample volume (L) to avoid and MEASUREMENT steps appearing
analyte breakthrough or overloading on the second page of the method is
given here.
BLANKS: Each set should have at least 2 field blanks,
up to 10% of samples, plus 6 or more CALIBRATION: Summary of type of standards used
media blanks in the case of coated
sorbents, impinger solutions, or other RANGE: Range of calibration standards to be
used; from LOQ to upper limit of
measurement (Note: More
ACCURACY concentrated samples may be diluted
in most cases to fall within this
Data are for experiments in which known atmospheres of calibration range.)
the substance were generated and analyzed according to
the method. Target accuracy is less than 25% difference ESTIMATED LOD: Limit of detection (background + 3a)
from actual concentration at or above the OSHA PEL.
PRECISION (Sr): Experimental precision of spiked
samplers
APPLICABILITY: The conditions under which the method is useful, including the working range in mg/m3 (from the LOQ to
the maximum sampler loading) for a stated air volume are given here.
INTERFERENCES: Compounds or conditions which are known to interfere in either sampling or measurement are listed.
OTHER METHODS: Methods from the 2nd edition ("P&CAM" and 'S" methods) which are related to this one, as well as
similar OSHA and literature methods are keyed to REFERENCES.
Figure 1 . Layout of front page of methods.

5. METHOD CLASSIFICATION
Methods in the fourth edition of the NIOSH Manual of Analytical Methods are classified
into three Evaluation categories: Full, Partial, and Unrated. Classification is based on the
results of laboratory testing and evaluation criteria as described in Chapter E, Development
and Evaluation of Methods.
The data from these evaluations are summarized in the EVALUATION OF METHOD section
in each method. This section may also contain other corroborating data, e.g.,
collaborative testing, Proficiency Analytical Testing (PAT) data, or field data from NIOSH
Sequences. For Partially Evaluated methods, this section will state which evaluation
points were not tested, thus providing the user with information on which to make a
reasonable judgment on the quality of the data obtained.
Evaluation: Full
Fully evaluated methods are methods that have been tested and have met all the
factors of the NIOSH evaluation protocol as presented in Chapter E.
Evaluation: Partial
Partially evaluated methods are methods that have been subjected to some of the
evaluation experiments but have not received a full evaluation (i.e., Short-term
Method Development). These may also include methods that were fully tested but
did not meet one or two of the evaluation criteria, e.g., some of the earlier-
developed methods that do not meet the current ±25% accuracy criterion.
Evaluation: Unrated
Unrated methods have not been tested by NIOSH, but have been developed by a
recognized independent source such as the Occupational Safety and Health
Administration (OSHA).
6. USER EXPERIENCE WITH THE METHODS
NIOSH seeks to make these methods useful in industrial hygiene analyses. Therefore, the
experience of people using the methods is important to us. Suggestions for improvement
and questions relating to this Manual are welcome and should be directed to the Manual
Coordinator. A comment form has been included in the back of this Manual for this use;
it can be mailed or FAXed.

C. QUALITY ASSURANCE
by David L. Smith, CIH; Michele L. Bolyard, CIH; and Peter M. Eller, Ph.D., CIH
Contents: Page
1. Role of Laboratory Quality Assurance Program 6

2. Organization 7
a. Quality Assurance Coordinator 7
b. Sample Clerk 8
3. Quality Assurance in Sampling 8
4. Quality Assurance in Measurement 9
a. Methods 9
b. Standards 9
c. Blanks 10
d. Blind Samples 10
e. Recovery Studies 11
f . Duplicates 11
5. Interlaboratory Testing 11
6. Reporting 12
7. Laboratory Notebooks 12
8. Instrument Maintenance 13
9. Sample Tracking 14
10. Quality Assurance Records 14
11. References . 14
1 . ROLE OF LABORATORY QUALITY ASSURANCE PROGRAM
Analytical data are used to make a variety of decisions, i.e., to decide whether a particular
chemical agent is present in a workplace atmosphere, whether a hazard to workers' health
exists in that atmosphere, or whether a workroom atmosphere complies with applicable
standards. Errors in such data can have a variety of costly effects [1 ]. The consequences
of erroneous data may lead to the wrong decision being made as to whether a
non-compliance situation exists. If the analytical results are a part of a larger experiment,
perhaps the wrong conclusion might be reached or the results might be uninterpretable.
If the presence or absence of a particular agent is erroneously reported, a threat to
workers' health may be allowed to continue. It is the role of a laboratory's quality
assurance program to provide the necessary safeguards to minimize these occurrences and
to provide a means of detecting errors when they do occur. There are many good texts
and articles addressing the subject of laboratory quality control [2,3,4,5]. The purpose
of this chapter is to address some of the aspects of quality control as they relate to
industrial hygiene laboratory quality control.
It is not possible to design a quality assurance program to fit all laboratories since no two
laboratories serve the exact same purpose or operate in exactly the same manner. Each
laboratory must set its own operating procedures and quality control practices, and
document them in a Quality Assurance Manual [2,3,5]. This chapter, therefore, will not

to set forth concrete recommendations for implementing a quality assurance program, but
rather will present aspects of laboratory quality assurance and quality control which should
be addressed by each laboratory.
A successful quality assurance effort cannot be achieved through the efforts of only one
individual. A laboratory's quality assurance coordinator needs the assistance and
cooperation of all laboratory personnel to be effective. To this end, it is necessary to
discourage adversarial relationships between quality control personnel and bench chemists.
Analysts must be trained and made aware of the purpose and value of quality assurance
functions and, in turn, the quality assurance program must be designed so that its
functions are based on sound goals directed toward improving the performance of both
the individual analyst and the laboratory as a whole.
Frequently, analytical results are challenged months or years afterthe analysis is complete.
In order to support the original data, an effective, complete, record-keeping system must
be maintained. Another chemist must be able to reconstruct the exact treatment to which
the samples were subjected solely from a laboratory's records. Furthermore, if the
appropriate quality control checks were performed with the analysis and documented,
there can be no doubt regarding the results.
2. ORGANIZATION
A laboratory, just as any other organization, should have a clearly defined organizational
structure. Responsibilities of each member of the laboratory staff should be in writing and
understood by all. In this way, confusion regarding tasks which need to be performed can
be avoided.
The specific organizational structure of the laboratory will vary, depending on the
laboratory's function. Two functions which relate to quality assurance should be assigned
in every laboratory: the quality assurance coordinator and the sample clerk. The size and
nature of the laboratory may preclude assignment of a full-time position to these functions;
however, a laboratory member should be assigned these duties and it should be
understood that they are to have top priority.
a. Quality Assurance Coordinator
The quality assurance coordinator's functions will depend on the size and nature of the
laboratory. This professional has overall responsibility for assuring that reported data meet
established standards for precision and accuracy and that these results can be supported
scientifically by the various quality control checks performed with the analysis. One of
the major functions of this individual is to perform audits of the quality control system and
to implement changes that eliminate recurring errors [2,3,4,5]. The quality assurance
coordinator should not be under the direct supervision of management responsible for
day-to-day laboratory operation. In this way, conflicts between the laboratory's dual
responsibilities of providing analytical results in a rapid fashion while maintaining quality
can be avoided. The quality assurance coordinator should also serve as a resource person
for chemists or managers on questions or problems related to quality assurance and should

have a working knowledge of statistics, including quality control charting, and
experimental design.
b. Sample Clerk
The sample clerk's functions will also vary, depending on the size and function of the
laboratory. As a minimum, the sample clerk is responsible for the receipt and log-in of
samples. Field samples should be stored in a secure location under proper conditions
(temperature, etc.) until analysis. Logging and tracking of samples in the laboratory is
important so that the history of these samples can be documented and processed in a
timely manner. The sample clerk may also be given the responsibility of maintaining chain
of custody documentation.
3. QUALITY ASSURANCE IN SAMPLING
Quality assurance procedures should not be overlooked by personnel performing field

sampling. The field sampling parameters often have more effect on precision and
accuracy of the final result than parameters of the measurement [2,4,5,6,7]. Field
personnel should become familiar with sampling and measurement methods which they
will use. The methods usually specify the proper sampling media to be used, the correct
flow rate and sample volume, as well as special precautions on sample handling, shipping
and possible interferences.
Sampling equipment must be maintained in reliable working order. It is desirable to have

one person or group given responsibility for the care, maintenance and stocking of field
sampling equipment. This person or group should periodically inspect and repair all
equipment and keep track of the use and location of sampling equipment when it is signed
out. Sampling pumps should be calibrated with each use. This calibration should be
performed with the sampler in line. Since differences in pressure drop across the sampler
will affect flow rate, it may be necessary to perform the calibration with the actual
sampler to be used.
The exact sampling time must be known in order to accurately estimate the sampled
volume. Recording only the start and stop time assumes that the pump functions properly
over the entire sampling period. Occasional spot checks for proper operation should be
made throughout the sampling period.
Since many modern analytical techniques are extremely sensitive, special care must be
taken to avoid contamination of field samples [8]. Samples must not be stored or shipped
with bulk materials which might spill or otherwise present the possibility for
contamination. The glassware or other containers used in sampling and shipping should
be subjected to any cleaning procedures recommended in the analytical method.
Careful record keeping in the field is also important. Pertinent information such as
temperature, humidity, possible interfering compounds, sampling location, etc. should be
documented. Special care should be taken in sample labelling and in preparation of
paperwork accompanying the samples so that confusion in the laboratory is avoided.

Field blanks are used to estimate contamination which may occur immediately before and
after sampling, during shipment, or while awaiting measurement in the laboratory. The
nature and number of blanks taken will depend on the method and sampling situation;
therefore, field sampling personnel must attempt to determine what sources of
contamination are possible in the specific situation at hand. The field blank strategy must
then be designed accordingly. Where possible, a written sample protocol should be
developed before actual sampling begins [3,4,9,10]. The protocol should contain a
description of the environment being sampled; the assumptions made in derivation of the
model of that environment; when, where, and how the sampling will be done; and how
many samples will be taken. Samplers should be identified by batch or lot number of
sampling media.
4. QUALITY ASSURANCE IN MEASUREMENT
Certain quality control checks should be performed with each sample set [2,4] to further
support the reported results on actual field samples. The exact number and nature of
these checks depend on the specific method and circumstances under consideration and
should be thought of as an integral part of the method itself (i.e., a measurement should
not be considered completed without the quality control checks also being completed).
Each analyst must take an independent responsibility for assuring that the analytical
quality control system works. This can be accomplished by using known spiked samples
which closely simulate field samples with regard to concentration and interferences. Since
the analyst is most familiar with the methods being used and should know what range of
recoveries to expect, problems with the system can be detected early. We will attempt
to recommend specific quality control checks to be performed with the methods in NMAM;
however, our recommendations cannot be expected to cover all situations. The user of
these methods should consider adding additional quality control checks as appropriate.
a. Methods
First, and perhaps most important in the area of quality control, a laboratory must have
adequate measurement procedures. These methods should be written so that there is no
doubt in the analyst's mind of the exact steps which must be performed and so that future
references to the work can be as exact as possible. The methods used should be
evaluated, where possible (either by the laboratory itself or by some other organization),
to verify that the methods perform satisfactorily. Factors which could be evaluated
include the recovery of the analyte of interest from both spiked samples and generated
samples, the stability of collected samples or possible interferences to accurate use of the
method. Methods should be tested for ruggedness so that critical steps in the analysis
can be identified. Experimental designs have been published which permit rapid evaluation
of a number of factors involved in the analysis (e.g., [1 1]).
b. Standards
Standard solutions may be for either identification or quantitation of the analyte of

interest. The bulk material used for preparation of standards should be of sufficient purity
to avoid errors in the identification or quantitation. Where available, Standard Reference
Materials (SRMs available from the U.S. National Institute of Standards and Technology)

or other well-characterized standards are useful for assuring that results are consistent
with other organizations and agencies [3]. Laboratory reagents and standards should also
be properly labelled with contents, and receipt and expiration dates.
For quantitation, sufficient numbers of standards should be prepared so that adequate

confidence intervals on reported values can be obtained [3,12]. As a guideline, we
recommend that calibration curves be prepared with triplicate points at each of at least
five different concentration levels. The standard curve should be prepared so that linearity
can be assured over the range of the curve. Also, it is important that the concentration
of standard solutions be chosen to bracket the actual samples. In this way, extrapolation
outside the range of standards is avoided. The concentration of standard solutions should
be chosen to be consistent with the purpose of the sampling. That is, if it is desired to
demonstrate whether exposure standards are being met, then the standard curve should
be constructed to bracket the concentrations which would be encountered at or near the
applicable exposure standard. If it is desired to demonstrate whether a compound is
present in the atmosphere being sampled, then the calibration curve should be constructed
closer to the limit of detection. During measurement, working standards should be
interspersed with field samples. In this way, it should be possible to detect if instrument
drift becomes significant. Internal standards are useful for correcting instrument response
for the actual amount of sample injected into a chromatograph. The internal standard
should be chosen so that its retention time is reasonably close, without peak overlap, to
the peak of interest.
c. Blanks (also see page 24)
A particular analysis may involve several types of "blank" measurements including reagent
blanks, media blanks or field blanks. Reagent blanks measure the signal contribution from
solvents, acids or other reagents used by the laboratory in preparing samples for analysis.
Media blanks measure the signal contribution from the collection media (impinger solution,
filter, sorbent tube, etc.) and field blanks measure signal contribution of the media plus
any contamination which may have occurred during handling, shipping and storage before
analysis. The nature and number of blank measurements will depend on the method and
circumstances, but the purpose of all blank measurements is to help prevent errors in
identification and quantitation of field samples [3].
d. Blind Samples
Blind samples are prepared by someone other than the analyst performing the
measurement and are to provide an independent check on the accuracy and precision of
the measurement.
If blind samples cannot be prepared with confidence, their use should be avoided. In these
cases, confusion may result when discrepancies occur and it will not be possible to say
for certain whether the measurement or the blind sample was in error.
The results should be used in conjunction with control charting techniques to identify
errors or malfunctions in the system [2,1 2,1 3]. To accomplish this goal, quality assurance

personnel should work closely with laboratory personnel to quickly identify and eliminate
trouble spots.
It will not always be possible to isolate the source of error in the results of a blind sample.
In these instances, it should be recognized that it will not be possible to defend
quantitative results for that particular sample set; therefore, reporting of results where
these discrepancies occur should be avoided.
e. Recovery Studies
Recovery studies should be performed as a part of the measurement whenever the analyte
of interest must be liberated or separated from the sampling media. The analyte of
interest should be added to the media at levels consistent with the field samples. These
"spiked" samples should then be treated in the same manner as the field samples.
Corrections for recovery should be made whenever the measured recovery is significantly
different from 100%. Even if recovery has historically been 100%, recovery studies can
be useful as additional analytical and calculation checks. It is often helpful for a laboratory
to maintain a record of past recovery studies so that current data may be compared for
discrepancies. Samples for which estimated recovery is less than 75% should be reported
as "semiquantitative."
f. Duplicates
Duplicate preparations of bulk materials are useful as an indication of the uniformity of the
bulk material. Duplicate injections or measurements from air samples are of lesser
importance since preparations from air samples are generally fairly uniform in nature. True
duplicates of air samples are useful as an indication of both the reproducibility of the entire
sampling and measurement method and as an indication of the uniformity of the
atmosphere being sampled.
5. INTERLABORATORY TESTING
Assignable analytical uncertainty can be considered as consisting of interlaboratory and

intralaboratory variability. A knowledge of the magnitude of these two sources of
variability is essential in order to interpret and use analytical data properly. Intralaboratory
variability can be estimated from the results of analysis of blind samples. Interlaboratory
testing requires the cooperation and coordination of a number of independent laboratories
[2,11].
Interlaboratory testing can also be useful for defining the relationship of data reported by
different laboratories using either the same or different measurement techniques
[12,15,16]. Participation in such studies can be useful for uncovering errors in
methodology or identifying critical steps in the procedures.
The Proficiency Analytical Testing (PAT) Program operated by the American Industrial
Hygiene Association in cooperation with NIOSH is useful for measuring a laboratory's
performance on a variety of common industrial hygiene samples, including solvent vapors
8/1 5/94 1 1 NIOSH Manual of Analytical Methods

on charcoal tubes and metals, asbestos and silica on filters. Participation in this program
by laboratories performing industrial hygiene analysis is strongly encouraged.
Similarly, the American Industrial Hygiene Association (AIHA) operates a laboratory

accreditation program for industrial hygiene laboratories. Site visits and application
reviews can provide a useful review of a laboratory's overall quality assurance system, as
well as the adequacy of personnel, facilities and equipment. Appendix E of [2] lists over
twenty other proficiency and check sample programs. An extensive listing of laboratories
accredited in specific test protocols is also available [17].
6. REPORTING
The detail and nature of the analytical report will depend on the function of the laboratory.
As a minimum, the report should include a description or reference to the method used,
any deviations or special circumstances encountered with the sample set, estimates of the
limits of detection and quantitation, the date of analysis, as well as the results themselves.
The report should be signed by the analyst and at least one other person who is
responsible for approving the report. The laboratory should adopt a standard report format
and attempt to maintain that format with all reports.
The limit of detection (LOD) is defined as the amount of the analyte which can be
distinguished from background. The limit of quantitation is that amount of analyte above
which the precision of the reported results is better than a specified level. There are
numerous methods of determining these quantities and many opinions as to which method
is correct. The laboratory should decide on a method for determining these quantities and
be consistent to the extent possible in its use. In NMAM, the American Chemical Society
definition of LOD (i.e., a sample giving a signal three times the standard deviation of
background) is used [4,18].
Sample data should be corrected for recovery or desorption efficiency and for reagent and
media blank response. However, field blanks should be treated like field samples
(corrected for reagent blanks, media blanks, and recovery). If correction for contamination
in the field blanks is necessary, this correction should be performed by the person who
submitted the sample.
Data should be reported simply and concisely and in a manner that "their meaning is not
distorted by the reporting process [4,12,13]." Attention should be given to the number
of significant figures reported. Generally, only the last figure reported should be in doubt.
7. LABORATORY NOTEBOOKS
Laboratory notebooks are used for recording all experimental and analytical notes and data
[19]. New notebooks should be logged out to a chemist. The notebook remains the
property of the laboratory and should be kept in a central location by the laboratory after
it is filled.
Notebooks used in the laboratory should be hard-covered and bound. Use of notebooks
with removable pages (e.g., loose-leaf notebooks) should be discouraged. The pages of

the notebook should be numbered and any entries made by an individual other than that
to whom the book was assigned should be noted. Some laboratories require that the
individual notebook pages be signed by the chemist for legal reasons.
The notebook should contain all information gathered by the chemist pertaining to the
sample. Where appropriate, lab number, field number, sequence number and other
identifying numbers are noted. Measurements requested, identification of the method,
modifications to the method and the sample originator should be included. A description
of the sample (whether bulk material, charcoal tube, etc.) should be included. Data on
quality assurance aspects of the sample set such as blank values, recovery studies and
duplicate determinations should also be included. Formulae used to calculate results and
a sample calculation should be shown.
If permanent retention of computer printouts, recorder charts or similar items is deemed

necessary, they should be pasted, taped or stapled in the notebook, if practical.
The minimum data entered in the notebook should be sufficient to enable another chemist
to derive the same results as the original worker, with no other source of information. In
addition to this minimum data, any other facts appropriate and pertinent to the sample
analysis are to be entered.
A chemist's notebook is always subject to inspection by his colleagues, supervisors or

inspectors from outside the laboratory. Therefore, it is imperative that the notebook be
maintained in a professional manner and contain all pertinent information that may be
required by other parties, regardless of the particular importance of that information to the
chemist. Furthermore, the notebook must be maintained in such a manner that it can
withstand challenges as to the validity, accuracy or legibility of its contents.
8. INSTRUMENT MAINTENANCE
Laboratory instrumentation must be maintained in proper operating condition. We have

found that in numerous cases the cause for out-of-control quality control samples has been
traced to faulty instrument performance. In many of these instances, the operator was
unaware that instrument performance had degraded. Performance checks can be useful
in documenting instrument performance over time and in detecting deviations. To be of
use, performance check procedures should be quick and easy to perform. Appendix C of
[2] gives details of suggested performance checks for a variety of instruments. Where
appropriate (e.g., balances, microscopes) periodic calibration should be performed and
documented. Records of calibration should be recorded in the logbook for that instrument.
An instrument's maintenance history is often valuable in troubleshooting problems with

that instrument. The record of instrument maintenance should be maintained in an
"instrument logbook" and kept near that instrument or in a recognized location.
Service contracts or maintenance agreements for instrument repair are useful for assuring
that instrumentation is serviced by qualified personnel and maintained in proper operating
condition.

9. SAMPLE TRACKING
A laboratory should have a mechanism for logging and tracking samples after they are
received in the laboratory so that all samples can be processed in the most efficient
manner. The exact system used for sample tracking will depend on the size and nature
of the laboratory and may range from hand-entry logbooks to sophisticated
computer-based systems. The system should include a means of cross-referencing
laboratory sample numbers with field sample numbers and it should be possible to
determine the chemist, instrument, and other aspects of the sample set from the field
number.
Sample tracking systems may also be used to produce management statistics which may
aid in forecasting future sample loads or point to problem areas in sample turn-around.
10. QUALITY ASSURANCE RECORDS
Maintenance of quality assurance records aids in recalling details of a particular analysis

at a future date. A condensation of quality assurance data can be used as supporting
evidence to field personnel should the need arise. Quality assurance records can also be
used to track various quality assurance parameters over time (such as desorption
efficiency or blank values).
Computerized recordkeeping systems should be backed up periodically. Archive copies

of computer data require specialized storage conditions and these archive copies may not
be reliable for extended periods of time.
Filing of records should be current and accurate. If rapid retrieval of data is not possible,
then maintenance of quality assurance records loses its purpose. The primary purpose is
to provide a system to furnish information rapidly regarding the status of specific sample
sets.
11. REFERENCES
[1 ] Hunter, J. S. "The National System of Scientific Measurement," Science. 210, 869

(1980).
[2] Garfield, F. M. Quality Assurance Principles for Analytical Laboratories. Association
of Official Analytical Chemists, AOAC International, Arlington, VA (1991).
[3] Taylor, J. K. Quality Assurance of Chemical Measurements, Lewis Publishers,
Chelsea, Ml (1987).
[4] Keith, L. H. Environmental Sampling and Analysis: A Practical Guide, Lewis
Publishers, Chelsea, Ml (1991).
[5] Dux, J. P. Handbook of Quality Assurance for the Analytical Chemistry Laboratory.
Van Nostrand Reinhold, New York (1986).
[6] Kratochvil, B. and J. K. Taylor. "Sampling for Chemical Analysis," Anal. Chem., 53.
924A-938A (1981).
[7] Cali, J. P. and W. P. Reed. Accuracy ]n Trace Analysis: Sampling. Sample
Handling, Analysis, NBS Spec. Publication 422, Vol 1, 41 (1976).
[8] Kosta L. Talanta, 29, 985-992 (1982).

[9] Leidel, N. A., K. A. Busch, and J. R. Lynch. Occupational Exposure Sampling
Strategy Manual, U.S. Department of Health and Human Services, Publ. (NIOSH)
77-173 (1977).
[10] Leidel, N. A. and K. A. Busch. Statistical Design and Data Analysis Requirements,
Chapter 3 in L. V. Cralley and L. J. Cralley, Eds., Patty's Industrial Hygiene and
Toxicology, Vol. \\\, 2nd Edition, Theory and Rationale of Industrial Hygiene Practice.
John Wiley & Sons, NY (1984).
[11] Youden W. J. and E. H. Steiner. Statistical Manual of the Association of Official
Analytical Chemists, AOAC, Washington, DC (1975).
[1 2] Taylor, J. K. Statistical Techniques for Data Analysis, Lewis Publishers, Chelsea, Ml
(1990).
[13] Kelley, W. D., T. A. Ratliff, Jr., and C. Nenadic. Basic Statistics for Laboratories -
A Primer for Laboratory Workers, Van Nostrand Reinhold, New York (1992).
[14] Horwitz, W., L. R. Kamps, and K. W. Boyer. "Quality Assurance in the Analysis of
Foods for Trace Constituents," J. Assoc. Off. Anal. Chem., 63, 1344-54 (1980).
[15] DeVoe, J. R., Ed. ACS Syrnp. Ser. No. 63. American Chemical Society,
Washington, DC (1977).
[16] Shulman, S. A., J. H. Groff, and M. T. Abell, "Performance of Laboratories
Measuring Silica in the Proficiency Analytical Testing Program," Amer.lnd.Hyg.
Assoc.J., 53: 49-56 (1 992).
[17] American Association for Laboratory Accreditation, A2LA 1993 Directory of
Accredited Laboratories, Gaithersburg, MD (1993).
[18] NIOSH/DPSE Standard Operating Procedure, "SOP018 Limits of Detection and
Quantitation," Cincinnati, OH (1991).
[1 9] Kanare, H. M., Writing the Laboratory Notebook, American Chemical Society,
Washington, DC (1985).

D. GENERAL CONSIDERATIONS FOR SAMPLING AIRBORNE CONTAMINANTS If
by Charles S. McCammon, Ph.D., CIH, NIOSH/REGION VIII
Contents: Page
1. Choosing Measurement Methods and Sampling Media 16

2. Figuring Sampling Parameters 19
a. Sampling for Gases and Vapors Using Solid Sorbents 20
b. Pushing a Method to the Limit 20
3. Bulk Samples 21
a. Bulk Air Samples 21
b. Bulk Liquids and Solids 22
4. Blanks 23
5. Direct-Reading Methods 23
6. Sampling Strategy 24
7. Sampling Technique 24
a. Calibration of Personal Sampling Pumps 24
b. Sampling Instructions for Solid Sorbent Tube Sampler 27
c. Sampling Instructions for Filter Sampler 28
d. Sampling Instructions for Filter + Cyclone Sampler 29
8. References . 30
1. CHOOSING MEASUREMENT METHODS AND SAMPLING MEDIA
As proper advance planning minimizes sampling and measurement costs and labor and
contributes to a smooth, successful survey, many things must be considered before
collecting field samples [1 ]. The first step is to define sampling objectives. These may
include documenting exposures in particular work settings, determining
compliance/non-compliance with existing Federal or local standards or recommended
exposure limits, or trying to determine the source of a problem. Sampling parameters
that should be defined might include type of sample (area vs. personal), contaminant(s)
to be sampled, duration of samples, potential interferences and expected contaminant
concentrations (or contaminant concentration of interest). Once these parameters are
defined, then the proper analytical method and sampling media can be selected. Other
general information needed to plan a survey properly include the number of employees,
the sampling strategy plan (discussed later), process flow diagram, material safety data
sheets on all process materials, the physical states of the substances to be sampled,
and potential hazards involved in collecting and shipping the samples.
An accredited analytical laboratory should be used and it is essential to consult with the
analytical laboratory before sampling to ensure that the measurement methods available
can meet the defined sampling needs. This step should be an early part of survey
planning. The laboratory can also assist in choosing sampling media which are
compatible with the sampling needs and the measurement methods available. The

APPLICABILITY section of the individual methods in NMAM can be helpful in choosing
which of the available methods is best for a particular situation.
Whether through consultation with the laboratory or through reading the specific
measurement method, the sampling media will be specifically identified, e.g., pore size
and type of filter, concentration and amount of liquid media required, and specific type
and amount of solid sorbent (see Tables 1 and 2 for common types, characteristics and
behavior of solid sorbents*). If specific brand name products are called for, no
substitutions should be made. Most sampling media are well defined through research
and testing; deviations from specifications are undesirable. For example, most organic
contaminants are sampled with a dual section tube containing 1 00 mg front and 50 mg
backup sections of 20/40 mesh activated coconut shell charcoal. If larger mesh
charcoal or a different type of charcoal were to be used, the sampling capacity and
recovery efficiencies for the contaminant of interest might change from that which is
specified in the method.
The physical state of the contaminant(s) being sampled may also be a factor in
determining the media required. In the case of polyaromatic hydrocarbons (PAHs), for
example, the proper sampler consists of a membrane filter to trap particulate matter and
a solid sorbent tube to trap the vapors of certain PAHs so that total collection is
assured.
The sampling pump used to collect the sample must also be compatible with the
sampling needs and the media used. Specifically, the pump must be capable of
maintaining the desired flow rate over the time period needed using the sampling media
specified. Some pumps may not be able to handle the large pressure drop of the media.
This will be true for fine mesh (smaller than 40 mesh) solid sorbent tubes, small pore
size filters or when attempting to take a short-term sample on a sorbent tube of a
higher than normal pressure drop at a flow rate of 1 L/min or greater. As a rule of
thumb, all high flow pumps (1 to 4 L/min) can handle at least 3 kPa (12 inches of
water) pressure drop at 1 L/min for 8 hrs. Some pumps can handle up to 7.5 kPa (30
inches of water) pressure drop at flows up to 2 or 3 L/min. Most low flow pumps
(0.01 to 0.2 L/min) can handle the pressure drops of available sorbent tubes without
problems except that the nominal flow rate may decrease for certain models. All
pumps should be calibrated with representative sampling media prior to use. It is good
practice to check the pump calibration before and after use each day. As a minimum,
calibration should be done before and after each survey.

Table 1. Types and uses of solid sorbents [2]*.
Activated charcoal
By far the most commonly used solid sorbent. Very large surface area:wt. ratio.
Reactive surface, high adsorptive capacity. This surface reactivity means that
activated charcoal is not useful for sampling reactive compounds (e.g., mercaptans,
aldehydes) due to poor desorption efficiency. The high capacity, however, makes it
the sorbent of choice for those compounds which are stable enough to be collected
and recovered in high yield. Breakthrough capacity is a function of type (source) of the
charcoal, its particle size and packing configuration in the sorbent bed.
Silica gel
Less reactive than charcoal. Due to its polar nature, it is hygroscopic and shows a
sharp decrease in breakthrough capacity with increasing humidity.
Porous polymers
Lower surface area and much less reactive surface than charcoal. Adsorptive capacity
is, therefore, generally lower, but reactivity is much lower as well.
Ambersorbs
Properties midway between charcoal and porous polymers.
Coated sorbents
One of the sorbents upon which a layer of a reagent has been deposited. The
adsorptive capacity of such systems usually approaches the capacity of the reagent
to react with the particular analyte [3].
Molecular sieves
Zeolites and carbon molecular sieves which retain adsorbed species according to
molecular size. A limiting factor is that the water molecule is of similar size to many
small organic compounds and is usually many orders of magnitude higher in
concentration than the species of interest. This unfavorable situation may result in the
displacement of the analyte by water molecules. Drying tubes may be used during
sampling to eliminate the effects of humidity [4].
Thermal desorption
May contain several different sorbents in order to collect a wide range of different
chemicals [5]. These tubes are generally used in situations where unknown chemicals
or a wide variety of organics are present, e.g. in indoor environmental air quality
investigations. Analysis is often by gas chromatography/mass spectrometry (GC/MS).
*NOTE: Solid sorbents are used for the collection of vapors only. Aerosols are not
collected effectively by most sorbent beds, but may be collected by other components of
the sampler (e.g., a prefilter, or the glass wool plugs used to hold the sorbent bed in
place).

Table 2. Factors affecting the collection behavior of solid sorbents [2].
Temperature
Since all adsorption is exothermic, adsorption is reduced at higher temperatures.
Additionally, if there is a reaction between an adsorbed species and the surface or
between two or more adsorbed species (e.g., hydrolysis or polymerization), the rate
of such reactions increases at higher temperatures.
Humidity*
Water vapor is adsorbed by polar sorbents; their breakthrough capacity for the analyte
is thereby reduced. This effect varies from substantial for more polar sorbents, such
as charcoal and silica gel, to a smaller one for Ambersorbs and porous polymers.
Sampling flow rate*

Breakthrough volume of a solid sorbent bed tends to be smaller at higher sampling flow
rates, particularly for coated solid sorbents. For sorbents such as charcoal whose
breakthrough capacity is significantly reduced by high humidity, lower sampling flow
rates may actually result in smaller breakthrough volumes [6].
Concentration*
Breakthrough capacity (mg adsorbed) of solid sorbent bed increases (but breakthrough
volume (L of air sampled) decreases) as the concentration of contaminant in air increases
[8].
*NOTE: It is important to distinguish between equilibrium (saturation) adsorptive capacity

and kinetic (breakthrough) adsorptive capacity of the solid sorbent. Breakthrough capacity
is the important characteristic in actual sampling situations; it may be significantly affected
by sampling flow rate and relative humidity of the air being sampled and may be
significantly less than saturation capacity, which is not dependent on sampling flow rate
or relative humidity.
2. FIGURING SAMPLING PARAMETERS
Once the sampling media and measurement method are chosen, then the specific sampling
parameters need to be determined [7], For most methods, this will not pose a problem as
the flow rate recommended in the method can be used for the desired sampling period,
e.g., 1 to 3 L/min for 8 hrs for most aerosols or 10 to 200 mL/min for 8 hrs for most
sorbent tube samples. Generally, the parameters which must be considered are flow rate,
total sample volume, sampling time (tied into the two previous parameters), and limit of
quantitation (LOQ) (see Glossary of Abbreviations, Definitions and Symbols). Some of
these variables will be fixed by sampling needs, e.g., sampling time or by the
measurement method of choice (LOQ or maximum sampling volumes). The choice of
these variables can best be explained through the use of the following examples.

Examples:
a. Sampling for Gases and Vapors Using Solid Sorbents

Given parameters: Method 1501 for Styrene
Recommended Sample Volume: 5 L
Useful Range of the Method: 85 to 2560 mg/m3 (20 to 600 ppm)
OSHA PEL: 850 mg/m3 (200 ppm) - Ceiling
425 mg/m3 (100 ppm) - TWA
Recommended Flow Rate: 0.2 L/min
Breakthrough Time: 1 1 1 min @ 0.2 L/min and 1710 mg/m3
Breakthrough Capacity 38 mg
Suppose it is desired to determine both ceiling and TWA exposures of workers

exposed to styrene and the concentrations are unknown.
Ceiling Determination: If sampling were done at 0.2 L/min for 30 min and a total
sample volume of 6 L collected which is above the 5 L recommended sample volume,
would this a problem? Probably not. For instance, in the breakthrough test, a
concentration of 2 times the OSHA Ceiling Standard (1710 mg/m3) was sampled at
0.2 L/min for 1 1 1 min (22.2 L) before breakthrough occurred, collecting a total weight
of 38 mg of styrene. Of course, this test was conducted in a dry environment with
only styrene present. A safety factor of 50% should be allowed to account for
humidity effects. Thus, if sampling is done for about 55 min at 0.2 L/min, levels of
styrene up to 400 ppm could still be collected without sample breakthrough.
Also to be considered are the other organics present. If a concentration of 200 ppm
acetone exists in this environment, then an additional safety factor should be added.
An arbitrary 50% reduction in total sampling time or 28 min at 0.2 L/min might be
done. This is very close to the original sampling time of 30 min. With the safety
factors built in, collecting a 6-L sample should not be a problem. Alternately, the flow
could be reduced to 0.1 L/min and be well within the 5-L total volume.
TWA Determination: In this same situation, the goal is to collect 8-hr samples for
comparison to the 1 00 ppm TWA. If sampling was done at 0.05 L/min, then the total
sample volume would be 22.5 L, substantially above the 5-L recommended sample
volume. If the flow was dropped to 0.02 L/min, then the sample volume would be
9 L. This sample volume might be acceptable if the styrene concentrations are around
100 ppm and no other competing organics are present, e.g., acetone. However, the
safer approach would be to collect two consecutive samples at 0.02 L/min for 4 hrs
(total sample volume of 4.8 L each).
b. Pushing a Method to the Limit, Limit of Quantitation

Given Parameters: Method 1009 for Vinyl Bromide (VB)
Recommended Sample Volume: < 10 L @ 0.20 L/min or less
Working Range: 0.3 to 33 ppm (1 .3 to 145 mg/m3) for a 6-L
air sample; this equals 8 to 355 //g VB per
tube
Limit of Detection: 3 //g VB per tube

In this particular example, let us say that the object is to estimate exposure to vinyl
bromide down to 0.1 ppm (0.44 mg/m3), which is below the working range. In order
to collect 8 fjg of vinyl bromide (the limit of quantitation) at this concentration, 20 L
of air will have to be collected. This volume is substantially above the maximum
recommended sample volume of 10 L. Since the recommended sample volume is
generally a conservative value used to protect against breakthrough under worst case
conditions (i.e., high humidity and high concentrations), considerable leeway exists for
the size of the air sample. In this example, the 20-L air samples should be taken at
0.2 L/min or slower, and the possibility of breakthrough should be monitored by
observing the relative amounts of analyte on the backup sections of the samples.
The best approach is to consult with the analytical laboratory and then to take a
sufficient number of samples to determine the useful limits of the sampler in the
particular application. The presence of high relative humidity and other organic
solvents will severely reduce the number of active sites available on the sorbent for
collection of the contaminant of interest. In pushing a method to the limit, it is often
necessary to sample beyond the breakthrough volume, while observing recommended
maximum sampling flow rate, in order to obtain the sensitivity to determine the
concentration of interest. If this is done, then the risk must be accepted that the
method may not work outside the limits tested.
3. BULK SAMPLES
The addition of bulk samples can often make the difference between a successful or
unsuccessful sampling effort. This is especially true where there is mixed solvent
exposure or unknown dust exposure and for determining silica content of dusts. The
primary purpose of bulk samples is to provide the analytical laboratory with a large
enough sample for qualitative and sometimes quantitative analysis. The two major
types of bulk samples are bulk air and mass bulk (liquid or solid) samples.
a. Bulk Air Samples
Generally, a bulk air sample is defined as a large volume area sample collected for the
purpose of qualitative analysis. A good example is multiple solvent exposure where
the exact identity of the airborne solvents is unknown, e.g., painting operations. For
most organic solvents, a bulk air consists of a charcoal tube (or whatever sorbent is
called for) collected at 1 L/min for an hour or more. Although the sample is likely to
exhibit breakthrough, this does not matter since one is primarily interested in what
substances are present rather than their exact concentrations (the latter aim is
accomplished through the separate collection of proper samples). Any questions
concerning how or whether or not a bulk air sample is needed should be addressed to
the analytical laboratory prior to sampling. In the case of silica, either a bulk air or
solid bulk (e.g., a rafter sample) or both are suggested so that enough material will be
available to determine free silica content.

b. Bulk Liquids and Solids
Collection of bulk materials may be needed to establish the substances present in the
workplace and, in some cases, to establish the relative levels of certain substances
present in the raw material. A good example of the latter is the case of mixed solvent
exposure when determining if a certain contaminant of interest is present, e.g.,
benzene. In some cases, a list of 30 solvents may be present (from Material Safety
Data Sheets), but it is not certain which ones are present or in what proportions. This
example is also true for dusts, as was discussed previously for silica, or for metals
which may exist in trace quantities.
In choosing bulk samples, the end goal must be considered: qualitative and/or
quantitative analysis. In the case of a painting operation, it is preferred to have the
bulk samples separated by contaminants of interest, i.e., solvent fraction separate
from the pigment fraction. This allows the laboratory to analyze the different portions
of the paints without having to go through a lengthy separation process. In general,
the cleaner the bulk, the easier it will be for the laboratory to conduct the analysis.
In many cases, the industrial hygienist is interested in a "dirty" bulk. Any information
that can be given to the laboratory on what may or may not be present will help speed
up the analysis. Advance consultation with the laboratory is desirable.
In choosing bulk dust samples, the sample should be representative of the airborne
dust to which the workers are being exposed. Usually this is a settled dust sample
collected from rafters or near the workers' job site. In other cases, a process dust
sample is chosen to determine the composition of the material before it is airborne.
In cases where the choice is not clear, do not follow the adage that "more is better."
Bulk samples should be limited in number to optimize the laboratory's time. A good
approach, when in doubt as to what bulks are needed, is to collect several but to
allow the laboratory to analyze only those needed to answer questions as they arise.
When shipping bulks, care must be taken to preserve the integrity of the samples and
to follow established Department of Transportation (DOT) shipping regulations. Only
5 to 10 ml of the liquid or solid is needed, so keep bulk sample sizes small. In
general, leak-proof glass containers are best since they will not react with most
chemicals; however, polyethylene containers can be used in the majority of cases. A
convenient container is a 20-mL scintillation vial with PTFE-lined cap. Specific
chemicals for which polyethylene containers should not be used include aromatic
compounds, chlorinated hydrocarbons and strong acids. The lids of the containers
should be sealed with shrink bands or tape for further assurance against leakage.
These containers should be labeled as required by DOT under their regulations, 49CFR
Part 171-1 77. For most materials classified as "Flammable" or "Poisonous," amounts
up to 1 quart can be shipped by any carrier. Most bulk dusts are not covered by DOT
regulations. Specific restrictions and labelling requirements should be checked prior
to shipping any samples.
In the case of volatile bulk samples (and some air samples), consideration should be
given to shipping the samples on dry ice or with bagged refrigerant (e.g., "blue ice").
Again, check with the carrier you plan to use as there may be restrictions on the

amount of dry ice they will accept in a package (usually 5 pounds or less is
acceptable). Specific labels are usually required when dry ice is used.
4. BLANKS (See also page 10)
Certain numbers of blanks are required by the analytical laboratory for each set of samples
to be analyzed. The specific method being used should be consulted concerning the number
and type of blanks required. There are two types of sampler blanks: field and media
blanks. Field blanks are clean samplers taken to the sampling site, handled in every way
as the air samples, except that no air is drawn through them. Media blanks are simply
unopened, new samplers which are sent with the samples (these blanks are not usually
taken to the field). It is also recommended that additional blind field blanks be sent along
with the field samples, labelled as field samples, as a further check on the analysis. Blanks
are good insurance to deal with contamination, but the best approach is to avoid sample
contamination by being careful. The recommended practice for the number of field blanks
is two field blanks for each 10 samples with a maximum of 10 field blanks for each sample
set. Approximately five media blanks should also be included. This number should be
increased for media which are coated or impregnated with reagent. Again, consult the
specific method for the number and type of blanks as these numbers will vary.
Another frequently-used practice is to include blind spiked samples as a quality control

check of the analytical laboratory (see page 11). See the following chapter for a detailed
discussion of spiking procedures.
5. DIRECT-READING METHODS
The variety of types and costs of direct-reading methods available is large and expanding,
including detector tubes (both short- and long-term), aerosol monitors, integrating passive
monitors for certain gases and portable instrumentation for gas chromatography or infrared
spectroscopy [8]. Many direct-reading instruments now used for personal or area
measurements have evolved from laboratory or process control instruments [9].
Some of the considerations (i.e., specificity and sensitivity) for the use of direct-reading
methods for quantitative determinations are similar to those already given for classical filter
or sorbent methods. In many cases, direct-reading instruments, which are physically small
and portable, qualify as personal sampling devices.* These offer the additional advantages
over classical methods by reducing labor and analytical costs and may be the methods of
choice when instantaneous results are important, even at the expense of some degree of
sensitivity or specificity. In general, manufacturers' instructions should be followed in the
calibration and use of these devices. Due to the severe conditions to which direct-reading
instrument may be subjected, performance checks and preventive maintenance on a periodic
*NOTE: A portable instrument is defined as weighing less than 4.5 kg (10 Ibs.) and
powered by self-contained batteries [10]. For personal monitoring, the instrument
configuration should be such that the breathing zone can be monitored. Alarms, both
audible and visual, and hard-copy documentation are desirable.

basis or before each use are very important. Many direct-reading instruments are powered
by Ni-Cd batteries which can fail to provide a full charge over the full sampling period unless
frequently or fully discharged and recharged several times just prior to use. An additional
responsibility, that of field calibration of the direct-reading instrument, falls on the field
sampling personnel.
6. SAMPLING STRATEGY
To obtain the maximum amount of information during the course of a survey with a
minimum amount of samples, a statistical sampling strategy should be developed before
conducting any survey [1 1]. Several pieces of information must be known in advance to
plan a sampling strategy, including the size of the workforce to be sampled, the accuracy
of the sampling and measurement method to be used and the confidence one wishes to
have in predicting the exposure of the workforce.
For example, to determine with 90% confidence that at least one worker from a workplace
subgroup will be in the top 10% of the exposures occurring in the group, the number of
employees to sample would be chosen from Table 3. Other tables are given in the
publication for confidence limits of 95% and for the top 20% of exposures. Again,
judicious use of sampling statistics will optimize the number of samples needed.
Table 3. Minimum sample size (n) for including (@ 90% confidence level) at least one high
risk employee* [1 1].
Size of Employee Group (N):

1 23456789 10 11-12 13-14 15-17 18-20 21-24 25-2930-3739-4950 oo
Minimum Number of Measured Employees (n):

1 2 3 4 5 6 7 7 8 9 10 11 12 13 14 15 16 17 18 22
'Exposure in highest 10% of N.
7. SAMPLING TECHNIQUE
The following are suggested general techniques for active sampling using some of the more
common samplers. These instructions elaborate on those given in NMAM methods.
Consult individual methods for details of sample size.
a. Calibration of Personal Sampling Pumps
The accuracy of determination of the concentration of a toxic substance in air is no greater

than the accuracy with which the air volume is measured. Therefore, accurate calibration
of the airflow rate through the sampling train is necessary. The frequency of calibration
depends on the use, care and handling to which the pump is subjected. In addition, pumps
must be recalibrated if they have been abused and after each repair. Ordinarily, pumps

should be calibrated in the laboratory and the field, both before field use and after each field
survey.
The choice of a reference instrument will depend on where the calibration is to be

performed. For laboratory use, primary standards, such as a spirometer or soap-bubble
meter, are recommended [1,2]. Several electronic soap-bubble calibrators and one dry-cell
calibrator are commercially available as primary calibrators. Other instruments, such as a
wet-test, mass-flow or a dry-gas meter, may be used. The following instructions are for the
soap-bubble meter. If another instrument is used, equivalent procedures should be followed.
(1) Set up the apparatus as shown in Figure 1 .
(2) Make certain that the rechargeable batteries will power the pump for the
entire sampling interval by one of the following methods: 1 ) run the pump for
that length of time, checking for satisfactory operations; 2) test the battery
independently of the pump using a current capacity tester [12]. Fully recharge
the batteries.
(3) Turn the pump on and moisten the inner surface of the soap-bubble meter
with the soap solution. Draw bubbles upward until they travel the entire
length of the buret without breaking.
(4) Adjust the pump to the desired nominal flow rate. Check the water
manometer. The pressure drop across the sampler should not exceed 2.5 cm
Hg (13 inches) of water.
(5) Start a soap bubble in the buret and measure the time, with a stopwatch, that
it takes to traverse two calibration marks. For a 1 000-mL buret, a convenient
calibration volume is 500 mL. Repeat the determination at least twice more.
Average the results and calculate the flow rate by dividing the calibration
volume by the average time.
(6) Record the following data:

a. volume measured;
b. elapsed time;
c. pressure drop;
d. air temperature;
e. atmospheric pressure;
f. serial number of the pump;
g. pump model; and
h. date and name of operator.
(7) If the sampling pump used for sample collection uses a variable area flow
meter (rotameter) for flow rate indication, the calibrated flow rate must be
adjusted for the actual air pressure and temperature during sampling. The
expression for this correction is [13]:

V (Corrected volume, L) = Q t (PCTS/PSTC) 0.5
where: Q = indicated flow rate (L/min)

t = sampling time (min)
Pc = pressure during calibration of sampling pump
(kPa or other pressure units)
Ps = pressure of air sampled (same units as Pc)
Tc = temperature during calibration of sampling pump (K)
Ts = temperature of air sampled (K).
This correction is not used for non-rotameter sampling pumps.
Solid Sorbent
Tube
Cyclone in
; Holder
/ Assembly
Soap
Bubble
Meter f
(Inverted
1-Liter
Buret )
Personal
Sampling
Pump
Beaker
Figure 1 . Calibration Apparatus.
8/15/94 2Q NIOSH Manual of Analytical Methods

b. Sampling Instructions for Solid Sorbent Tube Sampler
Use these instructions for active personal sampling (i.e., pumped sample airflow) for
substances which are retained on solid sorbents such as activated charcoal, silica gel,
porous polymers, etc.
(1) Calibrate each personal sampling pump at the desired flow rate with a
representative solid sorbent tube in line (alternatively, use a flow restrictor to
provide a pressure drop equal to that of the average solid sorbent tube). Use a
bubble meter or equivalent flow measuring device.
(2) Break the ends of the solid sorbent tube immediately before sampling to provide
an opening at least one-half of the internal diameter at each end.
(3) Connect the solid sorbent tube to a calibrated personal sampling pump with
flexible tubing with the smaller sorbent section (backup section) nearer to the
pump. Do not pass the air being sampled through any hose or tubing before
entering the solid sorbent tube. Position the solid sorbent tube vertically during
sampling to avoid channeling and premature breakthrough.
(4) Prepare the field blanks at about the same time as sampling is begun. These field
blanks should consist of unused solid sorbent tubes from the same lot used for
sample collection. Handle and ship the field blanks exactly as the samples (e.g.,
break the ends and seal with plastic caps) but do not draw air through the field
blanks. Two field blanks are required for each 1 0 samples with a maximum of 1 0
field blanks per sample set.
(5) Take the sample at an accurately known flow rate as specified in the method for
the substance and for the specified air volume. Typical flow rates are in the range
0.01 to 0.2 L/min. Check the pump during sampling to determine that the flow
rate has not changed. If sampling problems preclude the accurate measurement
of air volume, discard the sample. Take two to four replicate samples for quality
control for each set of field samples.
(6) Record pertinent sampling data including location of sample, times of beginning
and end of sampling, initial and final air temperatures, relative humidity and
atmospheric pressure or elevation above sea level.
(7) Seal the ends of the tube immediately after sampling with plastic caps. Label
each sample and blank clearly with waterproof identification.
(8) Pack the tubes tightly with adequate padding to minimize breakage for shipment
to the laboratory. In addition to the sample tubes and field blanks, ship at least
six unopened tubes to be used as media blanks so that desorption efficiency
studies can be performed on the same lot of sorbent used for sampling.

(9) Ship bulk samples in a separate package from the air samples to avoid
contamination of the samples. Suitable containers for bulk samples are glass with
a polytetrafluproethylene (PTFE)-lined cap, e.g., 20-mL glass scintillation vials.
c. Sampling Instructions for Filter Sampler
Use these instructions for personal sampling of total (respirable and non-respirable)
aerosols. Methods requiring these instructions specify FILTER as the sampling
method. These instructions are not intended for respirable aerosol sampling.
(1) Calibrate the personal sampling pump with a representative filter in line using a
bubble meter or equivalent flow measuring device.
(2) Assemble the filter in the two-piece cassette filter holder. Support the filter by
a stainless steel screen or cellulose backup pad. Close firmly to prevent sample
leakage around the filter. Seal the filter holder with plastic tape or a shrinkable
cellulose band.
(3) Remove the filter holder plugs and attach the filter holder to the personal sampling
pump with a piece of flexible tubing. Clip the filter holder to the worker's lapel.
Air being sampled should not be passed through any hose or tubing before
entering the filter holder.
blanks should consist of unused filters and filter holders from the same lot used
for sample collection. Handle and ship the field blanks exactly as the samples,
but do not draw air through the field blanks. Two field blanks are required for
each 10 samples with a maximum of 10 field blanks per sample set.
(5) Sample at a flow rate of 1 to 3 L/min until the recommended sample volume is
reached. Set the flow rate as accurately as possible (e.g., within ± 5%) using
the personal sampling pump manufacturer's directions. Take two to four replicate
samples for quality control for each set of field samples.
(6) Observe the sampler frequently and terminate sampling at the first evidence of
excessive filter loading or change in personal sampling pump flow rate. (It is
possible for a filter to become plugged by heavy particulate loading or by the
presence of oil mists or other liquids in the air.)
(7) Disconnect the filter after sampling. Cap the inlet and outlet of the filter holder
with plugs. Label the sample. Record pertinent sampling data including times of
beginning and end of sampling, initial and final air temperatures, relative humidity
and atmospheric pressure or elevation above sea level. Record the type of
personal sampling pump used and location of sampler.
(8) Ship the samples to the laboratory as soon as possible in a suitable container
designed to prevent damage in transit. Ship bulk material to the laboratory in a
glass container with a PTFE-lined cap. Never store, transport or mail the bulk

sample in the same container as the samples or field blanks. In addition to the
samples and field blanks, ship five unopened samplers from the same lot for use
as media blanks.
d. Sampling Instructions for Filter + Cyclone Sampler
Use these instructions for personal sampling of respirable aerosols (ACGIH definition
[14]). Methods requiring these instructions specify CYCLONE + FILTER as the
sampling method.
(1 ) Calibrate the pump to the rate specified by the cyclone (1 .7 L/min for the 1 0-mm
nylon cyclone or 2.2 L/min for the Higgins-Dewell cyclone [14]), with a
representative cyclone sampler in line using a bubble meter or a secondary flow
measuring device which has been calibrated against a bubble meter. The
calibration of the personal sampling pump should be done close to the same
altitude where the sample will be taken.
(2) Assemble the pre-weighed filter in the two-piece cassette filter holder. Support
the filter with a stainless steel screen or cellulose backup pad. Close firmly to
prevent sample leakage around the filter. Seal the filter holder with plastic tape
or a shrinkable cellulose band.
(3) Remove the cyclone's grit cap and vortex finder before use and inspect the
cyclone interior. If the inside is visibly scored, discard this cyclone since the dust
separation characteristics of the cyclone might be altered. Clean the interior of
the cyclone to prevent reentrainment of large particles.
(4) Assemble the two-piece filter holder, coupler, cyclone and sampling head. The
sampling head rigidly holds together the cyclone and filter holder. Check and
adjust the alignment of the filter holder and cyclone in the sampling head to
prevent leakage. Connect the outlet of the sampling head to the personal
sampling pump by a 1-m piece of 6-mm ID flexible tubing.
(5) Clip the cyclone assembly to the worker's lapel and the personal sampling pump
to the belt. Ensure that the cyclone hangs vertically. Explain to the worker why
the cyclone must not be inverted.
blanks should consist of unused filters and filter holders from the same lot used
for sample collection. Handle and ship the field blanks exactly as the samples,
but do not draw air through the field blanks. Two field blanks are required for
each 10 samples with a maximum of 1 0 field blanks per sample set.
(7) Turn on the pump and begin sample collection. If necessary, reset the flow rate
to the pre-calibrated value, using the manufacturer's adjustment procedures.
Since it is possible for a filter to become plugged by heavy particulate loading or
by the presence of oil mists or other liquids in the air, observe the filter and
personal sampling pump frequently to keep the flow rate within ± 5% of the

target flow rate. The sampling should be terminated at the first evidence of a
problem.
(8) Disconnect the filter after sampling. Cap the inlet and outlet of the filter holder
with plugs. Label the sample. Record pertinent sampling data including times of
beginning and end of sampling, initial and final air temperatures and atmospheric
pressure or elevation above sea level. Record the type of personal sampling
pump, filter, cyclone used and the location of the sampler.
(9) Ship the samples and field blanks to the laboratory in a suitable container
designed to prevent damage in transit. Ship bulk samples in a separate package.
(10) Take two to four replicate samples for every set of field samples to assure quality
of the sampling procedures. The set of replicate samples should be exposed to
the same dust environment, either in a laboratory dust chamber or in the field.
The quality control samples must be taken with the same equipment, procedures
and personnel used in the routine field samples. The relative standard deviation,
sr, calculated from these replicates should be recorded on control charts and
action taken when the precision is out of control.
8. REFERENCES:
[1] First, M. W. "Air Sampling and Analysis for Contaminants: An Overview," pp 1-

19 in Air Sampling Instruments, 7th ed.. S. V. Hering, Ed., ACGIH, Cincinnati, OH
(1989).
[2] Melcher, R. G. "Laboratory and Field Validation of Solid Sorbent Samplers," pp
149-165 in Sampling and Calibration for Atmospheric Measurements, ASTM STP
957, J. K. Taylor, Ed., American Society for Testing and Materials, Philadelphia
(1987).
[3] Kennedy, E. R. "Sampling Reactive Materials," pp 175-188 in Advances in Air
Sampling, ACGIH, Lewis Publishers, Chelsea, Ml (1988).
[4] Langhorst, M. "A Hollow Fiber Device for Separating Water Vapor from Organic
Vapors." Am. Ind. Hyg. Assoc. J. 44:592 (1983).
[5] Hodgson, A. T., J. Binenboym, and J. R. Girman, "A Multisorbent Sampler for
Volatile Organic Compounds in Indoor Air," pp 143-157 in Advances in Air
Sampling, op.cit.
[6] Foerst, D. "A Sampling and Analytical Method for Vinylidene Chloride in Air,"
Am. Ind. Hyg. Assoc. J., 40, 888-893 (1979).
[7] Eller, P. M. "Operational Limits of Air Analysis Methods," Appl. Ind. Hyg. 1(2):
91-94 (1986).
[8] Nader, J. S., J. F. Lauderdale, and C. S. McCammon, "Direct-Reading Instruments
for Analyzing Airborne Gases and Vapors," pp 507-581 in Air Sampling
Instruments, op.cit.
[9] Assessment of Engineering Control Monitoring Equipment, Final Report, NIOSH
Contract 210-79-001 1, submitted by Enviro Control, Inc., available from NTIS,
Springfield, VA 22161 as Order Nos. PB83-1 52629 (Vol. 1) and PB83-1 52637
(Vol. 2) (June, 1981).

[10] Woebkenberg, M.L. NIOSH/DPSE, personal communication.
[11] Busch, K. A. and N. A. Leidel, "Statistical Models for Occupational Exposure
Measurements and Decision Making", pp 31 9-336 in Advances in Air Sampling,
op.cit.
[12] Kovein, R.J., P. A. Hentz, "A Digital Current Capacity Tester for Rechargeable
Batteries." Appl. Ind. Hyg. 3(21:51-54 (1988).
[13] Okladek, J., "An Overview of Flow Metering Devices", Amer. Lab. 20(1 ): 84-90
(1988).
[14] TLVs, Threshold Limit Values for Chemical Substances and Physical Agents and
Biological Exposure Indices for 1993-94, pp 42-45, ACGIH, Cincinnati, OH
(1993).
[15] Higgins, R. L. J. and P. Dewell, "A Gravimetric Size Selecting Personal Dust
Sampler", pp 575-586 in Inhaled Particles and Vapors II, C. N. Davies, Ed.,
Pergammon Press, Oxford (1967).

E. DEVELOPMENT AND EVALUATION OF METHODS
by Eugene R. Kennedy, Ph.D., Thomas J. Fischbach, Ruiguang Song, Ph.D.
Peter M. Eller, Ph.D., Stanley A. Shulman, Ph.D., NIOSH/DPSE and R. DeLon Hull,
Ph.D., NIOSH/DBBS
Contents: Page
1. Method Development 32
a. Preliminary Experimentation 33
b. Recovery of Analyte from Medium 33
c. Stability of the Analyte on the Medium 35
2. Method Evaluation 35
a. Feasibility of Analyte Generation 35
b. Capacity of the Sampler and Sampling Rate 37
c. Sampling and Analysis Evaluation 38
d. Sample Stability 39
e. Precision, Bias, and Accuracy 39
3. Field Evaluation 40
4. - Documentation 41
5. Appendix - Accuracy and Its Evaluation 41
6. References 44
Figure 1 . Nomogram Relating Accuracy to Precision and Bias 46
Table I Values of the Bias and the Precision Required to 47
Obtain Designated Accuracy in Percentage Units
1. METHOD DEVELOPMENT
The development and evaluation of analytical methods that are useful, reliable and accurate
for industrial hygiene monitoring problems require the application of some general
guidelines and evaluation criteria. The guiding objective in this work requires that, over a
specified concentration range, the method provide a result that differs no more than ±25%
from the true value 95 times out of 100. The application of consistent evaluation criteria
and guidelines is particularly important when methods are developed by different
individuals and organizations (e.g., contractors or outside laboratories) and compiled into
a single manual. Adherence to guidelines should minimize overlooking potential problems
in the methodology during its development, as well as provide cohesiveness and uniformity
to the method that is developed. This chapter provides an outline of a generalized set of
evaluation criteria prepared by NIOSH researchers for the evaluation of sampling and
analytical methodology [1].
In the development of a sampling and analytical method, there is a logical progression of

events that cover a search of the literature to gather pertinent information and the
preliminary experimentation for selection of analysis technique and sampling medium. To
initiate the development of a method, the identity of the analyte must be as fully defined
as possible. Physical and chemical properties of the analyte should be defined so that

procedures for proper handling and use of the analyte can be prepared. These also aid in
establishment of analyte purity. Potential sources of this information include chemical
reference books, health hazard evaluation reports, bulk sample analyses, material safety
data sheets, chemical process information, etc.
Since innovation is a key element in the sampling and analytical method development
process, detailed experiments for the initial development of the sampling approach and
optimization of the analytical procedure are better left to the discretion of the researcher.
During development, it should be recognized that appropriate, statistically designed
experiments will optimize the amount of information obtained. Therefore, consultation with
a statistician about appropriately designed experiments will be of value during this phase
of the research.
a. Preliminary Experimentation
Several key points, including calibration and selection of measurement technique and
sampling media, should be studied during the initial method development experiments. The
selection of sampling medium and procedure is a decision that usually is made early in the
method development process. The physical state of the analyte (i.e., gas, aerosol, vapor,
or combination thereof) plays an important factor in the selection of an appropriate
sampler. Analytes which can exist in more than one physical state may require a
combination of sampling media in one sampler for efficient collection [1]. Where possible,
commonly available and easily used samplers should be investigated initially. As the
preliminary testing of a sampling method progresses, further modification in the sampling
medium or sampler design may be required and may affect the measurement procedure.
Sampler design and media selection considerations should include U.S. Department of
Transportation regulations and restrictions for shipment back to a laboratory for analysis.
Since industrial hygiene analytical methods are geared toward measuring personal
exposure, the size, weight, and convenience of the sampler are important elements in
sampler design. The personal sampler should allow freedom of movement and should be
unobtrusive, unbreakable, and not prone to leakage. The pressure drop across the sampler
should not be so great as to limit sample collection times to * 10 h with personal sampling
pumps. For situations where only a short term sample will be required (i.e., 15 min for
ceiling determinations), this £ 10 h recommendations can be reduced to s 1 h. The use
of potentially toxic reagents should be avoided unless they can be used safely. Reagents
used should not pose any exposure hazard to the worker wearing the sampler or to the
industrial hygienist taking the samples.
b. Recovery of the Analyte from the Medium
During the course of method development experiments, the ability to recover the analyte
from the sampling medium should be determined. A suggested experiment to accomplish
this entails the fortification of sets of 6 samplers with amounts of analyte equivalent to
sampling concentrations of 0.1, 0.5, 1.0, and 2.0 (or higher) times the exposure limit for
a minimum of 4 h at the typical sampling rate used for that type of sampler. If the analyte

has a ceiling or short-term exposure limit, the amount of analyte fortified should be
adjusted for the shorter sampling time required for this type of exposure limit. If the
sampler has a backup section, then a like number of separate backup sections should be
fortified with amounts of analyte equivalent to 25% of the amount fortified on the front
sections of the samplers, since this amount has been used to characterize the breakthrough
limit of useful samples [2]. Samples (and backup sections) should be prepared for analysis
and analyzed according to previously determined procedures. Results of these analyses
should be expressed in terms of estimated percent recovery according to the following
formula:
Percent Recovery,,,. = (Amount of analyte found on sampler) x 10Q%

(Amount of analyte fortified on sampler)
After initial analyses of the samples, the samples should be reseaIed and analyzed on the
following day, if possible. If the sample workup procedure results in a solution of the
sample, these solutions should be recapped after the initial analysis if possible and
reanalyzed on the following day using fresh standards.
The recovery of the analyte should be calculated for the primary and backup media in the
sampler. Although complete recovery of the analyte from the sampler is most desirable,
at a minimum, the estimated recovery of the analyte from the primary collection medium
should be greater than or equal to 75% for concentrations equivalent to sampling 0.1 , 0.5,
1 .0, and 2.0 times the exposure limit. If recovery varies with analyte loading, results
should be graphed as recovery versus loading during calibration of the method, so that
appropriate correction can be made to sample results, as long as recovery is greater than
75% [3]. If estimated recovery does not exceed 75%, the method is not suitable for
monitoring at this limit.
Estimated recovery from any backup media should be noted so that appropriate corrections
can be applied if breakthrough of the sampler has occurred during sampling. The recovery
of the analyte from the medium in the backup section of a sampler may be different from
that of the front section, since the backup section of a sorbent-based sampler usually
contains only half of the sorbent of the primary section. If the same volume of desorption
solvent is used for both the primary and backup sections of the sampler, the desorption
equilibrium can be shifted, since the backup section is being desorbed by twice the volume
(i.e., on a mL solvent/mg sorbent basis) [4].
Reanalysis of the samples on the day after initial analysis indicates if immediate analysis
after sample preparation is required. Often when processing a large number of samples,
it may be necessary to prepare the samples for analysis as a batch. In these instances, the
last samples may not be analyzed for up to 24 h or more after preparation because of the
time required for analysis. If samples prepared for analysis exhibit time-dependent stability
after desorption, analyses must be conducted within acceptable time constraints. Analysis
and reanalysis results should agree within 5% of each other.

c. Stability of the Analyte on the Medium
An extension to the experiment described above may be performed to investigate potential

stability problems early in the experimentation. An additional set of fortified samples at
each of the 4 concentrations should be prepared and analyzed after 7-days' storage at
room temperature. Recovery should be similar to the above results within experimental
error. Discrepancies larger than those expected by experimental error indicate sample
stability problems that will need correcting by additional developmental effort (e.g.,
refrigerated storage). Comparison of results can be performed with statistical tests, such
as an analysis of variance (ANOVA) [5] test of the "Day" difference or a paired t-test [6]
of the means of the Day 1 and Day 7 storage results.
2. METHOD EVALUATION
After the initial development experiments for the method have been completed and a
method has been proposed, the sampling and analysis approach should be evaluated to
ensure that the data collected provides reliable, precise, and accurate results. Specifically,
the goal of this evaluation is to determine whether, on the average, over a concentration
range of 0.1 to 2 times the exposure limit, the method can provide a result that is within
±25% of the true concentration 95% of the time. For simplification, the true
concentration is assumed to be represented by an independent method. An experimental
approach for collecting the data necessary for this determination is described below.
As part of the evaluation of a method, the sampling of a generated atmosphere is needed

to more adequately assess the performance of a method [8,9,10]. This allows the
determination of 1) the capacity of the sampler; 2) the efficiency of analyte collection by
the sampler; 3) the repeatability of the method; 4) the bias in the method; 5) interferences
in the collection of the sample. Concentration ranges to be used in the evaluation of the
method should be based on several factors. These ranges, at a minimum, should cover
0.1 to 2.0 times the exposure limit. In some instances, higher multiples of the exposure
limit can be added if needed (e.g., 10 times the exposure limit). In situations where
multiple exposure limits (i.e., from different authorities) exist for an analyte, the lowest
exposure limit should be used to set the lower limit of the evaluation range (0.1 times
lowest exposure limit) and the highest limit used to calculate the upper limit of evaluation
range (2 times the highest exposure limit). Intermediate evaluation concentrations should
be within these exposure limits. The toxicity of an analyte (e.g., suspected
carcinogenicity) may indicate that a concentration lower than that calculated by the
exposure limit should be included in the measurement and evaluation ranges. Previous
monitoring information from other methods may indicate that typical concentrations of the
analyte may be below or above a concentration range based on the exposure limit. In this
case, this lower or upper level may be included in the method evaluation.
a. Feasibility of Analyte Generation
In order to provide a realistic test of the method under study, air concentrations covering
the range from 0.1 to 2 times the exposure limit of the analyte should be generated. The

generated atmospheres should be homogeneous in concentration and representative of the
environment encountered when sampling for the analyte in the workplace.
When attempting to generate a concentration of an analyte, the impact of environmental

conditions, such as temperature, pressure, humidity, and interferences, on sampler
performance and/or generation should be considered. The effect of elevated temperature
on the collection medium of a sampler may decrease the capacity of the sampler or may
decompose the analyte during generation and sampling. Reduced pressure may also reduce
the capacity of a sampler. High relative humidity in many instances has been observed to
reduce sampler capacity [3]. In other instances it has increased sampler capacity [11]. A
typical interference(s) should be generated along with the analyte to approximate a typical
workplace sampling environment.
Generation of particulate material can be extremely complex [12,13], especially if particles

of a required size range must be generated for the evaluation of a specified sampler inlet
design. The aerodynamic performance of the generator is a factor in the generation of this
type of atmosphere and should be evaluated carefully. Appropriate, independent methods
should be available to verify particle size, if this is a critical element in the generation.
The concentration of the generated atmosphere should be verified either by well

characterized gravimetric/volumetric means or by analysis of replicate samples (if possible)
by an independent method at each concentration used. Further details on this verification
are included in the literature [1]. A statistician should be consulted for advice on the
design and sample sizes to accomplish this validation. Ideally, the independent method
should not be biased and should provide an accurate estimate of the concentration
generated, assuming error is randomly distributed around the mean. Also the precision and
bias of the independent method should be homogeneous over the concentrations
investigated. (See Reference 1 for the definitions of these attributes.) In instances where
the concentration of the generator can be based only on calculations using flow rates in
the generator and the amount of analyte injected, the generation system should be well
characterized [1] so that analyte losses are minimized.
In some instances, generation of an analyte may be difficult and even hazardous. As an

alternative to direct generation in these cases, samplers may be fortified with an amount
of analyte expected to be sampled over a specified period of time at a specific flow rate.
When this is necessary, fortification of the sampler by vaporization of a known amount of
analyte onto the sampling medium is a more appropriate method, since this approach more
closely approximates a generated atmosphere. The alternative of direct application of a
solution of analyte onto the collection medium is less desirable but may be necessary in
some instances. After fortification, air, conditioned at both high and low humidity, should
be drawn through samplers at the flow rate and time period used in the calculations for the
amount of analyte expected to be collected. In the method report, the fact that samples
were not collected from a generated atmosphere should be discussed.

b. Capacity of the Sampler and Sampling Rate
To determine the applicability of the sampling method, the capacity of the sampler should
be determined as a function of flow rate and sampling time. This is particularly important
if the analyte has both a short-term exposure limit (STEL) and a time-weighted average.
Flow rates typical for the media selected should be used. These may range from 0.01 -
4 L/min, depending on sampler type. At extremely low flow rates (ca. 5 mL/min), the
effect of diffusion of the analyte into the sampler must be considered. Flow rates should
be kept at a high enough rate to prevent diffusion from having a positive bias in the
sampler. Sampling should be performed at three different flow rates covering the range
appropriate for the particular sampler type, unless the sampler is designed to operate at
only one flow rate. Sampling times should range from 22.5 min for STELs to 900 min (1 5
h) for time-weighted averages. Shorter sampling times (e.g., 7.5 to 22.5 min) may be used
for ceiling ® measurements. Flow rates should be based on accurately calibrated sampling
pumps or critical orifices. The amount of analyte collected at the lowest flow rate and
shortest sampling time should be greater than the limit of quantitation of the method. The
generated concentration used for capacity determination should be at least 2 times the
highest published exposure limit and verified by an independent method.
Sampling should be conducted at ambient, elevated (>35 °C), and low (<20 °C)
temperatures to assess the effect of temperature on sampling. To assess the effect of
humidity on capacity, sampling should be performed at both low and high humidities
U20% and :>80%, since both have been observed to affect capacity [11,3]. Triplicate
samplers at three different flow rates should be included to verify capacity at each of the
six different humidity and temperature levels. For samplers which contain backup sampling
media, only the front section of the sampler should be used. A means is required to
quantitate analyte in the effluent from the sampler. This may involve the use of a backup
sampler, continuous monitor or other appropriate means which can provide a measure of
analyte concentration in the sampler effluent (ca. 1 - 5% of the influent concentration).
If the mass of analyte found on a backup sampler totals 5% of the mass found on the front
sampler or if the effluent concentration of the sampler contains 5% of the influent
concentration, breakthrough has occurred and the capacity of the sampler has been
exceeded.
If the analyte is a particulate material and collected with a filter, the capacity of the filter
is defined by the pressure drop across the sampler or by the loading of the filter. For 37-
mm filter-based samplers, pressure drop should be less than 40 inches (101 6 mm) of water
for total loading less than 2 mg. Larger filters may tolerate higher loadings.
If the collection process is based primarily on adsorption, breakthrough time should be

proportional to the inverse of the flow rate [14]. This relationship can be checked by
plotting the 5% breakthrough time versus the inverse of the flow rate. If the resulting plot
is a straight line, then this relationship should hold for all flow rates in the flow rate range
studied. Some nonlinearity in the plot may be noted due to experimental variability and
assumptions made to simplify the relationship of breakthrough time and flow rate. Results
from these experimental trials should provide a prediction of the capacity of the sampler

at various flow rates and sampling times. If the flow rates and sampling times used in the
experiment do not provide for sufficient capacity, a lower flow rate range may have to be
studied and the experiment repeated.
With samplers which use reagents for collection of the analyte, the amount of the reagent
in the sampler will also be a limiting factor in the capacity of the sampler, based on the
stoichiometry of the reaction. Other factors, such as residence time in the sampler and
kinetics of reaction between analyte and reagent, may affect the capacity of this type of
sampler.
The combined temperature and humidity conditions that reduce sampler capacity to the
greatest extent should be used in all further experiments. The Maximum Recommended
Sampling Time (MRST) for a specific flow rate is defined as the time at which sampler
capacity was reached, multiplied by 0.667. This adds a measure of safety to this
determination. The relationship of breakthrough time with flow rate can be used to adjust
flow rates to optimize specific sampling times.
c. Sampling and Analysis Evaluation
To assess the performance of a method, certain additional experimental parameters should

be evaluated through a series of defined experiments. The effect of environmental
conditions (e.g., pressure, interferences) on sampling efficiency of the sampling medium
can be evaluated by a factorial design [15]. The temperature, relative humidity, flow rate,
and sampling times, determined in the experiment described above to have most severely
limited sampler capacity, should be used in these experimental runs. At a minimum, the
effect of concentration on method performance should be investigated. Three sets of 12
samples should be collected from an atmosphere containing concentrations of 0.1, 1.0,
and 2.0 times the exposure limit at the humidity determined above to have reduced
sampler capacity for the MRST determined in the preceding experiment. If the analyte has
a short-term or ceiling exposure limit in addition to a 8-hour time-weighted average, an
additional 1 2 samplers should be collected at the STEL or C limit for the recommended
sampling period at the appropriate flow rate. Potential interferences in the work
environment should be included in the generation experiments to assess their impact on
method performance. Concentrations up to 2 times the exposure limit value for the
interference should be included. Other environmental factors may be studied, but will
require a more comprehensive experimental design.
The effects of environmental conditions on analyte recovery should be assessed. A

factorial design can be used to evaluate these factors to determine which exert a
significant effect on analyte recovery. Those factors which are found to influence analyte
recovery should be investigated further to determine if their impact is predictable. If these
effects are not predictable, the utility of the method will be limited, based on the conditions
defined by this experiment. If only concentration is evaluated, the analyte recovery should
be the same at all concentrations after correctable biases have been included, such as
desorption efficiency.

d. Sample Stability
To assess sample stability, samples should be collected from a generated atmosphere,

stored under defined conditions (i.e., ambient or refrigerated, light or dark), and analyzed
at specified time periods. A concentration of 0.5 times the lowest exposure limit should
be sampled with 30 samplers for a minimum of 14 the MRST. The humidity and
temperature of the generator should be at the same level as defined in the sample capacity
experiment to reduce sample capacity. The samplers should be divided randomly into one
group of 12, one group of 6, and four groups of 3, with the group of 12 analyzed as soon
after collection as possible (Day 0). The group of 6 samplers should be analyzed after 7
days. The four remaining sets of 3 samplers should be analyzed after 10, 14, 21, and 30
days. The conditions of storage are determined by the nature of the analyte. If there is
an indication of analyte instability on the sampling medium, refrigeration of the samplers
may be required. However, storage for the first 7 days should be at room temperature.
Samples should be stable for a minimum of 7 days under ambient conditions to simulate
shipping to a laboratory for analysis. If the average analysis results of the samplers
analyzed on day 7 differs from the set analyzed on day 0 by more than 10%, the method
does not meet the sample stability criterion. Either additional precautions, such as
shipment on ice and refrigerator storage, may be required or the method may have to be
modified to address this problem. If a plot of recovery versus time indicates that recovery
decreased by more than 10% after the initial 7-day storage period, sample instability is a
problem. If samples need to be stored for longer periods, more restrictive storage
conditions are required. Remedial action, such as cold storage may solve this longer term
storage problem. After remedial precautions have been instituted in the method, the
sample stability of the method must be redetermined.
e. Precision. Bias, and Accuracy
Results from four sets of samplers used in the analyte recovery experiment, the sampling
and analysis experiments (e.g., the environmental parameters experiments), and the sample
stability experiment can be used for the estimation of precision, bias, and accuracy of the
method. A more exacting treatment of this is described elsewhere [1]. Sampler results
from the multi-level factorial design at the 0.1 , 1 .0, and 2.0 times the exposure limit value;
the sampler stability experiment (at 0.5 times the exposure limit); and the environmental
factors experiment are used in the calculations of method precision. The calculations for
the estimated method precision, SrT, have been described previously [1,16,17,18]. Before
obtaining a pooled estimate of method precision from the four sets of samplers listed
above, the homogeneity of the precision over the range of concentrations studied should
be checked using a test, such as Bartlett's test [1,16,17]. If the precision is not found to
be constant over concentrations, the sample set collected at 0.1 x exposure limit should
be removed and Bartlett's test recalculated. Homogeneity of the method precision at all
concentration levels is an assumption required to obtain pooled estimate of method
precision.
Bias is assumed to be homogeneous over the evaluation range. This assumption should
be tested by estimating the bias at each concentration and testing these for homogeneity

using the procedures described in the literature [1]. Method bias should be less than 10%.
A test for this is also described [18].
The bias and precision estimates can be used with the graph presented in Figure 1 or in
Table I to estimate accuracy [19]. The bias and precision estimates are plotted on the x-
and y-axes of the graph. The intersection of these points on the parabolic grid in the graph
can be used to estimate the accuracy of the method. This procedure gives an estimate of
method accuracy but does not yield the statistic required to test compliance of the method
with the ±25% accuracy criterion. Techniques for the latter determination are discussed
in the Appendix and elsewhere [1].
If the results for 4 concentrations fail the 25% accuracy criterion, then the set of samples
collected at 0.1 x exposure limit should be excluded from the data set. The pooled SrT and
the bias should be recalculated on this reduced data set before performing the accuracy
analysis described in the previous paragraph.
For the 12 samplers collected at the ceiling limit, the accuracy analysis described above
should be repeated using only the data collected at the ceiling limit.
3. FIELD EVALUATION
While field evaluation is not required in method evaluation, it does provide a further test
of the method, since conditions which exist in the field are difficult to reproduce in the
laboratory. Also unknown variables may affect sampling results when field samples are
taken. This type of evaluation is recommended to further study the performance of the
method in terms of field precision, bias, interferences and the general utility of the method.
Both the collection of area samples and personal samples should be included in the field
evaluation of the method. Area samples should provide an estimate of field precision and
bias. Personal samples may confirm these values and also provide a means to assess the
utility of the method. A statistical study design should be prepared, based on the
variability of the method and the statistical precision required for estimates of the
differences in analyte concentrations yielded by the independent method and the method
under evaluation [20].
If this type of statistically designed study is not feasible, a minimum of 20 pairs of samples
of the method under study and an independent method should be used for personal
sampling. Placement of the samplers on the workers should be random to prevent the
biasing of results due to the "handedness" of the worker. Workers sampled should be in
areas where both low and high concentrations of the analyte may be present.
As a minimum, sets of 6 area samplers paired with independent methods should be placed
in areas of low, intermediate, and high analyte concentration. If the atmosphere sampled
is not homogeneous, precautions may have to be taken to ensure that all samplers are
exposed to the same concentrations. This can be done by using field exposure chambers,
such as those described in the literature [21,22].

Field precision and bias of the area sampler results of the method under study should
compare with laboratory evaluation results, provided that precautions have been taken to
ensure that all samplers have been exposed to the same homogeneous atmosphere.
Differences in precision and bias should be investigated. Sources of variation should be
studied and corrections implemented where necessary. Evaluation of personal sampler
results should be done cautiously, since observable differences may be due to work
practices or other situations which are beyond the control of the method.
A field evaluation of a method also allows the developer of the method to determine its
ruggedness. Although this may be a subjective judgement, first hand experience with the
method in the field may suggest changes in the sampler or method that may make the
method more easily used in the field and less subject to variability.
4. DOCUMENTATION
Development and evaluation research on a sampling and analytical method should be

documented in a final report. The report should describe what was determined about the
method. If the results of the statistical analysis of the data indicate there is not 95%
confidence that the accuracy of the method is less than or equal to ±25%, the report
should state this fact. In some instances, the method may actually have an accuracy of
less than 25%, but a larger sample size must be used to prove this statistically (See
Appendix 1 of Reference 1).
The final report can be either a technical report or a failure report. The technical report
(acceptable method developed) documents the successful development of the method.
This report may be prepared in a format appropriate for submission to a peer-reviewed
journal for publication. The failure report (no acceptable method developed) documents the
research performed on an attempted method development for an analyte or analytes. The
report should describe the failure of the method, as well as other areas of the method
research that were successful. Recommendations to solve the failure of the method may
be included.
If an acceptable method is developed, a sampling and analytical method should be prepared

in appropriate format. The format of the resulting method should provide clear instructions
for the use of the method. Sampling, sample workup, and analysis procedures should be
clearly described. The necessary equipment and supplies for the method should be listed
clearly in the method. A summary of the evaluation of the method should be included, as
well as a discussion of method applicability and lists of interferences and related
references. As a check on the clarity and performance, new methods should be reviewed
and submitted to a user check (i.e., the method is used to analyze spiked or generated
samples of known concentration by someone other than the researcher who developed it)
and to a collaborative test, if feasible.
5. APPENDIX - ACCURACY AND ITS EVALUATION
In the development of a sampling and analytical method, one of the goals is to minimize
the measurement error to the lowest feasible and practical levels. It is assumed that all

feasible corrections to reduce error have been made in the laboratory experimentation
process. Method evaluation requires adequate characterization of the magnitude and
distribution of the uncorrectable error that cannot be prevented. One might consider a
hypothetical experiment in which a method is used repeatedly to measure the same
concentration, T, under the same conditions. These measurements would tend to exhibit
a pattern or statistical distribution, here assumed to be normal, with a mean, //, and
standard deviation, o. The distribution can be characterized in terms of two components:
its location relative to T, which is the systematic error termed bias (B), is given by (/7-T)/T;
and its spread, which is the random error termed imprecision (SrT), is given by O//y. The
bias and imprecision are used to determine the inaccuracy of the method but they are also
important characteristics of the error in and of themselves as will be discussed below.
Accuracy refers to the closeness of the measurements to T but it is defined in terms of the
discrepancy of the measurements from T. Inaccuracy (I) is defined as the maximum error,
regardless of sign, expressed as a percentage of T that occurs with a probability of 0.95.
Thus, an inaccuracy (or accuracy) of 20% means that on the average 95 of every 100
measurements will differ from T by no more than 0.2T. The accuracy criterion for single
measurements mentioned at the beginning of this chapter, often termed the "NIOSH
Accuracy Criterion," requires I to be less than or equal to 25%.
Accuracy, bias, and imprecision have the following relationship:
0.95 = 0| '~B l-d ~'~B | (1)
where <D(x) denotes the probability that a standard normal random variable is less than or
equal to x. A practically exact numerical solution to Equation (1) can be readily
programmed in PC-SAB* [23]. A DOS program, ABCV. EXE, is also available which solves
for I (denoted by A in the program), SrT (denoted by CV in the program), or B when the
values for the other two quantities are input. An estimate of I can be obtained in either
case by entering estimates of B and SrT. An approximate solution, which is accurate to
about 1.1 percent, is given as follows [19]:
I =1.57 (B+1)-SrT + ^(0.39 (B + 1)-SrT)2 + B2 for theoretical or true I

\ (2)
I = 1.57 (B+1)-SrT + ^(0.39 (B+1)-SrT)2 + B)2 for estimates of I
Also, the nomogram in Figure 1 can be used to solve for I or an estimate of I by entering
B and SrT or their estimates. Procedures for obtaining "best" single point and 95%
confidence interval estimates of B, and SrT and a 90% confidence interval estimate for I
are given in Kennedy et al [1].

The 90% confidence interval for I can be used to infer whether the method passes or fails
the 25% accuracy criterion for single measurements (AC) with 95% confidence as follows:
1) The method passes with 95% confidence if the interval is completely less than 25%.
2) The method fails with 95% confidence if the interval is completely greater than 25%.
3) The evidence is inconclusive if the interval includes 25% (there is not 95% confidence
that the AC is true or that it is false).
When researchers interpret the results from analyses of the type described above, it is
important to consider that most methods have many uses in addition to individual
measurement interpretation. Because accuracy is very important whenever any quantity
is to be estimated, the ideal ("other things being equal") is to use the most accurate
estimator regardless of its bias or imprecision. However, it is crucial to distinguish
between the accuracy of the source or "raw" measurements and that of the final
estimator, which might involve many intermediate analyses or operations. Unfortunately,
the most accurate input or raw measurements do not always produce the most accurate
final result unless the latter is a single measurement. The bias and imprecision of the
source measurements can be differentially affected by intermediate operations in producing
the final estimate. For example, if the final estimate is a function of a single average of
many source measurements, its bias is not affected by the averaging while imprecision is
reduced as a function of the square root of the number of measurements. Thus, a lower
biased method might be preferable to another even if the inaccuracy of the latter is less.
On the other hand, in comparative studies, the desired estimate is either a difference or
ratio of means of measurements in which there can be partial or complete cancellation of
the bias in the source measurements. Thus, the bias of the method used for the source
measurements may be of little importance. If there are several methods applicable for a
given user's project (regardless of whether all fulfill the AC for single measurements), the
analyst would be well-advised to consult with the user (preferably in advance of
measurement) to determine which of those methods would produce the most accuracy
for the final results or estimates needed by that particular user. Accuracy, bias, and
imprecision jointly form a complete or sufficient set for the efficient description of the
measurement error characteristic of any method.

6. REFERENCES
[I] Kennedy, E.R., T.J. Fischbach, R. Song, P.M. Eller, and S.A. Shulman. Guidelines
for Air Sampling and Analytical Method Development and Evaluation. NIOSH
Technical report, (DHHS (NIOSH) Publication No. 95-117) Cincinnati, OH: U.S.
Department of Health and Human Services, Public Health Service, Centers for
Disease Control and Prevention, National Institute for Occupational Safety and
Health, Division of Physical Sciences and Engineering, 1995.
[2] Streicher, R., E. Kennedy, and C. Lorberau: Strategies for the Simultaneous
Collection of Vapours and Aerosols with Emphasis on Isocyanate Sampling.
Analyst 7/5:89-97 (1994).
[3] Melcher, R., R. Langner, and R. Kagel: Criteria for the Evaluation of Methods for the
Collection of Organic Pollutants in Air Using Solid Sorbents. Am. Ind. Hyg. Assoe.
J. 35:349-361 (1978).
[4] Saalwaechter, A., C. McCammon, Jr., C. Roper, and K. Carlberg: Performance of

the NIOSH Charcoal Tube Technique for the Determination of Air Concentrations
of Organic Vapors. Am. Ind. Hyg. Assoe. J. 38:47 6-486 (1977).
[5] Posner, J., and J. Okenfuss: Desorption of Organic Analytes from Activated
Carbon. Am. Ind. Hyg. Assoe. J. 42:643-646 (1981).
[6] Box, G.E.P., W.G. Hunter, and J.S. Hunter: Statistics for Experimenters. New York,
NY: John Wiley & Sons, Inc., 1978. pp. 170-174.
NY: John Wiley & Sons, Inc., 1978. pp. 97-102.
[8] National Institute for Occupational Safety and Health: Gas and Vapor Generating
Systems for Laboratories by W. Woodfin (DHHS/NIOSH Publication No. 84-1 13).
Cincinnati, OH: U.S. Department of Health and Human Services, Public Health
Service, Centers for Disease Control and Prevention, National Institute for
Occupational Safety and Health, Division of Physical Sciences and Engineering,
1984.
[9] Nelson, G.O.: Controlled Test Atmospheres. Ann Arbor, Ml: Ann Arbor Science
Publishers, 1971.
[10] Nelson, G.O.: Gas Mixtures: Preparation and Control. Ann Arbor, Ml: Lewis
Publishers, 1992.
II 1] Cassinelli, M.E.: Development of a Solid Sorbent Monitoring Method for Chlorine

and Bromine in Air with Determination by Ion Chromatography. Appl. Occup.
Environ. Hyg. 6:215-226 (1991).

[12] Willeke, K., ed.: Generation of Aerosols and Facilities for Exposure Experiments.
Ann Arbor, Ml: Ann Arbor Science Publishers, Inc., 1980.
[13] Hinds, W.C.: Aerosol Technology. New York, NY: John Wiley and Sons, 1 982. pp.
379-395.
[14] Jonas, L.A., and J.A. Rehrmann: Predictive Equations in Gas Adsorption Kinetics.
Carbon 77:59-64. [1973].
NY: John Wiley and Sons, Inc., 1978. pp. 306-350.
[16] Anderson, C., E. Gunderson, and D. Coulson: Sampling and Analytical Methodology
for Workplace Chemical Hazards. In: Chemical Hazards in the Workplace, edited by
G. Choudhary. Washington, DC: American Chemical Society, 1981. pp. 3-19.
[17] Busch, K., and D. Taylor: Statistical Protocol for the NIOSH Validation Tests. In
Chemical Hazards in the Workplace, edited by G. Choudhary. Washington, DC:
American Chemical Society, 1981. pp. 503-517.
[18] National Institute for Occupational Safety and Health: Development and Validation
of Methods for Sampling and Analysis of Workplace Toxic Substances with a
Statistical Appendix by K. Busch by E. Gunderson, C. Anderson, R. Smith, and L.
Doemeny (DHHS/NIOSH Publication No. 80-133). Cincinnati, OH: U.S. Department
of Health and Human Services, Public Health Service, Centers for Disease Control
and Prevention, National Institute for Occupational Safety and Health, Division of
Physical Sciences and Engineering, 1980.
[19] Fischbach, T., R. Song, and S. Shulman: Some Statistical Procedures for Analytical
Method Accuracy Tests and Estimation. In preparation.
[20] European Committee for European Standardization (CEN), Workplace atmospheres -

Requirements and test method for pumped sorbent tubes for the determination of
gases and vapours (prEN 1076). Technical Committee 137, Working Group 2,
1993.
[21] Cassinelli, M.E., R.D. Hull, and P. A. Cuendet: Performance of Sulfur Dioxide Passive
Monitors, Am. Ind. Hyg. Assoe. J. 45:599-608 (1985).
[22] Kennedy, E.R., D.L. Smith, and C.L. Geraci, Jr.: Field Evaluations of Sampling and
Analytical Methods for Formaldehyde. In Formaldehyde - Analytical Chemistry and
Toxicology edited by V. Turoski. Washington, DC: American Chemical Society,
1985. pp. 151-159.
[23] SAS Institute, Inc.: SAS® Language Guide for Personal Computers, Release 6.03
Edition. SAS Institute, Inc. Gary, NC, 1988.

Figure 1 : Nomogram Relating Accuracy to Precision and Bias
JH
"
00

Table I: Values of the Bias (B) and the Precision (SrT) Required to Obtain Designated
Values of Accuracy (A) in Percentage Units.1
°rT
1%)
5 -3.5 0.9450'
6 -2.5 1.5589"
5 0.0 2.5511'
5 2.5 1.4829'
5 3.5 0.8811'
10 -7.5 1.6432'
10 -5.0 3.1999'
10 0.0 5.1022
10 5.0 2.8952"
10 7.5 1.4139'
15 -10.0 3.3777'
15 -5.0 6.3814
15 0.0 7.6530
15 5.0 5.7736
15 10.0 2.7636'
20 -10.0 6.7554
20 -5.0 9.4476
20 0.0 10.2043
20 5.0 8.5478
20 10.0 5.5271
25 -10.0 10.1284
25 -5.0 12.3869
25 0.0 12.7548
25 5.0 11.2072
25 10.0 8.2869
30* -15.04 10.7287

30* -7.5 14.5544
30* 0.0 15.3061
30* 7.5 12.5236
30* 15.0& 7.9299
35* -15.081 14.3038

35* -7.5 17.5897
35* 0.0 17.8574
35* 7.5 15.1353
35* 15.0& 10.5724
' Below the minimum attainable precision with a 5% pump correction.

$ Does not fulfill the Accuracy Criterion (±25% of the true value).
& Does not fulfill the bias criterion (±10%).
1 Note: the values shown in this table are population or theoretical values.

F. APPLICATION OF BIOLOGICAL MONITORING METHODS
by Alexander W. Teass, Ph.D., Raymond E. Biagini, Ph.D., D. Gayle DeBord, Ph.D., and
R. DeLon Hull, Ph.D., NIOSH/DBBS
1. INTRODUCTION
Biological monitoring is the assessment of worker exposure to a hazardous agent through

the measurement of a biomarker which results from contact with the agent. The biomarker
typically is the agent or its metabolite in a biological specimen derived from the worker;
examples are styrene in expired air, styrene in blood, and mandelic and phenylglyoxylic
acids (metabolites of styrene) in urine. The biomarker also can be an effect of the agent,
such as elevated levels of zinc protoporphyrin in blood, caused by exposure to lead.
Industrial hygiene professionals use biological monitoring to assess the risk to workers from
exposure hazards and to demonstrate the adequacy of control technologies and
intervention strategies.
This chapter provides an overview of the effective and appropriate application of the
biological monitoring analytical methods published herein. The analytical results should be
interpreted in light of what is known about the uptake, metabolism, and excretion of the
agent and the effect of the agent on the body. This chapter introduces these areas,
provides other considerations, and gives references to sources of more comprehensive
information on specific agents and situations. Additional resources on biological monitoring
include reviews [1-10], books [11-17], and methods and quality assurance manuals [18-
22].
2. GENERAL CONSIDERATIONS
A worker exposed to a chemical receives a dose of that chemical only if it is absorbed into
the body. Absorption can occur after dermal contact, inhalation, ingestion, or from a
combination of those routes. The extent of absorption from an exposure and the rate of
absorption depend on the properties of the chemical (especially its solubility in lipids and
water) and the route of exposure. Once absorbed, a chemical is distributed and partitions
into various tissues due to tissue variations in pH, permeability, etc. Highly water-soluble
chemicals may be distributed throughout the total body water, while more lipophilic
substances may concentrate in the body fat or other lipid-rich tissues, such as the brain.
The loss of chemical from the body can loosely be defined as elimination, which depends
on metabolism and excretion. Chemicals may be eliminated by numerous routes, including
fecal, urinary, exhalation, perspiration, and lactation. A chemical can be excreted from the
body without metabolism, in which case the parent compounds may be detectable in the
urine, breath, or fecal material. In other cases, the chemical may be metabolized through
oxidation, reduction, hydrolysis, or a combination of these processes, often followed by
conjugation with an endogenous substrate. Conjugation of a chemical or metabolite is a
pathway for excretion. The more important conjugation reactions include glucuronidation,
amino acid conjugation, acetylation, sulfate conjugation, and methylation. Metabolism and
excretion and the rates of metabolism and excretion can be affected by age, diet, general
health status, race, and other factors. In general, the metabolic products will be more

water soluble than the parent chemical. Where metabolism yields more than one product,
the relative amounts of each and the parent-metabolite ratios are affected by an
individual's general health status, diet, genetic makeup, degree of hydration, time after
exposure, and other factors. The kidney is the major organ of excretion and is the primary
route for water-soluble substances. These substances enter the urine by either glomerular
filtration, tubular secretion, or sometimes both mechanisms.
Biological monitoring has the potential to assess worker exposure to industrial chemicals
by all routes, including inhalation, skin absorption, and ingestion. Selection of an
appropriate biomarker for an exposure requires knowledge of the distribution, metabolism,
and excretion of the toxicant sufficient for selection of the proper compound to be
determined, biological medium to be sampled, and time for obtaining a specimen. Often,
most of the toxicological and pharmacological information available is from experimental
animals and, thus, not always directly applicable to humans.
Monitoring Goals. Air monitoring (or workplace environmental monitoring) and biological
monitoring have complementary goals and frequently are applied simultaneously in
industrial hygiene investigations.
1. Air monitoring. Air monitoring provides an estimate of the potential for exposure to
an agent. The presence of a health hazard is estimated by reference to
environmental exposure limits, such as the NIOSH recommended exposure levels, the
Occupational Safety and Health Administration (OSHA) permissible exposure levels,
or the threshold limit values (TLVs™) of the American Conference of Governmental
Industrial Hygienists (ACGIH). Compared with biological monitoring, air monitoring
offers advantages in certain situations. If the agent has acute toxic effects on the
respiratory tract or the eyes, air monitoring is the logical tool for controlling the
exposure. Air monitoring can be conducted continuously and, thus, can detect peak
exposures to dangerous chemicals.
2. Biological monitoring of exposure. A biomarker of exposure represents uptake of the

agent through all routes of exposure. Thus, compared to air monitoring, biological
monitoring offers a better estimate of the health risk in situations where routes of
exposure other than inhalation are significant.
a. The rate of disappearance of a biomarker determines the period of time after

exposure during which the level of the biomarker is still affected by the
exposure [7]. The levels of rapidly disappearing biomarkers primarily reflect
exposures during the previous several hours. On the other hand, biomarkers
which disappear over the course of several weeks reflect one, several, or
numerous exposure incidents occurring anytime during a period of several
weeks previous to the measurement.
b. Some toxicants accumulate in one or several parts of the body and are in
dynamic equilibrium with the sites of toxicity. In the case of polychlorinated
biphenyl (PCB), which accumulates in fatty tissue, the blood level of PCB
reflects the amount stored in the body.

c. When the site of critical action for a toxicant is known, the concentration of the
biomarker at that site can be used as a measure of the biologically effective
dose. Carboxyhemoglobin is such a biomarker for carbon monoxide poisoning.
In this case, the biomarker level is correlated with the health effect.
3. Biological monitoring of effect. This term is defined as monitoring reversible

biochemical changes resulting from exposures. The degree of change is less than
that which leads to injury and is not associated with a known irreversible pathological
effect [23]. Biological monitoring of effect is not health surveillance through which
individuals with early signs of adverse health effects are identified. Some examples
of biomarkers of effect are:
a. Zinc protoporphyrin in blood, levels of which increase with lead exposure,

because lead inhibits the biosynthesis of heme [24].
b. Protein and DNA adducts of aromatic amines in blood. These adducts can both
reflect the intensity of exposure and be correlated with the biologically effective
dose.
c. Antibodies produced against low-molecular-weight molecules [25]. Some

chemicals, while not immunogenic in their own right because of small size and
other limitations, may bind to constitutive polymers (such as host proteins) and
become immunogenic, causing the production of specific antibodies.
Alternatively, such exposures may lead to production of new antigenic
determinants, through nonadduct-forming reactions of the agent with selected
protein-carrier molecules. Antibodies can be made to these modified proteins
or to the parent hapten-conjugate [26]. In both cases, the antibodies may
remain in the human system much longer than the toxicant which initiated their
development.
Biological Matrices, The most common matrices usedJor biological monitoring are exhaled
air, blootr, and urine.
1. Monitoring exhaled air is limited to volatile chemicals. Exhaled air monitoring is not
suitable for chemicals inhaled as aerosols or for gases and vapors, which decompose
upon contact with body fluids or tissues, or which are highly soluble in water, such
as ketones and alcohols [3].
2. Blood is the medium which transports chemicals and their metabolites in the body.
Therefore, most biomarkers present in the body can be found in the blood during
some period of time after exposure [4].
a. A chemical in the blood is in dynamic equilibrium with various parts of the

body: the site of entry, tissues in which the chemical is stored, and organs in
which it is metabolized or from which it is excreted. Thus, the concentration
of a biomarker in the blood may differ between regions of the circulatory
system. This would be the case during pulmonary uptake or elimination of a

solvent, which would cause differences in concentration between capillary
blood (mainly arterial blood) and venous blood.
b. Two advantages of blood monitoring are: (1) The gross composition of blood
is relatively constant between individuals. This eliminates the need to correct
measured biomarker levels for individual differences. (2) Obtaining specimens
is straightforward and with proper care can be accomplished with relatively
little risk of contamination.
c. An important consideration in blood monitoring is that obtaining blood

specimens requires an invasive procedure and should be performed only by
trained persons.
3. Urine is more suitable for monitoring hydrophilic chemicals, metals, and metabolites
than for monitoring chemicals poorly soluble in water. The concentration of the
biomarker in urine usually is correlated to its mean plasma level during the period the
urine dwells in the bladder [5].
a. In some instances the urine concentration is affected by the amount of the

biomarker stored in the kidneys. Examples are cadmium and chromium.
b. The accuracy of the exposure estimate, using urine monitoring, depends upon
the sampling strategy. The most influential factors are time of collection and
urine output.
c. Measurements from 24-hour specimens are more representative than from spot
samples and usually correlate better with intensity of exposure. However,
collection, stabilization, and transportation of 24-hour specimens in the field are
difficult and often not feasible.
3. PRACTICAL CONSIDERATIONS
Selection of Methods. The occupational health professional and the laboratory scientist
should decide on appropriate methods so that the test results are interpretable to the
exposure situation. The following issues should be addressed:
1. The goal of the biological monitoring method should be consistent with the goal of the
industrial hygiene investigation. Is the goal to measure exposure or a health effect
related to the exposure?
2. The method needs to be evaluated for the required specificity and possible
interferences. If interferences from diet, drugs, alcohol, disease states, or other
workplace chemicals or agents exist, they must be accounted for.
3. The method should have a sufficiently low limit of detection to differentiate exposed
from nonexposed workers. A method developed when biological monitoring reference

levels were higher may be inadequate for measuring exposures at and below the
current guidelines.
4. Limitations of the sample matrix and its affect on the analysis need to be assessed.
In general, blood serum and urine specimens require different sample preparations and
may require separate methodologies to eliminate matrix effects.
5. Because of sample instability, some methods may be impractical or not feasible.
6. The method should have guidelines for interpretation of collected data. Such
guidelines are discussed in Interpretation of Results below.
7. To minimize the risk of harm to workers, when two biological monitoring methods will
provide the same information, the less invasive method should be used. Thus,
methods monitoring urine or exhaled breath are preferred over those monitoring blood.
Sampling Strategy. Strict attention to specimen handling and collection is essential for
quality data. The analytical laboratory should be consulted for sampling instructions.
Analytical methods should provide specific directions on the collection, storage, and
transportation of specimens to the laboratory. Adherence to these directions is of the
utmost importance to ensure sample integrity.
1. Timing of specimen collection should be appropriate. The method should include

instructions for the timing of specimen collection, that is, whether specimens should
be obtained during the work shift, at the end of the shift, or at some other time during
the work week. The longer the half-life of the xenobiotic, the less critical is the timing
of the collection [1 1].
2. The baseline of a biomarker should be evaluated when the toxicant accumulates in the
body, as do cadmium, lead, and polychlorinated biphenyl [1 1]. The baseline should
also be assessed, if there is large intersubject variability in the population, such as
when pseudocholinesterase in plasma is measured.
3. Care should be taken not to contaminate the specimen with either chemicals or
bacteria.
4. The proper preservative (for urine or blood samples) or anticoagulant (blood) should be
used, if appropriate.
5. Stability of the biomarker is assured through proper storage and shipment of the
specimen to the laboratory and proper storage by the laboratory.
Correction of Urinalysis Data for Dilution. Determination of biomarkers in individual urine

samples is confounded by urine dilution, which can vary substantially with fluid intake and
physical work load. In practice, this effect of urine dilution is reduced by adjusting the
measured concentration of the biomarker to a normal value [5,27], such as:

1. Specific gravity. This adjustment is made by multiplying the measured concentration
of the biomarker by the ratio of [(1.024 - 1)/(sp.g. - 1)], where sp.g. is the specific
gravity of the urine sample and 1 .024 is the assumed normal specific gravity value.
2. Urine output. The measured concentration of the biomarker is multiplied by the ratio
R/0.05, where R is the output for the sample in liters per hour. The urine output for
the sample is computed from the volume (liters) of the sample and the time (hours)
elapsed since the last voiding. The adjustment is to a mean output of 0.05 L/h.
3. Creatinine concentration. This is the most frequently used adjustment. Creatinine is

excreted by glomerular filtration at a relatively constant rate of 1 .0-1 .6 g/day. Urinary
creatinine concentration can be determined by spectrometric or kinetic methods based
on the Jaffe" alkaline picrate reaction, enzymatic methods, and methods based on mass
spectrometry and liquid chromatography [28]. The adjusted value is the quantity of
the biomarker per unit quantity of creatinine.
There are other considerations to be taken into account when adjusting urinalysis data for
dilution:
1. Adjustment to the creatinine level is not appropriate for compounds, such as methanol,
that are excreted in the kidney primarily by tubular secretion.
2. Since the mechanism of excretion of a biomarker can be altered if the urine is very
concentrated or very dilute, measurements on samples, having creatinine
concentrations outside the range 0.5 to 3 g/L or having specific gravities outside the
range 1 .010 to 1 .030, are unreliable [5].
3. Adjustment for creatinine concentration, while correcting for dilution, introduces

additional variation, which must be considered when the data are evaluated. Among
the factors affecting the rate of creatinine excretion are the muscularity of the subject,
physical activity, urine flow, time of day, diet, pregnancy, and disease [27].
Quality Assurance. Good data require the utilization of an effective quality assurance
program. In 1992, regulations implementing the Clinical Laboratory Improvement
Amendments (CLIA) of 1988 were published by the Health Care Finance Administration
and the Public Health Service to ensure that analysis of human specimens was done
accurately and under good quality control procedures [29]. Any analysis of human
specimens that can be used by a health care practitioner to assess the health of the
individual or used in the diagnosis, prevention, or treatment of disease or impairment falls
under the CLIA guidelines. Since, as a minimum, biological monitoring data are used to
prevent occupational disease or impairment, CLIA guidelines apply. Key components of
the CLIA quality assurance program include:
1. Strict management of specimen collection, handling, storage, and transportation, thus

ensuring sample integrity
2. Thorough verification of a method by the laboratory before use on field specimens

3. High level of analytical quality control
4. Participation in proficiency testing programs, if available
5. Documented instrument evaluation and maintenance programs
6. Investigation of communication failures and complaints
7. Documentation of performance and corrective actions
Ethical Considerations. There are several ethical issues that must be considered before
initiating a biological monitoring procedure [30, 31]:
1. Method should be appropriate for the requirements of the investigation.
2. Procedures should not threaten the health of the participant.
3. Risk of using invasive methods must be justified by the benefits.
4. Informed consent from the participant is required. This consent must be given when
the participant feels no fear of reprisals, if consent is withheld.
5. Results should be kept confidential and shared only with the occupational health
professional and the participant.
Laboratory Safety. When dealing with human specimens, a biosafety program is essential.
Pathogens such as hepatitis B and human immunodeficiency virus (HIV) may be present
in blood, saliva, semen, and other body fluids. Transmission can be by an accidental nick
with a sharp object; exposure through open cuts, skin abrasions, and even dermatitis or
acne; and indirectly through contact with a contaminated environmental surface. There
are five major ways to reduce the potential for exposure to biological pathogens [32, 33]:
1. Engineering controls, which include mechanical or physical systems used to eliminate

biological hazards, must be available. These are items such as biosafety cabinets or
self-sheathing needles.
2. Employee work practices are essential to minimize exposure to pathogens. Good

personal hygiene procedures and avoidance of needle recapping can lessen exposure
to pathogens.
3. Personal protective equipment, such as gloves and masks, should be used when
necessary.
4. Good housekeeping procedures, which involve cleanup of the work area, are essential
to avoid contamination of the laboratory.

5. Employees, who have been identified as potential exposure candidates, should be
vaccinated for hepatitis B.
Universal precautions that take into account the above five measures should be practiced
with every biological sample received. It is not possible to know if a particular sample may
contain pathogens; therefore, each sample should be treated as if contaminated.
4. INTERPRETATION OF RESULTS
A biological monitoring analytical result is a determination of the level of the biomarker in

the biological matrix from which the sample was taken, at the time it was taken.
Extrapolation from that datum to insight on the exposure of the worker requires knowledge
of how the human body responds to the agent.
1. Exposure can be estimated when a quantitative relationship between environmental

level and biomarker level has been demonstrated.
2. Health risk can be estimated when a quantitative relationship between a health effect
and biomarker level has been demonstrated.
3. Where knowledge of a biomarker is limited, one can only infer from its presence above
the background level that exposure has occurred.
Reference Levels. For a number of agents there exist published reference levels, termed
"biological action levels" by the World Health Organization [18], which serve as guidelines
for interpreting biological monitoring data. In the absence of published biomonitoring action
levels, biomarker levels indicating occupational exposure have been inferred by comparison
with the normal background levels of the biomarker.
1. Biomonitoring action levels vary in their derivation, some being from correlations with
exposure, others with health effects. These reference levels should be used only when
one has full understanding of their derivation. Sources of biomonitoring action levels
include:
a. Biological Exposure Indices (BED adopted by the American Conference of

Governmental Industrial Hygienists (ACGIH) [34];
b. Biological Tolerance Values for Working Materials (BAT) published by the

Deutsche Forschungsgemeinschaft's (DFG) Commission for the Investigation
of Health Hazards of Chemical Compounds in the Work Area [35];
c. Lauwerys' and Hoet's "Summary of Recommendations" in Industrial Chemical

Exposure. Guidelines for Biological Monitoring [11];
d. Occupational Safety and Health Administration (OSHA) standards [36, 37].

2. When biomarker data are available for exposed and nonexposed populations that are
otherwise similar, the upper limit of the range for the nonexposed population may
serve as a reference level. Levels of biomarker significantly above that limit suggest
occupational exposure to the agent. For those biomarkers for which there is no
measurable background level in nonexposed humans, this reference level is effectively
the detection limit of the analytical method. In any case, levels of the biomarker above
the reference level suggest there was occupational exposure, but give no information
on the potential health effect.
Variability. Biological monitoring data are subject to a number of sources of variability [2],
including:
1. Rates at which an agent is taken up by the body, metabolized, and excreted. These
vary from person to person and are affected by the person's age, sex, and physical
workload.
2. Route of exposure. For example, absorption through the lungs is much faster than
adsorption through the skin. Thus, the appearance and elimination of a biomarker will
be slower if the agent entered through the skin. If the biomarker is rapidly excreted,
the optimum timing for collection of biological samples will be different for the two
routes of entry.
3. Fluctuation in environmental exposure. Such fluctuations will be tracked by the levels

of rapidly eliminated biomarkers, those reflecting exposure of the immediately previous
several hours.
4. Personal protective equipment worn and a person's work practices.
5. Existence of a biomarker in both a free and a conjugated form, the relative proportions
of which can vary substantially from person to person. For example, aniline is present
in urine as both the free amine and as acetanilide, its acetyl derivative. Some persons
are genetically predisposed to excrete primarily free aniline; while others, primarily,
acetanilide.
6. Concurrent exposure to several agents that compete for the same biotransformation
sites in the body. This may lead to altered metabolism and excretion, which would
change the relationship between exposure or health effect and the level of the
biomarker [8].
7. Concurrent exposure to several agents, which are metabolized to the same biomarker.
This frustrates the interpretation of the biological monitoring data. For example,
trichloroacetic acid is a biomarker for trichloroethylene, 1 ,1 ,1-trichloroethane, and
perchloroethylene.
8. Consumption of alcoholic beverages [9], since ethanol is metabolized by three

pathways used for metabolism of other organic agents. After consumption of one
drink, the ethanol concentration in the blood is about 1000 times higher than from a

normal occupational exposure and may affect significantly the metabolism of industrial
chemicals.
9. Medications [10], health, and diet.
Because of the variability of biomarkers, judgments on the exposure or health risk of

workers frequently cannot be made based on a single determination. It may be necessary
to base conclusions on the data for a group of similarly exposed workers or on data from
a series of samples from a single worker.

5. REFERENCES
[I] Aitio, A. Biological Monitoring Today and Tomorrow, Scand. J. Work Environ.
Health, 20 special issue, 46-58 (1994).
[2] Droz, P. O. Biological Monitoring I: Sources of Variability in Human Response to

Chemical Exposure, Applied Industrial Hygiene, 4(1), F-20 (1989).
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II: Measurements in Exhaled Air, Applied Industrial Hygiene, 4(2), F-10 (1989).
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III: Measurements in Blood, Applied Industrial Hygiene, 4(3), F-1 1 (1989).
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IV: Measurements in Urine, Applied Industrial Hygiene, 4(4), F-1 6 (1989).
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Absorption, Applied Industrial Hygiene, 4(8), F-1 4 (1989).
[7] Droz, P. O., V. Fiserova-Bergerova (Thomas). Biological Monitoring VI:

Pharmacokinetic Models Used in Setting Biological Exposure Indices, Applied
Occupational & Environmental Hygiene, 7(9), 574 (1992).
[8] Ogata, M., V. Fiserova-Bergerova, P. O. Droz. Biological Monitoring VII:

Occupational Exposures to Mixtures of Industrial Chemicals, Applied Occupational
& Environmental Hygiene, 8(7), 609 (1993).
[9] Fiserova-Bergerova, V. Biological Monitoring VIM: Interference of Alcoholic

Beverage Consumption with Biological Monitoring of Occupational Exposure to
Industrial Chemicals, Applied Occupational & Environmental Hygiene, 8(9), 757
(1993).
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Industrial Chemicals, Applied Occupational & Environmental Hygiene, 9(5), 341
(1994).
[II] Lauwerys, R. R., P. Hoet. Industrial Chemical Exposure. Guidelines for Biological
Monitoring, Ch. 1, Lewis Publishers, Ann Arbor, Michigan (1993).
[12] Biological Monitoring of Exposure to Chemicals. Organic Compounds, M. H. Ho, H.

K. Dillon, Eds., John Wiley & Sons, Inc., New York (1987).
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Eds., John Wiley & Sons, Inc., New York (1991).

[14] Biological Monitoring and Surveillance of Workers Exposed to Chemicals, A. Aitio,
V. Riihimaki, H. Vainio, Eds., Hemisphere Publishing Corporation, Washington, D.
C. (1984).
[15] Biological Monitoring for Pesticide Exposure. Measurement, Estimation, and Risk
Reduction, R. G. M. Wang, C. A. Franklin, R. C. Honeycutt, J. C. Reinert, Eds., ACS
Symposium Series 382, American Chemical Society, Washington, D. C. (1989).
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New York (1993).
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1992, Kyoto, Japan, M. Ikeda, Ed., International Archives of Occupational and
Environmental Health, 65(1 Supplement) (1993).
[18] World Health Organization. Guidelines on Biological Monitoring of Chemical

Exposure at the Workplace, Volumes 1 & 2, WHO, Geneva (in press).
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Materials, Volumes 1-4, J. Angerer, K. H. Schaller, VCH Verlagsgesellschaft mbH,
Weinheim (1985-1994).
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Hazardous Substances, T. J. Kneip, J. V. Crable, American Public Health
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Publications, Davis (1980).
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Assurance Manual for Industrial Hygiene Chemistry," AIHA Laboratory Analysis
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Exposures in the Workplace. Guidance Note EH56 from Environmental Hygiene
Series HMSO, London (1 992) in World Health Organization. Guidelines on Biological
Monitoring of Chemical Exposure at the Workplace, Volumes 1 & 2, WHO, Geneva
(in press).
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Communities, Luxembourg (1983).

[25] Biagini, R. E., S. L. Klincewicz, G. M. Henningsen, B. MacKenzie, J. S. Gallagher,
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Bernstein, D. I. Bernstein. Immune Responses of Cynomolgus Monkeys to Phthalic
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to Assess Chemical Exposure with Emphasis on Creatinine Adjustments: A Review,
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G. AEROSOL PHOTOMETERS FOR RESPIRABLE DUST MEASUREMENTS
by Paul A. Baron, Ph.D., NIOSH/DPSE
Contents: Page
1 . Introduction 62
2. Principles of Operation 63
3. Sampling Considerations 64
a. Safety 64
b. Applications 64
4. Data Acquisition and Treatment 65
a. Calibration 65
b. Operation 65
5. Instruments 66
6. References 67
1. INTRODUCTION
This discussion will cover direct-reading aerosol photometers that are self-contained
(battery-operated) and portable (can be used while carried by one person). There is a
variety of direct-reading aerosol monitors using light-scattering detectors. These
instruments generally have advantages in reduced weight, improved ruggedness, and
continuous readout when compared with other direct-reading aerosol monitors. These
instruments can be used to provide accurate dust concentration measurements as
described below, though in most situations they are most useful for approximate or
relative concentration measurements. Their principle advantage is that of providing real
time information.
An aerosol is a group of particles suspended in the air. Aerosols can be introduced into
the body primarily through the respiratory system. Total dust measurements indicate
concentrations that can enter the nose and mouth of a worker as well as that which can
settle on the skin while the respirable fraction of dust is that portion which can reach the
lower or gas exchange part of the respiratory system.
The respirable fraction of the dust mass has been defined for sampling purposes by the
American Conference of Governmental Industrial Hygienists (ACGIH) as that fraction
collected by a device with a penetration curve (Figure 1) fitting the following points [1]:
Particle Size, urn * % Passing Selector

0 100%
1 97
2 91
3 74
4 50
5 30
6 17
7 9
8 'aerodynamic 5
10 diameter 1

There are other definitions of respirable dust [2,3,4] as well as empirical data indicating
deposition efficiency of dust in the respiratory system. Historically, the most commonly
used respirable dust sampling device in the U.S. is the 10-mm nylon cyclone. At a flow
rate of 1.7 L/min, the cyclone passes close to 50% of 4-micrometer aerosol particles.
However, it has been shown that the 1 0-mm cyclone has a somewhat sharper cutoff than
the ACGIH curve and, with certain size distributions, may introduce a bias with respect
to the ACGIH definition [5].
Aerosols are frequently classified according to their physical form and source. Aerosols
consisting of solids (e.g., coal, wood, asbestos) are designated dusts. Aerosols consisting
of liquid (e.g., oil, water, solvents) droplets are called mists. Submicrometer aerosols that
are formed from condensation or combustion processes are generally called fumes or
smokes. Some of these aerosols have a significant vapor pressure and will evaporate
when aged. The direct-reading photometer may detect these high vapor pressure aerosols
while the reference method for respirable dust (Method 0600) will not.
2. PRINCIPLES OF OPERATION
Light-scattering aerosol monitors (also called nephelometers or aerosol photometers)

operate by illuminating aerosol passing through a defined volume and detecting the total
light scattered by all the particles in that volume (Figure 2). This discussion will not
include single-particle counting photometers that are used to measure lower
concentrations such as in clean rooms and give information about individual particles.
However, there is an instrument listed below (Portable Dust Monitor from A. P. Buck, Inc.)
that uses single-particle counting to estimate mass concentration.
The light source of a photometer can be monochromatic such as a light-emitting diode or

laser or a broad-wavelength light source such as a tungsten filament lamp. The choice of
light source in different instruments has more to do with the ability to control the light
output level than with the wavelength of the output. The detector is generally a solid
state photodiode but can be a photomultiplier tube. The detection geometry varies from
one instrument to another. These instruments generally use a forward-scattering
geometry (i.e., less than 90°). The angle of scattering (theta) is defined with respect to
the beam of light passing through the aerosol in the detection volume. The smaller the
value of theta the more the detection is weighted toward larger particles.
The amount of light scattered by a particle into the detector is a complex function of the
particle size, shape and refractive index. For spherical particles of known refractive index
the instrument response can be calculated. However, in general, calibration must be
carried out experimentally. An example of instrument response as a function of particle
size for spherical particles of two different refractive indices is shown in Figure 1 . It can
be seen that there is a peak at approximately 0.6 mm and that there is a drop in
instrument response to larger particles. For comparison, the ACGIH definition of respirable
dust is superimposed on Figure 1 [6]. It can be seen that the size dependent response of
the photometer is somewhat similar to the desired response for a respirable sampler.
For quantitative measurements, it is necessary to calibrate with an aerosol similar in

refractive index and particle size to the one being measured. This is because aerosols with

different refractive indices can produce photometer responses differing by more than a
factor of ten. Since these instruments have specific size-dependent response to particles,
the size distribution of dust particles is also important in evaluating the mass response of
the instrument for a specific dust.
3. SAMPLING CONSIDERATIONS
Some portable photometers have been designed for intrinsic safety, i.e., for use in
potentially explosive atmospheres. This must be checked with the manufacturer to
ensure that a specific instrument meets the appropriate intrinsic safety requirements
(e.g., Underwriter's Laboratory or Mine Safety and Health Administration).
b. Applications
Photometers generally cannot be used to discriminate between different types of

aerosol. The instrument will respond to all types of aerosol present simultaneously in
the detection volume. Therefore, measurement of a small amount of a specific aerosol
in the presence of a large amount of interfering dust is not feasible with a photometer.
For example, if lead fume must be measured in the presence of a large percentage of
road dust, the photometer would not be the instrument of choice. However if lead
fume were the major aerosol component, use of the photometer would be appropriate
for monitoring lead exposure.
At high humidity, water droplets can exist in the air for extended periods of time and
be detected by a photometer. These droplets can change size rapidly in response to
small changes in humidity. Therefore, care should be taken when measuring aerosols
near water sprays and other high humidity locations. It has been found in some cases,
such as in cotton mills, that the aerosol produced by dried water sprays can be a
significant component of the workplace aerosol.
Aerosol photometers require that the aerosol be carried to the detection volume in
some fashion. Because of the inertial and electrical properties of aerosol particles,
there may be errors in transporting the aerosol to the detection volume. Most
photometers have a sampling pump that draws the aerosol into an inlet, through a
length of duct, and to the detector. Some instruments include a preclassifier (cyclone
or impactor) to make the overall response more similar to the respirable dust definition.
Some photometers rely on air convection or motion of the photometer to bring the
aerosol to the detector (passive sampling). In either case, there will generally be some
particles that are not detected due to losses in the instrument before they reach the
detector. Particles larger than 10 //m are especially likely to be lost. However, these
losses will generally be small for smaller particles unless there is high local air velocity
or unless the aerosol particles are highly charged.
A list of instruments is provided at the end of this chapter. Other instruments are
listed in various references [7,8]. Since instrument development is an active field, it

is suggested that current literature sources and the manufacturers be contacted for the
latest information.
4. DATA ACQUISITION AND TREATMENT
a. Calibration
Most photometers are factory-calibrated by comparing the instrument response in a

well-defined aerosol to measurements by the gravimetric method (e.g. Method 0600).
The instrument response at one or more concentrations is compared with the
gravimetric method result. In most cases, the photometer response is modified to read
directly in mg/m3. However, it should be remembered that this calibration is only valid
for the specific calibration aerosol and may differ by as much as a factor of ten when
used with an aerosol from a different source, different composition, or size distribution.
The factory calibration of this type is primarily useful to ensure that the instrument is
operating properly and responding the same as other similar instruments. It does not
ensure that the photometer will respond accurately to another aerosol.
An aerosol photometer measures a single parameter that is dependent on many

variables, e.g., particle size distribution, particle agglomeration, particle refractive
index, that can and do change in field situations. Therefore, it is necessary that the
aerosol photometer be calibrated in conditions closely approximating the aerosol to be
monitored. Calibration is carried out by comparing the time-weighted average
photometer readings directly with field measurements using Method 0600. Most
photometers do not protect the optical surfaces with a clean air sheath and should be
checked frequently for zero drift during calibration and routine monitoring.
b. Operation
Data can be collected in either manual or automated mode. Most direct-reading

photometers have a digital or analog readout indicating concentration. This allows
manual observation of measured concentration. In this mode the instrument is useful
for observing relative concentrations between different locations, for detecting leaks
in processes, for evaluating work procedures, etc. Some photometers also have an
output port that can be connected to a recorder or other data acquisition system. This
allows the instrument to operate unattended while it monitors work processes, filter
penetration breakthrough, etc. In some cases, the photometer and the data acquisition
system together are sufficiently small that they can be worn by a worker. These
photometers can be used to provide a time-dependent profile of exposure over a work
period as well as an integrated time-weighted average exposure. In addition, the
worker can be made aware of aerosol concentrations while carrying out his tasks so
that he can modify work practices to reduce exposure.
It should be noted that the concentration of any contaminant in the air can be highly
variable. Therefore, a single measurement of concentration, especially with a
direct-reading instrument, should only be considered in the context of other
measurements and the environmental conditions.

5. INSTRUMENTS
a. MIE. Inc.
Model RAM-1 Features: Active sampling, with 10-mm nylon cyclone, reference scatterer
built in, zero air built in, clean air protection for optics, several time constants for output,
dehumidifier available, permissible for explosive atmospheres (optional).
Model MINIRAM Features: Passive sampling, with active sampling attachments (optional)
that need a separate pump, automatically calculates running and shift average
concentrations, permissible for explosive atmospheres, zero air attachment (optional).
b. MST Measurement Systems, Inc.
Model P-5 Features: Active sampling, labyrinth classifier on inlet, integrating or

continuous readout, several measurement periods.
Model PCD-1 Features: Active sampling, respirable dust inlet, programmable parameters
include sampling period/alarm concentration/calibration factors, data acquisition built in.
Model PDS-1 Features: Passive sampling, allows personal monitoring, requires separate
readout unit or data logger.
c. ppm Enterprises
Model HAM Features: Passive sampling, active sampling attachments (optional), zero air
attachment, reference scatterer attachment.
Model Personal Aerosol Monitor Features: Passive sampling, zero air attachment,
reference scatterer attachment.
d. Sensidyne, Inc.
Model LD-1 Features: Active sampling, laser light source, 10- or 7-micrometer cut
impactor classifier built in, analog and digital readout, one-minute or operator-selected
measurement period, reference scatterer, zero air attachment.
e. A. P. Buck, Inc.
Portable Dust Monitor Features: Active sampling, laser diode light source, optional
cyclone for respirable sampling, pulse height analyzer for particle sizing information, data
logger built in, filter for reference mass built in.

6. REFERENCES
[1] Threshold Limit Values for Chemical Substances and Physical Agents and
Biological Exposure Indices for 1993-94, 42-45, ACGIH, Cincinnati, OH (1993).
[2] British Medical Research Council: Recommendations of the MRC Panels Relating
to Selective Sampling, Inhaled Particles and Vapours, Pergammon Press, Oxford
(1961).
[3] Ad Hoc Working Group Report to Technical Committee 146-Air Quality,

International Standards Organization, Recommendations on Size Definitions for
Particle Sampling, Am. Ind. Hyg. Assoc. J., 42(5), A-64 (1981).
[4] Air Quality - Particle Size Fraction Definitions for Health Related Sampling,
Technical Report ISO/TR 7708-1 983(E), International Standards Organization,
Geneva, Switzerland (1983).
[5] Bartley, D. L., and Breuer, G. M. Analysis and Optimization of the Performance
of the 10-mm Cyclone, Am. Ind. Hyg. Assoc. J. 43, 520 (1982).
[6] Marple, V. A., and Rubow, K. L, Respirable Dust Measurements, Report for U.S.
Bureau of Mines Contract No. JO1 13042 (1984).
[7] Hering, S., Ed., Air Sampling Instruments. 7th ed.. ACGIH, Cincinnati, OH (1 989).
[8] Willeke, K. and P. A. Baron, Eds., Aerosol Measurement: Principles, Techniques,

and Applications, Van Nostrand-Reinhold, New York (1993).

Experimentally deteimined and theoretically piedicted "mass
sensitivity" of the GCA HAM 1 to oleic acid and watei dioplets.
Included foi comparison is the ACGIH respirable dust
penetration curve [1] normalized to one at 100% penetration.
0.5
0.1
O Oleic Acid (Experimental)

0.05
— Oleic
WaterAcid
(Theoretical)
(Theoretical)
— ACGIH (Normalized to 1.0 at

1002 penetration)
0.01
0.2 0.5 1 2 5 10
Aerodynamic Diameter, |im
Figure 1
Diagram showing the components of an aerosol photometer.

Aerosol
Figure 2

H. PORTABLE ELECTROCHEMICAL SENSOR METHODS
by W. J. Woodfin, NIOSH/DPSE
Contents: Page
1 . Introduction 69
a. Safety 69
b. Applications 70
c. Environmental Conditions 70
a. Calibration 70
b. Sampling and Measurement Procedure 71
c. Limits of Performance 72
5. Manufacturers 72
6. References ... , , , , . 72
1. INTRODUCTION
Portable electrochemical sensor methods include instruments employing this technology

in the determination of oxygen and several toxic gases in the field, using battery-supplied
power. They range in size from those small enough to fit into a shirt pocket and weighing
less than one pound (0.45 kg) to larger units that weigh as much as six pounds (2.7 kg).
The basis for all electrochemical sensors is the use of a porous membrane (normally PTFE)
or capillary system which allows the gas to diffuse into the cell containing the liquid or gel
electrolyte and the electrodes (Figure 1). The exact configuration will vary with
manufacturers and between different toxic gases. When the gas comes into contact with
the electrolyte, a change in electrochemical potential between the electrodes is produced.
Associated electronic circuitry then will measure, amplify, and control this electronic
signal. Because the reaction is proportional to the concentration (partial pressure) of gas
present, the signal is easily translated into parts per million, percent, or ppm-hrs, and read
on the readout meter or stored in microprocessor circuits for later readout.
Some portable electrochemical monitors have been designed for intrinsic safety, i.e.,
for use in potentially explosive atmospheres. Check with the manufacturer to ensure
that a specific instrument meets the appropriate intrinsic safety requirements (e.g.,
Underwriter's Laboratory or Mine Safety and Health Administration).

b. Applications
Electrochemical sensors are available for, e.g., SO2, H2S, NO2, COCI2, CO and O2
[1,2,3]. Except for O2, the widest application for electrochemical sensors has been
as alarm/dosimeter systems rather than as continuous monitors. Because of the low
power requirements and small size, the electrochemical sensor is ideally suited for use
in combination monitors, that is, those that are able to monitor two or more
substances at once. Many combination monitors are available, including in one
package the sensors for oxygen deficiency, combustible gas, and toxic gas. The
oxygen and toxic gas sensors are usually electrochemical. Electrochemical sensors
may be located several meters away from the electronics/readout unit in order to
facilitate remote or pre-entry monitoring.
Because of the low power requirements of these devices, it is possible for them to be
used in lightweight, personal monitor/alarm devices. Electrochemical sensors for
oxygen deficiency, H2S, HCN, and others have been designed into
monitor/dosimeter/alarm packages that are small enough to fit into a shirt pocket, that
weigh less than one pound (0.45 kg) and that operate continuously for as long as four
months without changing the replaceable battery. Also, because of the low power
required, it is relatively easy to design them to be intrinsically safe.
c. Environmental Conditions
The environmental conditions (temperature, relative humidity, barometric pressure) of

the monitor at the time of calibration should be as near as possible to those that will
be encountered during use. Of these three, temperature is most important because
changes in temperature are most often encountered in the field and can cause bias in
the readings obtained. Even with the temperature compensating circuitry employed
in most sensors, some time is required for equilibrium to be reached. If it is not
possible to calibrate at the working temperature, the user must allow sufficient time
for field equilibration of temperature. Changes in barometric pressure are usually less
significant than temperature changes and so are of less concern to the user. Oxygen
monitors with pressure compensating circuitry should be employed whenever
pressures differing by 5 kPa (0.05 atmosphere) or more from the calibration pressure
[1,4] are encountered.
a. Calibration
The most simple example of field calibration of an electrochemical sensor is the oxygen
monitor which may be calibrated by placing it in fresh (outdoor) air and adjusting the
calibration potentiometer to make the readout meter read 20.9% O2. To determine if
it responds to oxygen deficiency, hold the breath for a few seconds, then slowly
exhale, directing the exhaled breath to the sensor. If it is functioning properly, the
meter will deflect downscale and the alarm circuit will be activated.

For electrochemical sensors used to monitor other chemicals (e.g. H2S, CO, NO2, SO2),
stable cylinders of calibration gases in the concentration range of interest as well as
other, less convenient chemical generation systems (e.g., permeation tubes) may be
used for calibration. These sensors may also be zeroed in fresh air or zero air from a
compressed gas cylinder or clean air prepared by filtration. The frequency of
calibration cannot be prescribed exactly, but a good rule is to calibrate at least once
a day at the start of a shift. Manufacturers instructions or user experience may dictate
more frequent calibration.
Always carry out the calibration procedure for toxic gases in a well-ventilated area,
preferably in a fume hood if one is available. Make sure that the calibration procedure
itself does not pressurize the sensing cell. This is especially important to observe
when pressurized cylinders of standard gases are used for calibration.
Overpressurization of the sensor can be avoided by using a pressure regulator on the
calibration gas cylinder or by installing a "tee" fitting in the line to reduce the stream
to atmospheric pressure. Another method is to fill a bag with gas from the cylinder
so that it can be presented to the sensor at atmospheric pressure from the bag.
Sensors should be replaced when they can no longer be calibrated or zeroed easily
during the routine calibration procedure.
b. Sampling and Measurement Procedure
(1) Toxic Gases
Electrochemical sensors used for toxic gases are normally used as dosimeter/alarms,
which means that the electronic circuitry provides a time weighted average (TWA) but
not necessarily a continuous readout of the concentration. The alarm circuit is
designed to activate whenever the preselected value is reached or exceeded for a
predetermined time (or number of counts). On some systems, the TWA value may be
obtained from the systems' microprocessor at the end of the shift by attaching it to
an accessory printer or plotter designed to display this information. Some units
provide a display of the current TWA which can be updated periodically or at the
user's command.
(2) Oxygen
Oxygen electrochemical sensors provide either a continuous or on demand display of

the present percent oxygen in the atmosphere, and the alarm circuitry is designed to
activate at the moment the concentration drops to 19.5% O2. Some models, designed
to be used in hospitals or as area monitors, have both upper and lower alarm levels so
that oxygen-enriched atmospheres may also be monitored. Many of these models
have output suitable for a strip chart recorder so that a permanent record of the
oxygen in the atmosphere may be maintained. The output of these devices is in % O2.
Method 6601 gives a recommended procedure for the use of oxygen monitors.

c. Limits of Performance
(1) Temperature Limits
Most manufacturers of electrochemical sensors specify the lower temperature limits,

usually 32 to 50 °F (0 to 10 °C), and upper limits, typically 120 to 140 °F (50 to
60 °C). These do not present a problem for most applications, but the user should be
aware that lower temperatures tend to result in longer response times. When used
outdoors in cold climates, ambient temperatures should be monitored to assure that
the lower limits are not exceeded.
Since many electrochemical sensors are battery-operated, it should be noted that

temperature extremes can adversely affect the performance or life of the batteries
used in these devices [5,6].
(2) Interferences
Electrochemical sensors designed to measure toxic gases may be non-specific (i.e.,

cross-sensitive to other compounds). Response specificity is determined by the
semi-permeable membrane selected, the electrode material, and the retarding potential
(the potential used to retard the reaction of species other than the analyte). Filtering
or pre-scrubbing of the sampled atmosphere is also an effective method that has been
employed by some manufacturers for some applications. However, not all
interferences have been eliminated.
5. MANUFACTURERS
Manufacturers of electrochemical sensors are too numerous to list. For example, there are
at least 16 companies that manufacture oxygen monitors with electrochemical sensors.
Consult current publications in the field of industrial hygiene and safety for manufacturers
of specific sensors [7,8].
6. REFERENCES
[1] Woodfin, W. J. and M. L. Woebkenberg. An Evaluation Of Portable Direct-Reading

Oxygen Deficiency Monitors, (NIOSH, unpublished, 1984).
[2] Air Sampling Instruments. 7th ed.. Ch. V, ACGIH, Cincinnati, OH (1989).
[3] Methods of Air Sampling and Analysis. 2nd ed., Morris Katz, Ph.D., Editor, Library of
Congress No. 77-6826, American Public Health Association (1977).
[4] NIOSH Criteria for a Recommended Standard. ..Working in Confined Spaces, U.S.
Department of Health, Education, and Welfare, Publ. (NIOSH) 80-106 (1979).
[5] Parker, C. D., et al. An Evaluation of Personal Sampling Pumps in Sub-Zero
Temperatures, U.S. Department of Health, Education, and Welfare, Publ. (NIOSH)
78-117 (1978).
[6] Evaluation of Rechargeable Batteries Used in Industrial Hygiene Equipment, Final
NIOSH Contract Report No. 210-78-0090 (1980).
[7] American Laboratory 1993 Buyers Guide, Am. Lab.. 25(5) (February 28, 1993).

[8] Pollution Equipment News 1993 Catalog and Buyers Guide, Rimbach Publishing, Inc.,
25(6) (November, 1992).
Electrochemical cell schematic
J.
Anode
Electrolyte
Cathode
Diffusion membrane
Figure 1

PORTABLE GAS CHROMATOGRAPHY
by Judd C. Posner, Ph.D., NIOSH/DPSE
Contents: Page
1 . Introduction 74
a. Injection 74
b. Separation 75
c. Detectors (FID, PID, ECD, TCD) 75
d. Limitations 76
a. Safety 77
b. Type of Sample 77
c. Column Selection 77
a. Types 78
b. Calibration 78
c. Procedure 79
d. Indications 79
5. References 79
1. INTRODUCTION
The term "portable gas chromatograph (GC)" as used here refers to any gas
chromatograph not requiring external electrical connections. The portable GC may range
in size and portability from a self-contained unit the size of a small suitcase easily carried
by one person to a much larger unit requiring auxiliary gas supply and requiring more than
one person to transport.
A portable GC consists of, at a minimum, an injection system, a separator (column), and

a detector.
a. Injection
There are two basic injection systems: (1 ) gas-tight syringe through a septum [1 ] and
(2) flushing and filling a sampling loop [2]. The loop is usually filled by means of an
on-board pump. Injection is usually accomplished by means of a valve system, either
manual or automatic.
The loop system is inherently more accurate, but the volume injected is fixed.
However, sample loops are available in a range of volumes. The gas-tight syringe is
not as accurate, but injection volumes between 10 //L and 1 mL may be selected as
appropriate for concentrations encountered in the field (the lower the concentration,

the larger the injection volume). Both injection systems may require purging to reduce
memory effects.
b. Separation
The sample is carried through the column by a carrier gas. Many systems have
refillable gas cylinders which must be charged before going to the field. Others may
need exterior carrier gas cylinders and regulators. It is important to check the carrier
gas requirements in the manual of instructions which goes with the particular portable
gas chromatograph. It is also important to consider the appropriate shipping
regulations concerning compressed gases.
Columns may be of two types, i.e., packed or capillary. The packed column can
accept a larger injection volume, but the capillary column has better separating power.
Therefore, the choice of a packed or capillary system depends on the complexity of
the atmosphere to be sampled and the desired detection limit. It should also be noted
that columns for portable GCs may require special geometries, material of construction
and hardware specific to the instrument. The users manual should be consulted for
information in this area.
The interaction between the injected sample containing one or more compounds in the
vapor phase and a liquid phase present, e.g., on the walls of a capillary column or
coated on a diatomaceous earth (solid support) in a packed column results in a
separation. The stronger the interaction between the component in the vapor phase
and the liquid phase, the more strongly the flow of the component will be retarded by
the column, i.e., the longer the retention time, tr [3].
The use of a heated column system greatly increases the flexibility of the analysis. As
in any isothermal situation, there will still be a usable window of retention time.
However, the retention time of any peak is a function of the temperature. As a rule
of thumb, the retention time doubles for every decrease in column temperature of 30
°C [4]. It is thus possible in many cases to select a temperature at which the peak of
interest will have a usable retention time on a particular column.
c. Detectors
After the sample leaves the column, it goes directly to the detector. Detectors vary
according to their selectivity, sensitivity, and linearity. The four most commonly used
in portable GCs are as follows:
(1 ) Flame ionization detector (FID) [5] - large linear range; moderate sensitivity; good
general detector for organics; low response to CS2, CO, CO2, CCI4; non-selective;
requires auxiliary gases (air and H2).
(2) Photoionization detector (PID) [6] - large linear range; high sensitivity; good
general detector for organics and some inorganic gases; generally lower response
to some small molecules, i.e., CH3CN, CH2CI2, CCI4, CH3OH and low-M.W.

hydrocarbons; selectivity can be introduced in some systems by using different
energy lamps, if available.
(3) Electron capture detector (BCD) [5] - small linear range; high sensitivity; very
selective - in general, responds to molecules containing halogen (fluorine, chlorine,
bromine, iodine) atoms, cyano groups or nitro groups; minimal response to
hydrocarbons, alcohols, ketones, etc.
(4) Thermal conductivity detector (TCD) [5] - good linear range; low sensitivity;
general non-selective detector for volatile compounds including all organics, as
well as inorganics such as ammonia, CO, SF6, NO, NO2, and SO2.
The choice of detector, and, therefore, in most cases, the instrument, will depend on
the chemical to be monitored, the nature of any other contaminants, and the
sensitivity required.
d. Limitations
Most portable GCs have no provision for heating the column, detector, or injection
port. This limits analyses to the more volatile compounds, and results in variation of
retention times with ambient temperature. Also, late-eluting peaks will be poorly
formed and will not be very useful for quantitation. This imposes a severe restriction
on the number of usable column packings for any given contaminant. It also affects
the ability of the system to work well in complex atmospheres, since all quantifiable
peaks must have short retention times, and those with long retention times will appear
as poorly-defined peaks which may interfere with quantitation of the well-shaped
peaks of later injections. Consequently, if contaminants other than the one of interest
are known or suspected to be present in the workplace atmosphere, it is essential that
these compounds be considered when the selection of a column is made in the
laboratory prior to field work.
There is a similar limit to the usable retention time region for a capillary column
operated isothermally. Its advantage is that within this usable region it does more
efficient separations. Some portable GCs have provision for backflushing the column,
which is useful in removing strongly adsorbed compounds which are trapped on the
front of the column.
An important point to remember is that an observed retention time does not constitute
unequivocal identification of a contaminant; an independent, specific identification
must be made to confirm the identity of any peak. However, the knowledge that the
compound in question is in use or is likely to be present plus the presence of a peak
with the expected retention time is strong evidence for the identity of the contaminant.
Thus, some knowledge of the chemicals and the processes in use in the atmosphere
to be examined is essential. Retention time on a second column of different retention
characteristics is a valuable aid to identification.

Such important parameters as the detector drift with time, retention time variation
with temperature, usable battery life, etc., should be determined in the laboratory prior
to use in the field.
a. Safety
The main safety consideration is the use of an FID in areas where a potential explosion
hazard may exist. Do not use a detector of this kind in any area where a flame would
not be permitted unless the instrument has been rated intrinsically safe. If an electron
capture detector is used, the radioactive effluent must be safety vented.
b. Type of sample
In contrast to laboratory-type GCs, portable GCs do not have heated injection ports.
Therefore, the sample must be a gas or vapor at room temperature. In general,
whether the sample is introduced by means of a loop or a gas-tight syringe, most
measurements give essentially instantaneous concentrations. Integrated samples may
be taken, if desired, by using gas bags, evacuated gas bottles and the like; in that
case, the sample concentration is averaged over the filling time of the sample
container. It is important to use only those sample containers in which the analyte is
stable.
c. Column Selection
Once the decision to use a portable GC has been made, in most cases, the critical
question becomes the selection of the column. The following are some hints to aid in
the selection of the column best suited to the analysis to be performed [3]:
(1) Retention time is proportional to column length.
(2) Retention time is proportional to the percent loading of the stationary phase.
(3) Column resolution is proportional to both loading and column length.
(4) Non-polar vapors (e.g., hydrocarbons, halogenated hydrocarbons) are separated

most efficiently by non-polar stationary phases; polar vapors (e.g., alcohols,
ketones, esters) by polar phases. Information on the polarity and selectivity of
stationary phases is available in the form of McReynolds constants which are
tabulated in the catalogs of various vendors of GC supplies. A useful discussion
of the use of McReynolds constants for column selection appears in the catalog
of Applied Science, Inc., 2051 Waukegan Road, Deerfield, IL 60015.
(5) Special columns have been developed for various types of separations. In the
catalogs of most suppliers of GC columns there is a section on applications and
many of the suppliers will be happy to discuss problems and suggest solutions.

a. Types
Data acquisition may be done automatically or manually depending on the particular

design of the portable GC. If the instrument does not have provision for automatic
data collection, then, in most cases, the output signal from the GC will have to go to
some external data collection and storage device, usually a recorder. In such a display,
the area under the peak of interest is proportional to the amount injected. However,
peak height, to a reasonable approximation, can be considered proportional to the
amount injected. This approximation is only true for measurements performed under
identical conditions, i.e., identical column, identical temperature, etc. Thus if there are
substantial changes in ambient temperature such as would be encountered, for
example, in going from an indoor to an outdoor location, and the GC is operating at
ambient temperature (unheated), then the peak height at each location must be related
to a standard run under the same conditions.
b. Calibration
As mentioned before, column selection should be done in the laboratory before going
into the field. Calibration should be done in the field. There are two reasons for this.
First, the potential differences in ambient temperatures between lab and field could
lead to errors as mentioned previously. Second, there is almost always drift in the
response of detectors with time. Therefore, calibration should always be done as
close to the time of actual use as possible. If experience shows that detector drift is
significant over the period of time that samples will be taken, then it will be necessary
to make frequent injections of standards during the course of the day. Even in the
event that drift does not seem to be a problem, occasional injections of standards
throughout the period of use is recommended to make certain that the instrument is
operating as expected.
Calibration standards may be of two types: commercially available certified gas

mixtures or gas bags prepared from a known gas or liquid aliquot of the desired
compound plus a carefully metered volume of diluent, usually air or nitrogen. It is
strongly advised that the preparation of standards be done in the laboratory as a
practice exercise before attempting it in the field, and that the ability to produce
accurate bag standards is verified in the laboratory by comparison with a standard
concentration.
If the injection system operates by means of a loop, the calibration curve should be of
the form of concentration vs. peak height (obtained from the recorder trace). If a
gas-tight syringe is used, then the calibration curve is more conveniently of the form
of amount (concentration, w/v, times volume injected) or volume (ppm times injection
volume) vs. peak height. The range of standards should encompass the expected
ambient concentration at the field site. If this is not known, then preliminary samples
should be taken to determine the range of expected concentrations. Duplicate
injections of each standard should be made and the average value used for the
calibration graph. From the data on the precision of the calibration graph, information

about the precision of the measurements and the limits of detection can be obtained
using standard statistical methods.
c. Procedure
Once the calibration graph has been generated, the next step is to gather field data.
This is done simply by injecting samples of the ambient air periodically into the
portable GC and obtaining concentration values by comparison with the calibration
graph. The frequency of sample taking is governed by the time necessary for the peak
of interest to appear (retention time) plus the time necessary for any other
contaminants to elute from the column. As it is seldom possible to know the exact
composition of the atmosphere to be sampled beforehand, the time between samples
will usually have to be determined in the field.
d. Indications
Portable GCs find their most common use as a tool for the gathering of concentration
data during industrial hygiene surveys. They may also be used for real time monitoring
of leaks, spills, etc., in order to make a judgment as to whether or not a dangerous
concentration may have been reached. Some instruments with
microprocessor-controlled acquisition and storage of data may be used to assess
trends over extended periods. An important consideration, however, is that portable
GCs should not, in general, be used for compliance measurements, nor are they meant
as substitutes for the usual analytical methods used for determination of exposure
such as those in this Manual. There are basically two reasons for this. First, there is
no provision for unequivocally identifying a peak obtained, such as could be done in
the laboratory using a GC/mass spectrometer system, and second because the
separation step in the portable GC is not, as explained previously, as efficient as that
obtainable with a laboratory analytical instrument. It is equally important to point out
that the field measurement is inherently much simpler and does not have the problems
with incomplete adsorption and desorption, sample storage instability, migration, and
breakthrough which some of the compliance methods have. Thus while the field
measurement is less exact than would be the case with a laboratory measurement, the
overall field sampling and measurement process may be, in fact, more exact.
5. REFERENCES
[1] Jerpe, J. and A. Davis, J. Chromatoq. Sci. 25(4): 154-57 (1987).

[2] Gaind, V. S., K. Vohra and F. Chai, Analyst 117(2): 161 (1 992).
[3] Hinshaw, J.V., LC-GC 10(11): 851-55 (1992).
[4] Giddings, J.C., ,L Chem. Ed. 39(11): 569-73 (1 962).
[5] McNair, H.M. and E.J. Bonelli, Basic Gas Chromatography, p. 1 1 8 (1 967).
[6] Berkley, R.E., J.L. Varns and J. Plell, Envron. Sci. Technol. 25(8): 1429-1444,
(1991).

J. SAMPLING AND CHARACTERIZATION OF BIOAEROSOLS*
by Paul A. Jensen, Ph.D., PE, CIH and Millie P. Schafer, Ph.D., NIOSH/DPSE
CONTENTS: PAGE
1. INTRODUCTION 81
a. General 81
b. Indoor and Outdoor Bioaerosols 81
c. Viable and Nonviable Bioaerosols 81
2. PRINCIPLES OF BIOAEROSOL COLLECTION 83

a. General Principles 83
b. Impaction 84
c. Filtration 85
d. Impingement 86
e. Characteristics of Several Bioaerosol Samplers 87
3. SAMPLING CONSIDERATIONS 91
a. Safety 91
b. Environmental Conditions 91
c. Flow Calibration 92
d. Culture Media 92
(1) Fungi 92
(2) Bacteria 93
(3) Thermophilic Actinomycetes 93
(4) Additional Media 93
e. Blanks 94
(1) Laboratory Media Blanks 94
(2) Field Blanks 94
4. PREPARATION, IDENTIFICATION, AND ENUMERATION PROCEDURES

FOR CULTURABLE BIOAEROSOLS 94
a. Sample Preparation 94
b. Enumeration 95
(1) Total Concentration (Colony Forming Units per cubic meter) 95
(2) Adjusted Concentration (CFU/m3) 95

(3) Limitations 96
c. Identification of Culturable Bioaerosols 96
(1) Classical or General Microbiology 96
(2) Clinical and Environmental Microbiology 97
d. Interpretation of Data 98

5. ADDITIONAL IDENTIFICATION AND ENUMERATION PROCEDURES
FOR NONVIABLE OR VIABLE BIOAEROSOLS 99
a. Microscopy 99
(1) Bright-Field or Light 99
(2) Phase Contrast 100
(3) Fluorescence 100
(4) Electron 100
b. Endotoxin Assay 1 00
c. Immunoassays 101
(1) Radioimmunoassays (RIA) 101
(2) Fluorescent Immunoassays (FIA) 102
(3) Enzyme Immunoassays (EIA) 102
d. Gene Probes 1 02
(1) Nick-translated DNA Probes 103
(2) Synthetic Oligomer DNA Probes 103
(3) Polymerase Chain Reaction (PCR) 103
(4) Restriction Fragment Length Polymorphic (RFLP) Analysis . 1 03
6. MANUFACTURERS 105
7. REFERENCES 107
^Revision of Jensen PA, Lighthart B, Mohr AJ, Shaffer BT [1994]. Instrumentation used with
microbial bioaerosol. In: Lighthart B, Mohr AJ, eds. Atmospheric microbial aerosols theory and
applications. New York, NY: Chapman & Hall, pp. 226-284.

1. INTRODUCTION
a. General
Bioaerosol monitoring is a rapidly emerging area of industrial hygiene. Bioaerosol

monitoring includes the measurement of viable (culturable and nonculturable) and
nonviable microorganisms in both indoor (e.g., industrial, office or residential) and
outdoor (e.g., agricultural and general air quality) environments. In general, indoor
bioaerosol sampling need not be performed if visible growth is observed.
Monitoring for bioaerosols in the occupational environment is one of the many tools
the industrial hygienist uses in the assessment of indoor environmental quality,
infectious disease outbreaks, agricultural health, and clean rooms. Contamination
(microbial growth on floors, walls, or ceilings, or in the HVAC system) should be
remedied. If personnel remain symptomatic after remediation, air sampling may be
appropriate, but the industrial hygienist should keep in mind that false negative
results are quite possible and should be interpreted with caution. Other exceptions
for which bioaerosol sampling may be appropriate include epidemiological
investigations, research studies, or if situations indicated by an occupational
physician and/or immunologist.
Sampling for fungi and bacteria (including Actinomycetes) is included in this

chapter. Less developed methods for bioaerosols such as viruses, protozoa,
antigenic fragments, algae, arthropods, and mycoplasmas are not addressed at this
time.
b. Indoor and Outdoor Bioaerosols
In general, indoor microflora concentrations of a healthy work environment are lower

than outdoor concentrations at the same location [ACGIH 1989, Step two; Macher
et al. 1995]. If one or more genera are found indoors, in concentrations greater
than outdoor concentrations, then the source of amplification must be found and
remedied. Bioaerosol sampling is often performed out of doors for pollen and fungi
to assist allergists in their treatment of patients by identifying taxa distribution and
concentration in air over time. On occasion, outdoor bioaerosol sampling is
conducted in an occupational environment (e.g., agricultural investigations and
sewage treatment plants). Indoor bioaerosol sampling is often conducted in
occupational (industrial and office environments) and nonoccupational (residential
and educational buildings) settings. When sampling is indicated, it is advisable to
sample before, during, and after the sampling area is occupied, including times
when the heating, ventilating, and air conditioning system is activated and
inactivated.
c. Viable and Nonviable Bioaerosols
Viable microorganisms are metabolically active (living) organisms with the potential
to reproduce. Viable microorganisms may be defined in two subgroups: culturable
and nonculturable. Culturable organisms reproduce under controlled conditions.

Information regarding environmental conditions and media to culture
microorganisms is shown in Sections 3. a. and 3.c. Nonculturable organisms do not
reproduce in the laboratory because of intracellular stress or because the conditions
(e.g., culture medium or incubation temperature) are not conducive to growth. As
the name implies, viable bioaerosol sampling involves collecting a bioaerosol and
culturing the collected particulate. Only culturable microorganisms are enumerated
and identified, thus leading to an underestimation of bioaerosol concentration.
Nonviable microorganisms are not living organisms; as such, they are not capable
of reproduction. The bioaerosol is collected on a "greased" surface or a membrane
filter. The microorganisms are then enumerated and identified using microscopy,
classical microbiology, molecular biological, or immunochemical techniques. When
sampling for culturable bacteria and fungi, the bioaerosol is generally collected by
impaction onto the surface of a broad spectrum solid medium (agar), filtration
through a membrane filter, or impingement into an isotonic liquid medium (water-
based). Organisms collected by impaction onto an agar surface may be incubated
for a short time, replica-plated (transferred) onto selective or differential media, and
incubated at different temperatures for identification and enumeration of
microorganisms [Tortora et al. 1989]. Impingement collection fluids are plated
directly on agar, serially diluted and plated, or the entire volume of fluid is filtered
through a membrane filter. The membrane filter is then placed on an agar surface
and all colonies may be replica-plated. Culturable microorganisms may be
identified or classified by using microscopy, classical microbiology, or molecular
biology techniques such as restriction fragment length polymorphic (RFLP) analysis.
Classical microbiology techniques include observation of growth characteristics;
cellular or spore morphology; simple and differential staining; and biochemical,
physiological, and nutritional testing for culturable bacteria. Analytical techniques
which may be applied to both nonviable and viable microorganisms, but not
distinguish between them, include polymerase chain reaction (PCR) and enzyme-
linked immunosorbent assay (ELISA). Such methods may be used to identify
specific microorganisms and to locate areas of contamination. Though these latter
methods are generally qualitative, current research efforts involve modifying the
methods to obtain semi-quantitative or quantitative results.
2. PRINCIPLES OF BIOAEROSOL COLLECTION
a. General Principles
Most aerosol sampling devices involve techniques that separate particles from the
air stream and collect them in or on a preselected medium. Impaction, filtration, and
impingement are three common sampling techniques used to separate and collect
the bioaerosol.

b. Impaction
Impaction is used to separate a particle from a gas stream based on the inertia of
the particle. An impactor consists of a series of nozzles (circular- or slot-shaped)
and a target. Perfect impactors have a "sharp cutoff' or step-function efficiency
curve. Particles larger than a particular aerodynamic size will be impacted onto a
collection surface while smaller particles proceed through the sampler [Hinds 1982].
Marple and Willeke [1976] have reported that high velocity, inlet losses, interstage
losses, and particle reentrainment affect the performance characteristics of an
impactor. The cut-diameter (dso) is a function of the Stk50. In other words, the
mass of the particles smaller than the d50 that are collected equals the mass of the
particles larger than the d50 that pass through the impactor. The collection
efficiency of the impactor approaches 100% when the aerodynamic diameter is
greater than the d50 [Hinds 1982]. Aerodynamic diameter (d.,e) is defined as the
diameter of a hypothetical sphere of unit density (pp = 1 g/crrr) that has the same
settling velocity as the particle [Hinds 1982]. Impactors are selected so that the
desired size particles will be collected. For the same aerosol sample, the mass and
count particle distributions will have distinctive means and medians; however, they
share the identical geometric standard deviation. The mass median aerodynamic
diameter (MMAD) is discriptive of the mass distribution. In other words, the MMAD
equals the diameter where particles larger than MMAD contribute half the collected
mass; and those particles smaller than MMAD contribute the other half. The count
median aerodynamic diameter (CMAD) is the median of the number of particles in
a given particle distribution.
Investigators are likely to employ stationary cascade impactors or individual

impactors used in survey instruments, either as the primary collection mechanism,
or as a preclassifier (for example to remove nonrespirable particles from the
sampled air stream). Cascade impactors consist of a stack of impaction stages:
each stage consists of one or more nozzles and a target or substrate. The nozzles
may take the form of holes or slots. The target may consist of a greased plate, filter
material, or growth media (agar) contained in petri dishes. Each succeeding stage
collects smaller particles. A filter may be used as the final stage so that all particles
not impacted on the previous stages are collected. The target may be weighed to
determine the collected mass, or it may be washed and the wash solution analyzed.
Filters may induce more particle bounce than greased or oiled plates. Although
personal cascade impactors are available, these devices are not as widely used in
personal sampling for bioaerosols as are filters [Macher and Hansson 1987].
Impactors used for the collection of airborne microorganisms may have range from
a single slit to more than 400 holes per stage. The particles impact onto growth
medium with one or more bacterial or fungal colonies forming at some impaction
sites. Multiple particles, each containing one or more organisms, passing through
a single hole may be inaccurately counted as a single colony. As the number of
organism-containing particles deposited onto the growth medium increases, the
probability that the next organism-containing particle will impact a "clean" hole
decreases. The basic formula for the coincidence correction follows:

111 1
Pr = N
N (N-1) (N-2) (N-r+1)
Andersen [1958] and Leopold [1988] stated that Pr is the estimated culturable
particle count given r culturable particles are observed on the sample plate, and N
is the total number of holes per impactor stage. For example, if 75% of the holes
have received one particle, the chance that the next particle will impact a "clean"
hole is one in four (25%) [Andersen 1958; Andersen 1984; Leopold 1988; Macher
1989].
c. Filtration
Collection of particles from a nonbiological aerosol sample is most commonly

achieved by filtration. Filter media are available in both fibrous (typically glass) and
membranous forms. Deposition occurs when particles impact and are intercepted
by the fibers or surface of filter membranes [Hinds 1982]. Thus, particles smaller
than the pore size may be efficiently collected. Sampling filter media may have pore
sizes of 0.01 to 10 urn. The efficiency of removing particles from the air depends
on the face velocity (i.e., the cross sectional air velocity of the filter holder). For
particles less than 1 urn, the overall efficiency decreases with increasing face
velocity [Liu et al. 1983; Lippmann 1995]. For particles greater than approximately
1 pm, the filter collection efficiency is greater than 99%. The overall efficiency of
membrane filters is approximately 100% for particles larger than the pore size
[Lippmann 1995].
Membrane filters are manufactured in a variety of pore sizes from polymers such
as cellulose ester, polyvinyl chloride, and polycarbonate. Polymeric membrane
filters lack rigidity and must be used with a support pad. The choice of a filter
medium depends on the contaminant of interest and the requirements of the
analytical technique. For gravimetric analysis, nonhygroscopic materials such as
glass fibers, silver, or polyvinyl chloride membranes are selected. For analysis by
microscopy, cellulose ester or polycarbonate membranes are the usual choices.
Filters are often held in disposable plastic filter cassettes during bioaerosol
sampling. The three-piece cassette may be used either in open- or closed-face
modes. Open-face sampling is performed by removing the end plug and the plastic
cover from the three-piece cassette and is used when the particulate must be
uniformly deposited (i.e., for microscopic analysis). If a three-piece cassette is used
in the open-face arrangement, the plastic cover is retained to protect the filter after
sampling is concluded. All plastic cassettes are securely assembled and sealed
with a cellulose shrink band or tape around the seams of the cassette to prevent
leakage past the filter.
Membrane filters for use in sampling are usually supplied as disks of 37- or 47-mm
diameter. Because the pressure drop across a filter increases with the air velocity

through the filter, the use of a larger (47-mm) filter results in a lower pressure drop
for a given volumetric flow rate. The use of the smaller (37-mm) filter concentrates
the deposit of the contaminant onto a smaller total area, thus increasing the density
of particles per unit area of filter. This may be helpful for direct microscopic
examination of low concentrations of organisms. In areas of high concentration, the
microorganisms may have to be eluted, diluted, and then refiltered for microscopic
analysis.
Filtration techniques are used for the collection of certain fungi and endospore-
forming bacteria that are desiccation-resistant. The sampled organisms are washed
from the surface of smooth-surface polycarbonate filters. The microorganisms in
the wash solution are either cultured or refiltered to distribute the microorganisms
uniformly on the membrane filter. In the latter case, the microorganisms are stained
and examined microscopically [Wolf et al. 1959; Fields et al. 1974; Lundholm 1982;
Palmgren et al. 1986a]. To culture the organisms, the membrane filter from each
sampling cassette is washed with a 0.02% Tween™ 20 (J.T. Baker Chemical Co.,
Phillipsburg, NJ) in aqueous solution (three 2-mL washes), with agitation. Some of
the recovered wash volume is serially diluted from full strength (1:10, 1 : 1 00, 1:1 000)
and 0.1 mL of each dilution is inoculated onto duplicate 100-mm x 15-mm petri
dishes containing the appropriate medium. Residual cultivable microorganisms on
the membrane filter from each sampling cassette are counted by placing the filter
on a medium in a Petri dish to allow the microorganisms to colonize. The Petri
dishes are incubated and the colonies are identified and enumerated [Muilenberg
et al. 1992]. This method of serial dilution allows flexibility in dealing with
unpredictable levels of spores by permitting a count of the spores collected on the
filter either directly or by serial dilution of the wash solution. An inherent weakness
in this procedure is that high analytical dilutions can statistically exclude taxa
present in the air sample at low concentrations. This dilution technique favors the
predominant fungi populations at the expense of minor populations.
d. Impingement
The liquid impingers are a special type of impactor. Impingers are useful for the
collection of culturable aerosols [White et al. 1975; Lembke et al. 1981; Henningson
et al. 1988]. Impingers such as the Greenberg-Smith impinger or the AGI-30 use
a liquid (e.g., a simple salt solution such as 0.3 mM phosphate-buffered dilution
water) as the collection medium. Additives to the collection medium such as
proteins, antifoam, or antifreeze aid in resuscitation of bacterial cells, prevent
foaming and loss of the collection fluid, and minimize injury to the cells. The jet is
positioned a set distance above the impinger base and consists of a short piece of
capillary tube designed to reduce cell injury when the air is dispersed through the
liquid and the particles are entrapped. The Greenberg-Smith and AGI-30 samplers
operate by drawing aerosols at nominal flow rates of 28.3 and 12.5 L/min,
respectively, through an inlet tube [Macher et al. 1995]. The d50 of these samplers
is approximately 0.3 urn [Wolf et al. 1959; Gown et al. 1957]. The AGI-30 inlet tube
is curved to simulate particle collection in the nasal passage [Cox 1987]. This
makes it especially useful for studying infectious airborne microorganisms by

separating respirable (collection fluid) and nonrespirable (inlet tube)
microorganisms. When the AGI-30 is used to recover total airborne organisms from
the environment, the curved inlet tube is washed with a known amount of collecting
fluid after sampling because larger particles (i.e., over 15 um) are collected on the
tube wall by inertial force. After sampling for the appropriate amount of time, 10 mL
of the full-strength collection fluid is filtered through a 0.45-um pore size membrane
filter. In addition, serial dilutions of the remaining collection fluid are handled
similarly [Greenberg et al. 1992]. The membrane filter is placed in a 100-mm by 15-
mm sterile plastic petri plate filled with the appropriate medium and incubated for
later identification and enumeration.
e. Characteristics of Several Bioaerosol Samplers
Once the purpose or the goal of bioaerosol sampling is determined, the appropriate
sampling method(s) may be chosen. The selected bioaerosol sampler(s) must be
capable of high efficiency particle collection within the physical and biological
conditions required by the microorganism(s) to be sampled. Experimental,
theoretical, and physical characteristics of several commonly used bioaerosol
samplers are shown in Table I. The physical characteristics (flow rate, diameter of
hole or width of slit, area of nozzle, and velocity of air through the nozzle) were used
to calculate the theoretical cut-diameters of the listed samplers. The theoretical
characteristics were discussed in the preceding subsections.
The particle size distribution of the bioaerosol is very important in the evaluation of
the data obtained using the selected sampler. If the selected sampler does not
provide particle size distribution data, then a cascade impactor such as the
Andersen 6-stage sampler also should be used. For example, if an SAS-Compact
sampler was the selected sampler for collection of culturable Escherichia coli, an
Andersen 6-Stage sampler should be used to determine the particle size distribution
at each location sampled. However, a membrane filter sampler is not appropriate
for sampling culturable E coli because the cells would desiccate and become either
nonviable or viable but not culturable under these conditions [Jensen et al. 1992].
In another example, an impactor with a d50 of 4 urn should not be used to collect
Aspergillus niger spores (dae ~ 1-3 um) because most spores would remain
entrained in the air passing through the instrument.
General guidelines for matching the appropriate sampler with the bioaerosol of
interest are shown in Table II. The bioaerosol of interest categories include
culturable bioaerosol sampling, and nonculturable and nonviable bioaerosol
sampling. Subcategones include free bacteria (i.e., mostly single cells), free fungi
(i.e., mostly single spores), and clumped bacteria and fungi with MMAD > 4 urn.
Culturable bioaerosol sampling instruments must minimize injury during the
collection process and maintain the culturability of the collected microorganisms.
Free bacteria and fungi are the bioaerosols of interest in some environmental
investigations, and the sampler must collect these small aerosols [Wright et al.
1969; Lee et al. 1973]. Often, however, the bioaerosols will be clumps of
microorganisms or microorganisms attached to another particle such as a skin scale

or piece of lint. When using any cultivable bioaerosol sampler, the investigator
must select sampling time, considering estimated concentration, such that 30-100
colonies (up to 300 in some situations) develop per plate [Tortora et al. 1989]. The
lower limit (30 colonies) is necessary to obtain sufficient statistical power for
comparison purposes. However, when a clean room or other environment having
extremely low levels of culturable bioaerosols is sampled, the lower limit of 30
colonies may not be achievable. In such a situation, a qualitative representation
must be used without accommodation of statistical validity. The upper limit (100-
300 colonies) is the maximum range in which one can easily count and differentiate
colonies. When nonviable microorganisms are sampled or when culturability is not
of concern, collection efficiency is the overriding concern. Table II is not an all
inclusive listing of bioaerosol samplers. Investigators should take special note of
the limitations listed at the bottom of the table.

Table I. Experimental, theoretical, and physical characteristics of several commonly used
bioaerosol samplers.
Sampler d50 tt holes Q Dj or Wj A|

True Theoretical
jon L/min mm BUT m/s
Andersen 6-Stage [Andersen 1958, 1984]

Stage 1 7.0 6.24 400 28.3 1.18 1.10 1.08
Stage 2 4.7 4.21 400 28.3 0.914 0.656 1.80
Stage 3 3.3 2.86 400 28.3 0.711 0.397 2.97
Stage 4 2.1 1.84 400 28.3 0.533 0.223 5.28
StageS 1.1 0.94 400 28.3 0.343 0.092 12.8
Stage 6 0.65 0.58 400 28.3 0.254 0.051 23.3
Andersen 2-Stage [Phillips 1990]

Stage 0 8.0 6.28 200 28.3 1.50 1.77 1.33
Stage 1 0.95 0.83 200 28.3 0.400 0.126 18.8
Andersen 1-Stage [Andersen 1958; Phillips 1990]

Stage N6 0.65 0.58 400 28.3 0.254 0.051 23.3
Mattson-Garvin Slit-to-Agar 0.53 1 28.3 0.152 6.23 75.7
Ace Glass All-Glass Impinger-30

0.30 12.5 1.00 0.785 265.
FBI Surface Air Sampler [Lach 1985]

Compact 2.0 1.97 219 90 1.00 0.785 8.72
Standard 2.0 1.52 260 180 1.00 0.785 14.7
BIOTEST Reuter Centrifugal Sampler [BIOTEST undated; Macher and First 1983]
Standard 3.8 7.5 280
RCS-Plus
Membrane Filter Samplers
Burkard Spore Trap (1,7-Day)

Standard Nozzle 3.70 10 2.00 28.0 5.95
High Efficiency Nozzle 2.17 10 2.00 10.0 16.7
Burkard (Personal) Sampler

Slit 1 10
Seive 4.18 100 20 1.00 0.785 1.94
Burkard May-Type Multi-Stage Impinger

Stage 1 10 20
Stage 2 4 20
Stage 3 20
Allergenco MK-2
Where:
= Cut-diameter or aerodynamic diameter above which the collection efficiency of the impactor approaches 100%, both the true and the
theoretical d50s are shown;
= Airflow rate;
= Diameter of seive or hole//Width of slit/;
= Area of holey or slit/; and
= Velocity of air through hole/ or slit/.

Table II. General guidelines for matching the appropriate sampler with the bioaerosol of
interest.
Sampler Cultivable Bioaerosol Sampling Non-Viable Bioaerosol

Sampling
Free Bacteria Free Fungi Clumped Bioaerosols Bioaerosols
MMAD < 4//m MMAD < 4//m MMAD s 4//m MMAD < 4 fjm MMAD 2 4//m
/A /A /A
Andersen 6-Stage
/A /A /A
Andersen 2-Stage
/A /A /A,H
Andersen 1 -Stage
/A /A /A
Mattson-Garvln Sllt-to-Agar
D,E
Ace Glass All-Glass lrnpinger-30
PBI Surface Air System
Compact G G /B
Standard G G /B
BIOTEST Reuter Centrifugal Sampler

/B
Standard
/B
RCS-Plus
Membrane Filter Samplers V C'

Burkard Spore Trap (1,7-Day)
Standard Nozzle
High-Efficiency Nozzle
Burkard (Personal) Sampler
Slit
Seive
Burkard May-Type Multi-Stage
Impinger C,D
Allergenco MK-2
Satisfactory for specified application.

A Concentrations greater than 5,000-7,000 CFU/m3 will overload sample;
B Concentrations greater than 1 ,000-2,000 CFU/m3 will overload sample;
C Good for very low to very high concentrations;
D Bioaerosols may be reaerosolized and drawn out of the impingers during sampling, resulting in
an underestimation of concentration and a decrease in precision;
E May overestimate concentration due to breaking up of clumps;
F For desiccation-resistant bacteria only;
Q May be acceptable with new sampling head being evaluated by PBI/Spiral Biotech;
H May underestimate conc, of large bioaerosols (MMAD > 10 //m) due to impactor entry losses;
I May underestimate concentration of small bioaerosols (MMAD •; 5 //m).

a. Safety
Investigators should use appropriate personal protective equipment (PPE) and

practice good personal hygiene when conducting indoor environmental quality,
disease outbreaks, and agricultural health investigations that have resulted in
medically diagnosed symptoms. PPE may include respiratory protection to prevent
inhalation of microbes and microorganism-resistant clothing to prevent the
transmission (bodily contact with microorganisms) to investigators. Good personal
hygiene practices include washing exposed skin and clothing thoroughly and
refraining from eating, drinking, or smoking in a contaminated area. These simple
steps will help minimize the ingestion, inhalation, or uptake of microorganisms.
All samplers, culture plates, equipment, etc. should be handled aseptically to

prevent contamination of the samplers and, more importantly, to prevent the spread
of potential human pathogens to the worker or the work environment [CDC/NIH
1992; McKinney et al. 1991]. All surfaces, including washed hands, harbor
microorganisms or spores unless they are specifically sterilized. Practically
speaking, however, not all objects may be sterilized. While disinfection with an
oxidizing chemical or alcohol destroys most vegetative cells, these agents do not
destroy all spores. Samplers should be disinfected or, if possible, sterilized after
each sample collection. Special care should be given to samplers with convoluted
inlets or air pathways where microorganisms may accumulate.
b. Environmental Conditions
Temperature and relative humidity (RH) should be recorded over the sampling
period. Airborne bacteria will dessicate (i.e., intracellular and extracellular water
evaporate) when exposed to unstaurated air. The degree of cellular stress and rate
of evaporation increase as relative humidity decreases and temperature increases
[Marthi and Lighthart 1990]. In field experiments (greenhouse), survival of certain
bacteria was 35- to 65-fold higher at 80% RH than at 40% [Walter et al. 1990]. In
laboratory experiments, survival of certain bacteria was virtually complete at low RH
but was reduced at RH values above 80% [Cox 1968]. Cox [1987] believes the
potential for the movement of the solvent water is an important environmental
criterion in assessing survivability of bacteria, viruses, and phages. Limited studies
have been made of temperature effects. Temperature induces morphological
changes in dimorphic fungi. For example, Histoplasma capsulatum, a pathogen,
exists as a spore or mycelial form below 25 °C. However, higher temperatures
have been shown to induce a transition from the mycelial form to the yeast form
[Salvin 1949]. Like most particles, freshly generated microbial aerosols are nearly
always electrostatically charged unless steps are taken to neutralize them. There
is very little published information about electric charges on actual workplace
aerosols, and even less on bioaerosols [Johnston et al. 1985]. In general, the effect
of electrical charge has been overlooked, resulting in the possible bias of sampling

results. At RH values above 70% RH, electrostatic phenomena are minimal [Hinds
1982; Cox 1987].
Sampling locations should be selected to assist in evaluation of your hypothesis.

If you are evaluating worker exposure, then the samplers should be placed in
inhabited areas where worker exposures may be measured. If you are evaluating
contamination of a ventilation system, then sampling in the system and at the
ventilation louvers would be appropriate. Care must be exercised to ensure people
do not tamper with the samplers and that you do not inadvertently aerosolize
microorganisms on surfaces or in duct-work.
c. Flow Calibration
Accurate airflow rates are very important in calculating the concentration of

microorganisms in the air. All samplers should be calibrated before and after
sampling to ensure the flow rate is within the manufacturer's specifications and does
not change from the initial calibration. Calibration may be performed using a
primary standard such as a spirometer or bubble calibrator. Where it is not possible
to calibrate using a primary standard, a secondary standard such as a dry gas
meter may be used. The calibration of such a secondary standard should be
traceable to a primary standard. See Chapter D. General Considerations for
Sampling Airborne Contaminants of this manual for further details on calibration of
airflow rates.
d. Culture Media
General detection and enumeration media are normally used in the collection of
fungi, bacteria, and thermophilic Actinomycetes. Plates can be replicated on
differential or selective media for identification after the organisms have been
collected. In addition, it may be advisable to concurrently use more than one type
of culture medium to collect aerosolized microorganisms, because of inherent
biases caused by media selection. The following are some general guidelines for
media:
(1) Fungi
Traditionally, malt extract agar (MEA) and rose bengal agar (RBA) have
been recommended as broad spectrum media for the collection and
enumeration of fungi [Morring et al. 1983; Surge et al. 1977; Smid et al.
1989]. MEA and RBA are generic terms and formulations vary from supplier
to supplier and laboratory to laboratory. One MEA recipe is a less nutritious,
unamended 2% MEA, which is reported to promote better sporulation than
MEA amended with glucose and/or peptone [Hunter et al. 1988; Strachan
et al. 1990]. With RBA, the colonies remain small; however, natural or
artificial light may make the medium toxic to some fungi. In addition,
pigmentation of the fungal growth on RBA complicates the identification
process. Based on the work of researchers in Australia and Holland,

dichloran glycerol 18 agar (DG-18) is recommended for identification and
enumeration of fungi [Hocking and Pitt 1980; Pitt et al. 1983; Verhoeff et al.
1990]. This medium is adequate for most fungi, including xerophilic fungi.
DG-18 does not have the disadvantages of RBA. To inhibit the growth of
bacteria, antibiotics, such as streptomycin, may be added to the RBA
medium [DIFCO 1984].
(2) Bacteria
Tryptic soy agar (TSA), casein soy peptone agar (CSPA) and nutrient agar
(NA) are broad spectrum media for the collection and enumeration of
bacteria. Special purpose media (i.e., selective media) are often used to
select for specific microorganisms of interest. As with the media for fungi,
chemicals may be added to the media which restrict growth of selected fungi
and bacteria [DIFCO 1984].
(3) Thermophilic Actinomycetes
Thermophilic Actinomycetes is a special class of bacteria that has been

associated with indoor environmental quality problems [Nevalainen 1989].
CSPA, TSA, and tryptone glucose yeast agar (also known as standard
methods agar [SMA] and standard plate count agar [SPCA]) are broad
spectrum media for the collection and enumeration of thermophilic
Actinomycetes [DIFCO 1984; Amner et al. 1989; ACGIH 1989, Bacteria].
(4) Additional Media
Other media for the detection and enumeration of fungi and bacteria may be
used. To discriminate for a general class of microorganisms by inhibiting or
eliminating other microorganisms, a selective medium containing an
antibiotic or other growth-restricting chemical may be used. To distinguish
among species, a differential media may be used. Differential media contain
indicators that permit the recognition of microorganisms with particular
metabolic activities. Different incubation times or temperatures can also be
used to get differential growth on the same medium. When a specific
medium (i.e., selective or differential) is needed, the investigator(s) should
refer to the most recent Manual of Clinical Microbiology published by the
American Society for Microbiology, DIFCO Manual: Dehydrated Culture
Media and Reagents for Microbiology published by DIFCO Laboratories, or
the various catalogues published by the American Type Culture Collection
(ATCC) [DIFCO 1984; Murray et al. 1995; Gherna et al. 1992; Jong and
Edwards 1991].

Blanks
(1) Laboratory Media Blanks
Laboratory media blanks are unexposed, fresh media samples. These

samples are generally not taken into the field. Before using any batch of
media, incubate at least three culture plates under the same conditions as
planned for the field samples, in order to check for sterility of the media.
Approximately five media blanks should be included with each sample set.
If the samples are to be analyzed by an outside laboratory, consult the
specific laboratory procedure for the number of blanks to be submitted.
(2) Field Blanks
Field blanks are simply unopened, fresh media samples that are handled in
every way the same as field samples, including labeling, except that no air
is drawn through the sampler. The recommended practice for the number
of field blanks is to provide two field blanks for every 10 samples with a
maximum of 10 field blanks for each sample set.
4. PREPARATION, IDENTIFICATION, AND ENUMERATION PROCEDURES FOR

CULTURABLE BIOAEROSOLS
a. Sample Preparation
Inoculated agar plates are incubated at the appropriate temperature for times
ranging from hours for a fast-growing bacterium to develop a microcolony; to days
for a fungus to develop into a visible colony, and perhaps sporulate; to weeks for
an organism such as drug resistant Mycobacterium tuberculosis to produce visible
colonies [ATS 1990]. As a rule, plates are incubated at the temperatures shown in
Table III [ACGIH 1989, Fungi and Bacteria; Baron and Finegold 1990].

Table III. Incubation temperatures and conditions for viable (culturable)
microorganisms.
Fungi 25 °C or
Room temperature with
natural light
Bacteria, environmental 25 to 30 °C
Bacteria, human-source 35 to 37 °C
Bacteria, thermophilic
Actinomycetes 50 to 56 °C
Laboratory media blanks and field media blanks must be handled in the same
manner as samples.
b. Enumeration
(1) Total Concentration (Colony Forming Units Per Cubic Meter)
The total concentration of culturable microorganisms is calculated by dividing the

volume of air sampled into the total number of colonies observed on the plate. A
colony is a macroscopically visible growth of microorganisms on a solid culture
medium. Concentrations of culturable bioaerosols normally are reported as colony
forming units (CFU) per unit volume of air. CFU is the number of microorganisms
that can replicate to form colonies, as determined by the number of colonies that
develop.
(2) Adjusted Concentration (CFU/m3)
Often, it is difficult to identify multiple colonies at one location on a plate

because of the lack of differential colony morphology or because the
chemicals secreted by one microorganism might inhibit the growth of other
microorganisms at that same location [Burge et al. 1977]. In addition, some
organisms produce large, spreading colonies while others produce
microcolonies. Also, the morphology of the colony of one microorganism
may completely obscure that of another, and a fast-grower might obscure
a slow-grower. In these cases, a statistical adjustment of the observed
number of colonies is needed to account for the probability that more than

one particle impacted the same site [Andersen 1958; Leopold 1988; Macher
1989]. The adjusted concentration of culturable microorganisms is
calculated by dividing the volume of air sampled into the adjusted number
of colonies observed on the plate (see section 2.b ).
(3) Limitations
Bioaerosol collection methods are "grab sample" techniques and, thus,

represent only approximations of transient microbial concentrations in
problematic atmospheres. Timely ascertainment of bioaerosol involvement
is not possible, because of the time-dependent nature of the cultivation of
samples and the subsequent enumeration of colonies.
The methods thus far pertain to culturable microorganisms. Microorganisms

that are stressed or injured either by environmental conditions or bioaerosol
sampling procedures may be viable, but not culturable [McFeters et al.
1982]. Certain species may be too fastidious to grow in laboratory culture.
For instance, some bioaerosols (e.g., Legionella pneumophila, Histoplasma
capsulatum or Pneumocystis carinii) are very difficult, if not impossible, to
collect and culture [Ibach et al. 1954; Dennis 1990].
c. Identification of Culturable Bioaerosols
The science of classification, especially the classification of living forms, is called

taxonomy. The objective of taxonomy is to classify living organisms to establish the
relationship between one group of organisms and another, and to differentiate between
them. Several criteria and methods for the classification of culturable microorganisms
and the routine identification of some are discussed in the subsections that follow.
Besides using these methods, the nonviable and nonculturable methods of identification
discussed in Section 5 also may be used with culturable microorganisms.
(1) Classical or General Microbiology
Classical microbiology includes general methods for classifying or identifying

microorganisms. The least specific of these is the observation of growth
characteristics. Growth characteristics include the appearance of the
microorganisms in liquid medium, colonial morphology on solid medium, and
pigmentation.
On the cellular level of bacteria, cell shape, cell size, arrangement of cells, and
presence (absence) of flagella, capsule, or endospores are characteristic of
general classes of microorganisms. Simple and differential staining may be
performed on bacteria. Simple staining is a method of staining microorganisms
with a single basic dye that highlights cellular size, cellular shape, cellular
arrangement, and presence (absence) of flagella, capsule, or endospore using a
microscope. Stains such as methylene blue, carbolfuchsin, crystal violet, or
safranin may be used for bacteria. A stain that distinguishes among structures or

microorganisms based on reactions to the staining procedure is called a differential
stain. Two examples of differential stains are the Gram stain and the acid-fast
stain. The mechanism of the Gram stain may be explained on the basis of
physical differences in the cell walls of these two general groups of bacteria
(Gram-positive and Gram-negative). The Gram-positive bacteria possess a cell
wall composed of a relatively thick peptidoglycan layer and teichoic acids. Gram-
negative bacteria possess a cell wall composed of a thin peptidoglycan layer and
an outer membrane which consists of lipoproteins, lipopolysaccharides, and
phospholipids [Tortora et al. 1989]. A few of the commercially available
identification kits require a Gram-stain prescreening to assure that the correct
reagents are used. Some species of bacteria, particularly those of the genus
Mycobacterium, do not stain readily. In the acid-fast staining process, the
application of heat facilitates the staining of the microorganism.
In general, fungi are classified by spore morphology or colonial morphology.

Stains such as lactophenol cotton blue, periodic acid-Schiff stain, or potassium
hydroxide (10% KOH) may be used.
Biochemical, physiological, and nutritional tests for bacteria evaluate cell wall
constituents, pigment biochemicals, storage inclusions, antigens, temperature
range and optimum, oxygen relationships, pH tolerance, osmotic tolerance, salt
requirement and tolerance, antibiotic sensitivity, energy sources, carbon sources,
nitrogen sources, fermentation products, and modes of metabolism (autotrophic,
heterotrophic, fermentative, respiratory). As a rule, batteries of such tests, rather
than any one individual test, are used to identify or classify microorganisms. A few
commercially available test batteries are discussed in the following subsection.
Fungi are very difficult to classify [Smith 1990].
(2) Clinical and Environmental Microbiology
All identification systems should permit the efficient and reliable differentiation
between microorganisms. Several modifications of classical biochemical
procedures have been used in recent years to facilitate inoculation of media, to
decrease the incubation time, to automate the procedure, and to systematize the
determination of species based on reaction patterns. Historically, clinical
microbiological techniques are used for analysis of environmental samples.
However, clinical strains and environmental isolates may differ, requiring
modification of clinically-based techniques.
(I) Biochemical Analyses
Several commercial multitest systems have been developed for identification

of members of the family Enterobacteriaceae and other pathogenic
microorganisms because of the high frequency of isolation of Gram-negative
rods in clinical settings. These microorganisms are indistinguishable except
for characteristics determined by detailed biochemical testing. These

systems require that a pure culture be examined and characterized.
Following is a listing of commercially available identification kits: API® 20E
(Analytab Products, Plainview, NY); Enterotube II and R/B Enteric (Roche
Diagnostics Systems, Nutley, NJ; Hoffmann-La Roche & Co., AG, Basel,
Switzerland); Micro-ID (Organon Teknika-Cappel, Durham, NC); Minitek and
Sceptor (BBL Microbiology Systems, Cockeysville, MD); and MicroScan
(American Microscan, Inc., Sacramento, CA). Automated identification
systems include Quantum II (Abbott Laboratories, North Chicago, IL),
Autobac IDX (General Diagnostics, Warner-Lambert Co., Morris Plains, NJ),
and AutoMicrobic System (Vitek Systems, Inc., Hazelwood, MO). All ten of
these multitest systems have documented accuracies greater than 90% in
clinical settings [Baron and Finegold 1990; Koneman et al. 1988]. Biolog
(Biolog, Inc., Hayward, CA) is one of the newest multitest systems on the
market, but its application to environmental and clinical samples is not well
documented [Amy et al. 1992; Miller and Rhoden 1991].
(ii) Cellular Fatty Acid Analysis
Cellular fatty acids (CFA) of bacteria are structural in nature, occurring in the
cell membrane or cell wall of all bacteria. When the bacteria are grown
under standardized growth conditions, the CFA profiles are reproducible
within a genus, down to the subspecies or strain level in some
microorganisms. The Microbial Identification System (MIS), developed by
MIDI (Newark, DE), provides a chromatographic technique and software
libraries capable of identifying various microorganisms based on their CFA
composition [Sasser 1990a; Sasser 1990b]. The chromatographic
technique is also known as gas chromatography fatty acid methyl ester
analysis (GC-FAME). MIS has a database containing the analysis libraries
for cultivable Gram-negative and Gram-positive bacteria, and yeasts. In a
comparison study [Amy et al. 1992], only 8 of 18 isolates, identified by either
API multitest or MIDI MIS, were identified accurately using Biolog multitest.
A prototype method for extracting and analyzing fungi is currently being
distributed by MIDI.
d. Interpretation of Data
Generally speaking, the literature is divided on whether identification is necessary or

recommended. If clinical or research aspects of the investigation would benefit by
identification of the source of an etiologic agent, the following general guidelines are
suggested:
Dose-response data are not available for most microorganism exposures. Indoor
bioaerosol levels must be compared to outdoor levels or to an asymptomatic control
area. In general, indoor levels are lower than outdoor levels, and the taxa are similar
[ACGIH 1989, Step two, Fungi, and Bacteria; Solomon et al. 1980]. The Bioaerosol
Committee of the American Conference of Governmental Industrial Hygienists (ACGIH)
states that outdoor airborne fungi concentration "routinely exceeds 1000 CFU/m3 and

may average near 10,000 CFU/m3 in summer months." No occupational exposure limit
for bioaerosols has been promulgated by the Occupational Safety and Health
Administration (OSHA). ACGIH [1989, Bacteria] also states that concentrations of less
than 100 CFU/m3 may be unhealthy to immunosuppressed people. However, the
population of microorganisms must be evaluated for potential toxigenic microorganisms
or microorganisms which emit volatile organic compounds. A low airborne concentration
of microorganisms, in and of itself, does not indicate a clean and healthful environment.
Where local amplification and dissemination of bacteria have not occurred in an

occupied, indoor environment, Gram-positive cocci (e.g., Micrococcus and
Staphylococcus) are normally dominant [Morey et al. 1986]. ACGIH states that airborne
human skin scales and respiratory secretions may contain Gram-positive cocci.
Detection of high levels of these microorganisms are an indication of over-crowding and
inadequate ventilation. Indoor air that tests high for Gram-negative bacteria indicates a
need to identify and eliminate the source of contamination. Concentrations ranging from
4,500-10,000 CFU/m3 have been suggested as the upper limit for ubiquitous bacterial
aerosols [Nevalainen 1989; ACGIH 1989, Bacteria]. These exposure limits, however, do
not apply to pathogenic microorganisms.
Actinomycetes (mesophilic and thermophilic) are commonly found in agricultural areas.

Their presence in indoor environments is an indicator of contamination [ACGIH 1989,
Bacteria; Banaszak et al. 1970; Lacey and Crook 1988]. Thermophilic Actinomycetes
at concentrations above 70 CFU/m3 in an affected person's work area have been
regarded as the threshold for triggering remedial action [Otten et al. 1986].
5. ADDITIONAL IDENTIFICATION AND ENUMERATION PROCEDURES FOR NONVIABLE OR

VIABLE BIOAEROSOLS
Classifying nonviable and nonculturable microorganisms cannot be performed using the

methods described in the previous section. Identification of nonviable or nonculturable
microorganisms or components of microorganisms can be performed using microscopy and
molecular biology techniques. In addition, microscopy techniques may be used for
enumeration of suspensions of viable and nonviable microorganisms [McCrone 1973].
a. Microscopy
(1) Bright-Field or Light
In bright-field or light microscopy, an ordinary microscope is used for simple

observation or sizing. Visible light from an incandescent source is used for
illumination and the specimen appears against a bright backfield. Objects smaller
than 0.2 um cannot be resolved. The image contrast (visibility) decreases as the
refractive index of the substance/microorganism under observation and the
mounting medium become similar. To maximize the contrast, the mounting
medium should have the same refractive index as glass or the immersion oil.
Membrane filters are often "cleared" by using the appropriate immersion oil. This

method is commonly used to observe various stained (killed) specimens and to
count microorganisms. In addition, pollen grains and fungi spores are often
identified and enumerated in this manner [Eduard et al. 1990].
(2) Phase Contrast
Phase-contrast microscopy is used when the microorganism under observation

(e.g., Escherichia coli) is nearly invisible and an alternative mounting medium is
not possible or permissible. A phase-contrast microscope uses a special
condenser and diffraction plate to diffract light rays so that they are out of phase
with one another. The specimen appears as different degrees of brightness and
contrast. One cannot see an object exactly matching the refractive index of the
mounting liquid; however, very slight differences produce visible images. This type
of microscope is commonly used to provide detailed examination of the internal
structures of living specimens; no staining is required.
(3) Fluorescence
Fluorescence microscopy uses ultraviolet or near-ultraviolet source of illumination

that causes fluorescent compounds in a specimen to emit light. Fluorescence
microscopy for the direct count of microorganisms has been described in a number
of studies. Direct-count methods to enumerate microorganisms found in soil,
aquatic, and food samples have been developed using acridine orange [Palmgren
et al. 1986a, Palmgren et al. 1986b, Karlsson and Malmberg 1989]. More recently,
this method was applied to airborne microorganisms and it was concluded that it
is of the utmost importance to combine viable counts with total count enumeration
in the study of microorganisms in work-related situations [Palmgren et al. 1986a].
(4) Electron
Electron microscopy uses a beam of electrons instead of light. Because of the

shorter wavelength of electrons, structures smaller than 0.2 urn can be resolved.
Scanning electron microscopy (SEM) is used to study the surface features of cells
and viruses (usually magnified 1, 000-1 0.OOOX); and the image produced appears
three-dimensional. Also, SEM permits visualization of microorganisms and their
structure (e.g., single spores or cells, clumps, chains, size, shape, or other
morphological criteria). Viable microorganisms cannot be distinguished from
nonviable microorganisms [Donham et al. 1986; Karlsson and Malmberg 1989].
Transmission electron microscopy is used to examine viruses or the internal
ultrastructure in thin sections of cells (usually magnified 1 0,000-1 00, OOOX); and the
image produced is not three dimensional.
b. Endotoxin Assay
A virulence factor possessed by all Enterobacteriaceae (as well as other Gram-negative

bacteria) is the lipopolysaccharide, endotoxin, found in the outer membrane of the cell
wall. Individuals may experience disseminated intravascular coagulopathy, respiratory

tract problems, cellular and tissue injury, fever, and other debilitating problems.
Amebocytes are carried "within the blood-like circulating fluid" of the Limulus polyphemus
(horseshoe crab). After exposure to the lysed amebocyte cells, a liquid suspension
containing trace levels of endotoxin (lipopolysaccharides) will gel. This test is called the
Limulus amebocyte lysate (LAL) assay. Clinical microbiology laboratories use this assay
to test for contamination by Gram-negative bacteria [Baron and Finegold 1 990]. Airborne
endotoxin has been found in high concentrations in agricultural, industrial, and office
environments [Milton et al. 1990; Rylander and Vesterlund 1982]. Endotoxin aerosol
measurement techniques lack comparability between results obtained in different
laboratories because of differing sampling, extraction, and analytical methods
(generically called the Limulus method) [Rylander and Vesterlund 1982; Olenchock et
al. 1983; Jacobs 1989; Milton et al. 1990]. Concentrations of endotoxin, a
lipopolysaccharide found in the cell wall of Gram-negative bacteria, determined using the
LAL assay method, have been correlated with patient symptoms in very few studies
[Rylander and Vesterlund 1982; Milton et al. 1990].
c. Immunoassays
The immunoassay is an analytical technique for measuring a targeted antigen, which is

also referred to as an analyte. A critical component of the immunoassay is the antibody,
which binds a specific antigen. The binding of antibody and targeted antigen forms the
basis for immunoassay, and numerous formats have been devised which permit visual
or instrumental measurements of this reaction. Antibodies are commonly employed to
detect organisms by binding to antigens, usually proteins or polysaccharides, on the
surface or "coats" of organisms. The analysis is usually performed in a complex matrix
without the need for extensive sample cleanup. Many immunoassays are now readily
available from commercial sources, permitting laboratories to rapidly develop in-house
immunochemical analytical capability without lengthy antibody preparation. Some of the
more widely used formats are as follows:
(1) Radioimmunoassays (RIA)
Radiolabelled antigen is quantitatively added to antibody along with various

concentrations of unlabeled antigen. The unlabeled antigen competes with the
radiolabelled antigen for binding to the antibody. Thus, the higher the
concentration of unlabeled antigen in the sample, the lower the level of
radiolabelled antigen-antibody complexes. The unbound antigens are removed
prior to determining the amount of radiolabelled antigen-antibody formed. A
standard curve is then constructed showing the effect of known amount of
unlabeled antigen on the amount of radiolabelled antigen-antibody formed. It is
now possible to determine the amount of an unknown, unlabeled antigen present
in a sample by determining where the value is located on the standard curve
[Garvey 1977]. Alternatively, radiolabelled antibody is employed.

(2) Fluorescent Immunoassays (FIA)
Utilization of fluorescent-labeled antibodies to detect bacterial antigens was

introduced by Coons et al. [1941 and 1942]. Various FIA techniques have now
evolved. These are referred to as: (1) direct FIA, to detect antigen (cell-bound)
using fluorescent antibody; (2) indirect FIA, to detect antigen (cell-bound) using
antibody and fluorescent antigamma globulin antibody; and (3) indirect FIA, to
detect serum antibody using antigen, serum, and fluorescent antibody. Various
fluorescent dyes, such as fluorescein, fluorescein isothiocyanate, and rhodamine
isothiocyanate, may be employed. A fluorescent microscope is used to evaluate
the samples and to count the number of fluorescent organisms [Garvey et al.
1977]. FIA is used to detect viruses and microorganisms.
(3) Enzyme Immunoassays (EIA)
The binding of an antibody or antigen to an enzyme, such as horseradish

peroxidase (HRP) or alkaline phosphatase (AP), is the basis of EIA techniques.
Enzymatic activity, in the presence of a chromogen, results in a colored end-
product. Quantitation is performed using a spectrophotometer [Monroe 1984].
Many, if not most, commercially available ElAs are enzyme-linked immunosorbent
assays (ELISAs). In this competitive-binding EIA, the antibody is coated onto the
surfaces of test tubes, or wells of a microtiter plate, and antigen-containing
samples and enzyme-linked antigen are added, resulting in a color change. The
more intense the color, the less antigen or analyte are present in the sample.
ELISAs can be qualitative or quantitative. A standard curve must be generated if
quantitative results are desired. ELISAs are now highly automated and efforts are
underway to commercially develop well-standardized kits containing appropriate
controls and materials.
d. Gene Probes
Diagnostic bacteriology, virology, and mycology are rapidly adapting molecular biology
techniques in addition to classical identification methods to identify organisms. Thus,
diagnostic assays utilizing nucleic acid or DMA probes have now been developed for the
detection of numerous pathogenic organisms. Prior to employment of a DNA probe, it
must first be demonstrated that the DNA probe is highly specific for the targeted
organism. For example, a DNA probe for Mycobacterium tuberculosis (Mtb) should not
detect other Mycobacteria species. However, it should detect all Mtb isolates. Described
below are various types of DNA probes and formats used for the detection of organisms.

(1) Nick-translated DNA Probes
An isolated genomic DNA fragment is enzymatically disrupted and some of the

DNA bases replaced with highly radioactive DNA bases [Sambrook et al. 1989].
The radioactive probe is now tested for its ability to bind (hybridize) the extracted
DNA or RNA from the organism of interest. Prior to hybridization, the targeted
DNA or RNA is either fixed to a membrane, microscope slide or resuspended in
an aqueous buffer. After hybridization, the unbound DNA probe is then removed
and the specimen DNA or RNA analyzed for bound DNA probe. Alternatively,
nonradioactive labeling is often employed, but these probes, in general, are less
sensitive than use of phosphorus-32 (32P) labeled DNA [Goltz et al. 1990].
(2) Synthetic Oligomer DNA Probes
A short single-stranded DNA segment, usually 20-60 bases in length is designed

and chemically synthesized. If the precise DNA sequence of the targeted
organism is known, a complementary probe, representing a perfect match to the
targeted DNA is designed. However, the precise sequence of the targeted DNA
is often not known. Instead, the starting point for probe design is the amino acid
sequence. In this situation, because of codon degeneracy, a single probe
exhibiting exact complementarity cannot be designed. Thus, an educated guess,
based on understanding the genetic code and codon usage, is used to design the
probe. This type of probe usually exhibits a high degree of matching, although
seldom is a perfect match achieved. Alternatively, a set or "family" of probes is
synthesized. These are designed to cover all possible DNA sequences in the
targeted organism. The probes are labeled, usually with 32P, prior to hybridization
experiments [Sambrook et al. 1989].
(3) Polymerase Chain Reaction (PCR)
First introduced in 1985, the PCR has revolutionized the way DNA analysis is
conducted in clinical and research laboratories. Application of the PCR results in
the amplification (the in vitro enzymatic synthesis of thousands of copies) of a
targeted DNA [Saiki et al. 1985]. Two synthetic, single-stranded DNA segments,
usually 18-25 bases in length, are bound to the targeted DNA. These serve as
primers and permit the rapid enzymatic amplification of complementary DNA. The
method is extremely sensitive and specific. Culturing of the targeted organism
prior to DNA extraction is often not necessary. This approach has been
successfully utilized to detect various organisms including Mtb [Brisson-Noel et al.
1989; Wren et al. 1990; Eisenach et al. 1991].
(4) Restriction Fragment Length Polymorphic (RFLP) Analysis
RFLP is widely utilized to distinguish genetic changes within a species. A pure

clone of each of the organisms of interest must be generated using standard
culturing techniques. The genomic DNA is isolated and cut with a series of
restriction enzymes. Each of these enzymes cut double-stranded DNA at a

unique, short sequence of DNA bases, generating genomic DNA fragments of
various sizes [Sambrook et al. 1989]. The DNA fragments are examined by sizing
them on agarose gels. Eventually, the region(s) of altered DNA is detected. The
fragment appears as a different size when compared to the other isolates.
Confirmation may be accomplished by using gene probes as described above.

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Impaction Samplers
Andersen 6-Stage, 2-Stage, Aeroallergen Rotorod

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(800)241-6898 Volumetric Spore Traps (Indoor/Outdoor,
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P.O. Drawer 4259 Filtration Samplers
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(904) 628-0200 Samplers and Supplies
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(617)891-9380
Gelman Sciences Inc.
Reuter Centrifugal Sampler 600 South Wagner Road
BIOTEST Diagnostics Corp. Ann Arbor, Ml 48106
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(201)625-1300 Millipore Corporation
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Allergenco MK-2 (617)275-9200
Allergenco/Blewstone Press (800)225-1380
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Impingement Samplers General Molecular and Micro-
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7. REFERENCES
ACGIH [1989]. Step two: On-site investigation, pp. 1-8; Fungi, pp. 1-10; Bacteria, pp. 1-7.
Committee on Bioaerosols, eds. In: Guidelines for the assessment of bioaerosols in the indoor
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NIOSH MANUAL OF ANALYTICAL METHODS
4th EDITION
Peter M. Eller, Ph.D., CIH

Editor
Mary Ellen Cassinelli

Associate Editor
A-D

Division of Physical Sciences and Engineering
Cincinnati, Ohio
August 1994
ACETALDEHYDE by GC 2538
CH,CHO MW: 44.05 CAS: 75-07-0 RTECS: AB1 925000
METHOD: 2538, Issue 1 EVALUATION: UNRATED Issue 1: 15 August 1994
OSHA : 200 ppm PROPERTIES: liquid; d 0.78 g/mL @ 20 °C;

NIOSH: carcinogen; lowest feasible level BP 20.4 °C; VP 100 kPa (750 mm Hg)
ACGIH: C 25 ppm; suspect carcinogen @ 20 °C; explosive range 4 to 60% v/v
(1 ppm = 1.801 mg/m3 @ NTP) in air
SYNONYMS: acetic aldehyde; ethanal.
SAMPLER: SOLID SORBENT TUBE TECHNIQUE: GAS CHROMATOGRAPHY, FID

[2-(hydroxymethyl)piperidine (2-HMP)
on XAD-2, 450 mg/225 mg] ANALYTE: oxazolidine derivative of acetaldehyde
FLOW RATE: 0.01 to 0.05 L/min DESORPTION: 5 mL toluene, 60 min ultrasonic
VOL-MIN: 1 L @ 100 ppm INJECTION

-MAX: 12 L VOLUME: 1 //L, splitless
SHIPMENT: routine TEMPERATURE-INJECTION: 250 °C

-DETECTOR: 300 °C
SAMPLE -COLUMN: 70 °C 1 min; 6 °C/min
STABILITY: 100% recovery after 21 days @ 0 °C [1] to 110 °C (hold 2 min)
30 °C/min to 260 °C
BLANKS: 2 to 10 field blanks per set (hold 1 min)
CARRIER GAS: He, 1 mL/min; makeup 29 mL/min
COLUMN: wide-bore, fused-silica capillary,

ACCURACY 15 m x 0.32-mm; 1-//m DB-1301 film
RANGE STUDIED: 180 to 720 mg/m3 [2] CALIBRATION: standard solutions of acetaldehyde
(3-L samples) on coated sorbent
BIAS: 0.2% RANGE: 4 to 2200 fjg per sample [2]
OVERALL PRECISION (SrT): 0.12 [2] ESTIMATED LOD: 2//g per sample [1, 2]
ACCURACY: ± 23.7% PRECISION (Sr): 0.090 @ 26 to 107 fjg per sample [1]
APPLICABILITY: The working range is 0.74 to 407 ppm (1.3 to 730 mg/m3) for a 3-L air sample.
INTERFERENCES: None identified. An alternative chromatographic column is a 2 m x 6-mm OD x 2-mm ID glass column
containing 10% UCON 50-HB-5100 + 2% KOH on 80/100 Chromosorb W-AW.
OTHER METHODS: This is an adaptation of OSHA Method 68 [1], and is a convenient alternative to Method 3507.
NIOSH Manual of Analytical Methods (NMAM), Fourth Edition, 8/15/94

ACETALDEHYDE: METHOD 2538, Issue 2, dated 15 August 1994 - Page 2 of 4
REAGENTS: EQUIPMENT:
1. Toluene, chromatographic quality, containing 1. Sampler: glass tube, 11 cm long, 8-mm OD,
0.02% (v/v) dimethylformamide or other 6-mm ID, flame sealed ends with plastic caps,
suitable internal standard. containing two sections of 40/60 mesh 2-
2. Acetaldehyde*, high-purity. Store in freezer at (hydroxymethyl) piperidine coated on XAD-2
ca. -20 °C. and separated by 2-mm glass-wool plug (front
3. 2-(Hydroxymethyl)piperidine (2-HMP). = 450 mg; back = 225 mg). Tubes are
Recrystallize several times from isooctane until commercially available (Supelco, Inc.
there is one major peak (>95% of area) by GC ORBO-25 or equivalent), or may be prepared
analysis. Store in desiccator. (see APPENDIX B).
4. Calibration stock solution, 31.2 mg/mL 2. Personal sampling pump, 0.01 to 0.05 L/min.
(APPENDIX A) with flexible connecting tubing.
5. Helium, purified. 3. Gas chromatograph, capillary column, FID,
6. Hydrogen, prepurified. integrator (page 2538-1).
7. Air, filtered, compressed. 4. Vials, 7-mL, glass, with PTFE-lined screw caps.
5. Ultrasonic bath or mechanical shaker.
6. Pipets, volumetric, 1- and 5-mL with pipet
* See Special Precautions bulb.
7. Flasks, volumetric, 10- and 25-mL
8. Syringe, 10 //L, readable to 0.1 fjL.
SPECIAL PRECAUTIONS: Acetaldehyde is toxic if inhaled or if it comes in contact with the eyes or skin
[3], and is an animal carcinogen [4]. Exercise appropriate precautions in handling this chemical.
SAMPLING:
1. Calibrate each personal sampling pump with a representative sampler in line.

2. Break the ends of the sampler immediately before sampling. Attach sampler to personal
sampling pump with flexible tubing.
3. Sample at an accurately known flow rate between 0.01 and 0.05 L/min for a total sample size of
1 to 12 L
4. Cap the samplers. Pack securely for shipment.
SAMPLE PREPARATION:
5. Place front section and front glass-wool plug of the sampler in a vial. Place back section and
center glass-wool plug in a separate vial. Discard rear glass-wool plug.
6. Add 5.0 mL to toluene to each vial. Cap each vial tightly.
7. Agitate in an ultrasonic batch for 60 min.
CALIBRATION AND QUALITY CONTROL:
8. Calibrate daily with at least six working standards covering the range of the samples.
a. Place 450-mg portions of coated XAD-2 sorbent, from the same lot as used to collect the air
samples, into vials.
b. Inject known volumes of calibration stock solution or a serial dilution thereof onto the
sorbent to obtain acetaldehyde working standards in the range 2 to 2200 //g. Cap vials.
NOTE: Prepare working standards ca. 16 h before air samples are to be analyzed to ensure
that the reaction between acetaldehyde and 2-HMP is complete.
c. Prepare three media blanks.
d. Desorb (steps 5 through 7) and analyze (steps 10 and 11) the working standards and media
blanks along with the samples and field blanks.

_ACETALDEHYDE: METHOD 2538, Issue 2, dated 15 August 1994 - Page 3 of 4_
e. Prepare calibration graph, ratio of peak area of analyte/peak area of internal Standard vs. //g
acetaldehyde.
9. Analyze three quality control blind spikes and three analyst spikes to ensure that the calibration
graph is in control.
NOTE: A desorption efficiency study is not usually necessary since standards are prepared on
the coated sorbent.
MEASUREMENT:
10. Set gas chromatograph to conditions given on page 2538-1. Set air and hydrogen flows on the
flame ionization detector to manufacturer's specifications. Inject 1-/A. sample aliquot via the
splitless injection technique. Retention time = 6.8 min for acetaldehyde under these conditions.
11. Measure peak area. Divide the peak area of analyte by the peak area of the internal standard on
the same chromatogram.
CALCULATIONS:
12. Determine the mass, //g, of acetaldehyde found in the sample front (Wf) and back (Wb) sorbent
sections, and in the average media blank front (Bf) and back (Bb) sorbent sections.
NOTE 1: If Wb > Wf/10, report breakthrough and possible sample loss.
NOTE 2: Under these conditions, there is typically no detectable acetaldehyde blank level.
13. Calculate concentration, C, of acetaldehyde in the air volume sampled, V (L):
C - ( W" * - -
EVALUATION OF METHOD:
This method was originally developed and fully validated by OSHA [2} over the range 180 to 720 mg/m3
per sample. A storage study was done by spiking commercially-available tubes with standard solutions
of acetaldehyde [1]. Recovery (26.8 and 107 //g/sample) was 100% after 21 days of refrigerated
storage. A migration study was also performed at the above concentrations. After 21 days refrigerated
storage, no acetaldehyde was detected on the back sections of the samples. Additional evaluation
information is available [2]. Field samples of acetaldehyde were also successfully analyzed by utilizing
this method [1]. This method has not been evaluated by NIOSH, except for the storage and migration
studies.
REFERENCES:
[1] Williams, Karen J. Analytical Report for Acetaldehyde Samples, NIOSH (MRSB) Sequence
#6384, Unpubl. NIOSH (1988).
[2] "OSHA Analytical Methods Manual, " U.S. Dept. of Labor, Occupational Safety and Health
Administration, OSHA Analytical Laboratory, Salt Lake City, UT, Method #68 (1988).
[3] NIOSH/OSHA Occupational Health Guidelines for Occupational Hazards, U.S. Department of
Health and Human Services, Publ. (NIOSH) 81-123 (1981), available as GPO Stock #017-033-
00337-8 from Superintendent of Documents, Washington, DC 20402.
[4] IARC Monographs on the Evaluation of the Carcinogenic Risk of Chemicals to Humans: Allyl
Compounds, Aldehyde, Epoxides and Peroxides, International Agency for Research on Cancer
Vol 36:101-132 Lyon, France (1984).
METHOD REVISED BY:
Karen J. Williams.

APPENDIX A: PREPARATION OF CALIBRATION STOCK SOLUTION
Prepare by diluting a known amount of acetaldehyde with toluene:

a. Determine the weight of a sealed 25-mL volumetric flask containing approximately 15 mL of
toluene.
b. Place the sealed volumetric flask and a 1-mL pipet in the same freezer used to store the
acetaldehyde.
c. After 30 minutes, remove the sealed volumetric flask, 1-mL pipet and the acetaldehyde.
d. Immediately pipet 1.0 mL of acetaldehyde into the cold flask, reseal the flask and allow it to
warm to room temperature.
e. Reweigh the flask and subtract the tare weight from the weight of the reweighed flask to
determine the weight of acetaldehyde added.
f. Dilute the contents of the flask to the mark with toluene.
g. Store the stock standards in a freezer. Prepare fresh stock standards every 10 days.
APPENDIX B: PREPARATION OF XAD-2 SORBENT COATED WITH 2-HMP
Weigh 125 g of crude XAD-2 adsorbent into a 1-L Erlenmeyer flask. Add about 200 mL of water to the
flask and then swirl the mixture to wash the adsorbent. Discard any adsorbent that floats to the top of
the water and then filter the mixture using a fritted Buchner funnel. Transfer the adsorbent back to the
Erlenmeyer flask and repeat the water wash and the filtration. Air-dry the adsorbent for about 2 min.
Transfer the adsorbent back to the Erlenmeyer flask and then add about 200 mL methanol to the flask.
Swirl and filter the mixture as before. Transfer the washed adsorbent to a 1-L evaporative flask and
remove the methanol using rotary evaporation. Cool the flask to room temperature and add 13 g of 2-
HMP and 200 mL of toluene to the flask. Swirl the mixture and then allow it to stand for an hour.
Remove the toluene using rotary evaporation. Seal the flask and allow the coated adsorbent to stand
overnight at ambient temperature.
Transfer the coated adsorbent to a Soxhlet extractor. Extract the material with toluene for about 24
hours. Replace the contaminated toluene with fresh toluene and continue the extraction for an
additional 24 hours. Replace the second aliquot of contaminated toluene with methanol and continue
the Soxhlet extraction for 4 hours. Transfer the adsorbent to a weighed 1-L, round-bottomed,
evaporative flask and remove the methanol using the rotary evaporation apparatus. Determine the
weight of the adsorbent and then add an amount of 2-HMP, which is 10%, by weight, of the adsorbent.
Add 200 mL toluene and swirl the mixture. Allow the flask to stand for 1 hour. Remove the toluene
using rotary evaporation. If the last traces of toluene are difficult to remove, add about 100 mL of
methanol to the flask, swirl the mixture and then remove the solvents using rotary evaporation.
XAD-2 adsorbent treated in this manner will often contain residual formaldehyde derivative levels of
about 0.1 //g/150 mg of adsorbent. The formaldehyde blank level and potential acrolein and
acetaldehyde chromatographic interferences should be determined at this time. If the formaldehyde
blank and/or any interference is determined to be too high, return the lot to the Soxhlet extractor,
extract with toluene again and recoat with 2-HMP. This process can be repeated until an acceptable
blank and/or level of chromatographic interferences is attained.
The coated adsorbent is now ready to be packed into sampling tubes. The sampling tubes should be
stored in the dark and separated by lot number. A sufficient amount of each lot of coated adsorbent
should be retained to prepare analytical standards for use with air samples from that lot number.

ACETALDEHYDE by HPLC 3507
ChUCHO MW: 44.05 CAS: 75-07-0 RTECS: AB 1925000
METHOD: 3507, Issue 2 EVALUATION: FULL Issue 1: 15 August 1987

Issue 2: 15 August 1994

NIOSH: carcinogen; lowest feasible BP20.4 °C; MP -123 °C;
ACGIH: C 25 ppm; suspect carcinogen VP 100 kPa (750 mm Hg; 99% v/v)
(1 ppm = 1.801 mg/m3 @ NTP) @ 20 °C; explosive range 4 to 60% in air
SYNONYMS: ethanal; acetic aldehyde.
SAMPLER: LIQUID IN BUBBLER TECHNIQUE: HPLC, UV

(midget bubbler containing 15 mL
Girard T solution @ pH 4.5) ANALYTE: Girard T derivative
FLOW RATE: 0.1 to 0.5 L/min SAMPLE PREPARATION: dilute 5 mL sample to 100. mL
with HPLC mobile phase
VOL-MIN: 6 L @ 200 ppm
-MAX: 60 L INJECTION VOLUME: 50 fjL
SHIPMENT: seal bubblers to prevent leakage COLUMN: 50 cm x 2-mm ID SS, Zipax SCX
before shipping; protect from light
DETECTOR: UV @ 245 nm for acetaldehyde
SAMPLE STABILITY: 1 week @ 25 °C in dark [1]
MOBILE PHASE: HPOJ-/HPO; buffer,
FIELD BLANKS: 2 to 10 field blanks per set 0.75 mL/min
CALIBRATION: standard solutions of acetaldehyde

in Girard T reagent
ACCURACY
RANGE: 2 to 60 mg per sample [1]
RANGE STUDIED: 170 to 670 mg/m3 [1]
(60-L samples) ESTIMATED LOD: 0.1 mg per sample [1]
BIAS: 1.2%
PRECISION (Sr): 0.024 @ 11 to 43 mg per sample [1]
OVERALL PRECISION 0.053 [1]
ACCURACY: ± 14.4%
APPLICABILITY: The working range is 18 to 372 ppm (33 to 670 mg/m3) for a 60-L air sample. The method is sensitive
enough for short-term exposure sampling and can be used to measure lower concentrations by diluting samples to less than
the recommended 100 mL.
INTERFERENCES: Other volatile aldehydes and ketones (e.g., acetone, acrolein, benzaldehyde, formaldehyde, furfural, methyl
ethyl ketone, and propionaldehyde) compete for the Girard T reagent which should be kept at a two-fold molar excess over
aldehyde concentration. Chromatographic conditions may be adjusted to resolve acetaldehyde from other aldehydes [1].
OTHER METHODS: This revises S345 [2]. Method 2538 is an adaptation of OSHA Method 68, which uses solid sorbent
collection and GC analysis. Other reported methods for acetaldehyde use collection in 2,4-dinitrophenylhydrazine solution [3,4].

1. Acetaldehyde.* 1. Sampler: bubbler, glass, midget, with fritted

2. Citric acid. glass stems, annealed,* with PTFE stoppers
3. Disodium hydrogen phosphate (Na2HPO4). for shipping.
4. Girard T reagent [(carboxymethyl)- 2. Personal sampling pump, 0.1 to 0.5 L/min,
trimethylammonium chloride hydrazide] with trap made from midget bubbler with stem
recrystallized from 95% ethanol. broken off and inert, flexible connecting
5. Water, distilled, deionized (DD). tubing.
6. Ethanol, 95%. 3. High pressure liquid chromatograph, with 245-
7. Sodium dihydrogen phosphate monohydrate nm UV detector, integrator, and column (page
(NaH2PO4-H2O). 3507-1) with 50-//L injection loop or
8. Girard T solution: 5.39 g citric acid, 6.63 g autosampler.
Na2HPO4, and 16.77 g Girard T reagent diluted 4. Syringe, 2-mL, Luer-lock.
to 500 mL with DD water. Store in annealed 5. Distillation apparatus for preparation of high
flask in the dark. Use within two weeks. purity acetaldehyde.
9. HPLC mobile phase: 0.22 M Na2HPO4 • H2O, 6. Flasks, volumetric, 1-L; 10-, 50-, and 100-mL;
0.019 M NaH2PO4-H2O in 20% ethanol. and 500-mL, annealed.*
Dissolve and dilute 31.2 g Na2HPO4 and 26.2 7. Pipets, 0.02- to 1-mL; 5-, 10-, and 15-mL
g NaH2PO4- H2O to 1 L with DD water. Filter 8. Marker, glass.
through 5-fjm PTFE filter and degas prior to 9. Cylinder, graduated, 250-mL
use. Bubble helium through the solution to 10. Filter, 5-//m, PTFE, 37-mm, with holder for
prevent bacterial growth. liquid filtration.
10. Calibration stock solution, 4.32 mg/mL 11. Balance, readable to 0.1 mg.
acetaldehyde in 0.2 M Girard T solution.
Weight 216 mg freshly-distilled acetaldehyde * Heat in an oxidizing atmosphere
into 50-mL volumetric flask containing 49 mL at 580 °C.
Girard T solution. Make to volume with Girard
T solution. Use within one day.
11. Helium.
* See SPECIAL PRECAUTIONS.
SPECIAL PRECAUTIONS: Acetaldehyde is extremely volatile and a fire hazard. Cool containers of
acetaldehyde to ice bath temperature to reduce pressure buildup and open in an exhaust hood only.
SAMPLING:
1. Calibrate each personal sampling pump with a representative sampler and trap in line.
2. Add exactly 15 mL Girard T solution to each bubbler using a 15-mL pipet. Mark the initial liquid
level in the bubbler with a glass marker. Make impinger-to-trap and trap-to-sampling pump
connections with flexible inert tubing.
3. Sample at an accurately known flow rate between 0.1 and 0.5 L/min for a total sample size of 6
to 60 L
NOTE: Higher flow rates will cause frothing of the collection medium. If amount of liquid
condensed in the trap is greater than 1 mL, collection efficiency of bubbler may be
reduced and sample may be invalid.
SAMPLE PREPARATION:
4. Tap bubbler stem lightly against bubbler body to drain contents into the body. If necessary,
bring samples up to the 15-mL mark with distilled water. Swirl bubbler to mix contents well. Do
not add solution collected in the trap to the sample.

5. Transfer a 5-mL aliquot to a 100-mL flask and bring to volume with HPLC mobile phase.
6. Calibrate daily with at least six working standards over the range 0.007 to 4 mg acetaldehyde
per mL (0.1 to 60 mg acetaldehyde per sample).
a. Add known amounts of calibration stock solution to Girard T solution in 10-mL volumetric
flasks and dilute to the mark. Dilute 5 mL of each of these solutions to 100 mL with HPLC
mobile phase. Prepare at least two blanks in the same manner.
b. Analyze together with samples and blanks (steps 8 and 9).
c. Prepare calibration graph (peak area vs. mg acetaldehyde per sample).
MEASUREMENT:
8. Set liquid chromatograph according to manufacturer's recommendations and to conditions given

on page 2507-1. Inject 50-//L sample aliquot with injection loop or autosampler.
NOTE: If peak area is above the linear range of the working standards, dilute with HPLC mobile
phase, reanalyze, and apply the appropriate dilution factor in calculations.
9. Measure peak area.
CALCULATIONS:
10. Determine the mass, mg of acetaldehyde found in the sample (W), and in the average media
blank (B).
11. Calculate concentration, C, of acetaldehyde in the air volume sampled, V (L):
C . <" - °)
Method S345 was issued on March 16, 1979 [2], and validated over the range 170 to 670 mg/m3 at
21 °C and 756 mm Hg using a 60-L sample [1,5]. Overall precision, SrT, was 0.053 with an average
recovery of 101.2% representing a non-significant bias. The concentration of acetaldehyde was
independently verified by calibrated gas chromatograph. Collection efficiency of a single bubbler was
determined to be > 0.998 when 61 -L air samples were taken at 0.5 L/min in atmospheres containing 670
mg/m3 acetaldehyde.
REFERENCES:
[1] Backup Data Report, S345, Acetaldehyde, prepared under NIOSH Contract 210-76-0123
(unpublished).
[2] NIOSH Manual of Analytical Methods, 2nd ed., Vol. 5, S345, U.S. Department of Health,
Education, and Welfare, Publ. (NIOSH) 79-141 (1979).
[3] Kuwata, K., M. Uebori and Y. Yamasaki. J. Chromatoq. Scj., 17, 264-268 (1979).
[4] Lipari, F. and S.J. Swarin. J. Chromatog.. 247, 297-306 (1982).

[5] NIOSH Research Report-Development and Validation of Methods for Sampling and Analysis of
Workplace Toxic Substances, U.S. Department of Health and Human Services, Publ. (NIOSH)
80-133 (1980).
METHOD REVISED BY:
Eugene R. Kennedy, Ph.D., NIOSH/DPSE; Method S345 was validated under NIOSH Contract 210-76-
0123.

ACETIC ACID 1603
CH.COOH MW: 60.05 CAS: 64-19-7 RTECS: AF1 225000
METHOD: 1603, Issue 2 EVALUATION: FULL Issue 1: 15 May 1989


NIOSH: 10 ppm; STEL 15 ppm BP118 °C; MP 17 °C;
ACGIH: 10 ppm; STEL 15 ppm VP 1 .5 kPa (1 1 .4 mm Hg) @ 20 °C;
(1 ppm = 2.46 mg/m3 @ NTP) explosive range 5.4 to 16% v/v in air
SYNONYMS: glacial acetic acid; methane carboxylic acid; ethanoic acid

(coconut shell charcoal,
100 mg/50 mg) ANALYTE: acetic acid
FLOW RATE: 0.01 to 1.0 L/min DESORPTION: 1 mL formic acid; stand 60 min
VOL-MIN: 20 L@ 10 ppm INJECTION VOLUME: 5 /A.

-MAX: 300 L
TEMPERATURE-INJECTION: 230 °C
SHIPMENT: routine -DETECTOR: 230 °C
-COLUMN: 130 to 180 °C, 10°/min
SAMPLE or 100 °C isothermal
STABILITY: at least 7 days @ 25 °C
CARRIER GASES: N2 or He, 60 mL/min
BLANKS: 2 to 10 field blanks per set
COLUMN: 1 m x 4-mm ID glass; Carbopack B 60/80
mesh/3% Carbowax 20M/0.5% H3PO4
ACCURACY CALIBRATION: standard solutions of acetic acid

in 88 to 95% formic acid
RANGE STUDIED: 12.5 to 50 mg/m3 [1]
(173-L samples) RANGE: 0.5 to 10 mg per sample
BIAS: 5.4%
ESTIMATED LOD: 0.01 mg per sample [2]
OVERALL PRECISION (SrT): 0.058 [1]
PRECISION (Sr): 0.007 @ 0.3 to 5 mg per sample [1,3]
ACCURACY: ± 15.5%
APPLICABILITY: The working range is 2 to 40 ppm (5 to 100 mg/m3) for a 100-L air sample. High (90% RH) humidity during
sampling did not cause breakthrough at 39 mg/m3 for 4.6 hrs [1].
INTERFERENCES: Formic acid contains a small amount of acetic acid which gives a significant blank value. High-purity formic
acid must be used to achieve an acceptable detection limit. Alternate columns are 3-m glass, 2-mm ID, 0.3% SP-1000 + 0.3%
H3PO4 on Carbopack A and 2.4-m x 2-mm ID glass, 0.3% Carbowax 20M/0.1% H3PO4 on Carbopack C.
OTHER METHODS: This revises Method S169 [3].

ACETIC ACID: METHOD 1603, Issue 2, dated 15 August 1994 - Page 2 of 4
1. Formic acid, aqueous 88% to 95%, 1 . Sampler: glass tube with plastic caps, 7 cm
high-purity (<0.02% acetic acid).* long, 6-mm OD, 4-mm ID, flame-sealed ends,
NOTE: The acetic acid content varies containing two sections of activated (600 °C)
from lot to lot of formic acid. coconut shell charcoal (front = 100 mg; back
Test each lot before use. = 50 mg) separated by a 2-mm urethane foam
2. Glacial acetic acid, reagent grade.* plug. A silylated glass wool plug precedes the
3. Propionic acid, reagent grade. front section and a 3-mm urethane foam plug
4. Eluent: Formic acid, 88% to 95%, follows the back section. Pressure drop
with 0.1% v/v propionic acid or across the tube at 1 L/min airflow must be
other suitable internal standard. less than 3.4 kPa. Tubes are commercially
5. Nitrogen, purified. available.
6. Hydrogen, prepurified. 2. Personal sampling pump, 0.01 to 1 L/min, with
7. Air, filtered. flexible connecting tubing.
3. Gas chromatograph, flame ionization detector,
integrator and column (see page 1603-1).
4. Vials, 2-mL, PTFE-lined caps.
5. Syringes, 1 0-/A. and other convenient sizes for
preparing standards, readable to 0.1 //|_.
6. Volumetric flasks, 10-mL
* See Special Precautions
SPECIAL PRECAUTIONS: Care should be taken to avoid skin contact with formic acid and/or acetic
acid. These reagents may cause severe burns.
SAMPLING:

3. Sample at an accurately known flow rate between 0.01 and 1 L/min for a total sample size of 20
to 300 L
4. Cap the samplers and pack securely for shipment.
SAMPLE PREPARATION:
5. Place the front and back sorbent sections of the sampler tube in separate vials. Discard the
glass wool and foam plugs.
6. Add 1.0 mL eluent to each vial. Attach crimp cap to each vial.
7. Allow to stand 60 min with occasional agitation.
8. Calibrate daily with at least six working standards over the range 0.01 to 10 mg acetic acid per
sample.
a. Add known amounts of acetic acid to eluent in 10-mL volumetric flasks and dilute to the
mark.
b. Analyze together with samples and blanks (steps 1 1 and 12).
c. Prepare calibration graph (ratio of peak area of analyte to peak area of internal standard vs.
mg acetic acid).

9. Determine desorption efficiency (DE) at least once for each batch of charcoal used for sampling
in the calibration range (step 8). Prepare three tubes at each of five levels plus three media
blanks.
a. Remove and discard back sorbent section of a media blank sampler.
b. Inject a known amount of acetic acid directly onto front sorbent section with a microliter
syringe.
c. Cap the tube. Allow to stand overnight.
d. Desorb (steps 5 through 7) and analyze together with working standards (steps 11 and 12).
e. Prepare a graph of DE vs. mg acetic acid recovered.
10. Analyze three quality control blind spikes and three analyst spikes to insure that the calibration
graph and DE graph are in control.
MEASUREMENT:
11. Set gas chromatograph according to manufacturer's recommendations and to conditions given
on page 1603-1. Inject sample aliquot manually using solvent flush technique or with
autosampler.
NOTE: If peak area is above the linear range of the working standards, dilute with formic acid,
reanalyze and apply the appropriate dilution factor in calculations.
12. Measure peak area. Divide the peak area of analyte by the peak area of internal standard on the
same chromatogram.
CALCULATIONS:
13. Determine the mass, mg (corrected for DE) of acetic acid found in the sample front (Wf) and
back (Wb) sorbent sections, and in the average media blank front (Bf) and back (Bb) sorbent
sections.
NOTE: If Wb > W,/10, report breakthrough and possible sample loss.
14. Calculate concentration, C, of acetic acid in the air volume sampled, V (L):
C . (W.»Wt-B,-Bt)
Method S169 was issued on May 13, 1977 [3], and validated over the range 12.5 to 50 mg/m3 at 22 °C
and 767 mm Hg using a 173-L sample [1,4]. Overall precision, SrT, was 0.058 with an average recovery
of 105.4%, representing a non-significant bias. The concentration of acetic acid was independently
verified by a total hydrogen analyzer. Desorption efficiency was 0.96 in the range 2.1 to 8.4 mg per
sample. Breakthrough (5% on back section) was never achieved and testing was discontinued after 4.6
hrs when 10.4 mg of acetic acid was collected without breakthrough for a 269-L sample at 90% RH. A
user check gave an estimated LOD of 0.01 mg per sample and a desorption efficiency of 1.01 in the
range 0.3 to 5 mg per sample [2].
REFERENCES:
[1] Backup Data Report for Acetic Acid, prepared under NIOSH Contract No. 210-76-0123, available
as "Ten NIOSH Analytical Methods," Order No. PB 275-834 from NTIS, Springfield, VA 22161.
[2] User check, UBTL, NIOSH Sequence #4213-K (unpublished, January 31, 1984).
[3] NIOSH Manual of Analytical Methods, 2nd ed., V. 4, S169, U.S. Department of Health, Education,
and Welfare, Publ. (NIOSH) 78-175 (1978).

Workplace Toxic Substances, U.S. Department of Health and Human Services, Publ.
(NIOSH) 80-133 (1980).
METHOD REVISED BY:
G. David Foley and Y. T. Gagnon, NIOSH/DPSE; S169 originally validated under NIOSH Contract
CDC-21 0-76-01 23.

ACETIC ANHYDRIDE 3506
(CH3CO)20 MW: 102.09 CAS: 108-24-7 RTECS: AK1 925000


NIOSH: C 5 ppm BP 139 °C; MP -73 °C;
ACGIH: C 5 ppm VP 4 mm Hg @ 20 °C;
(1 ppm = 4.17 mg/m3 @ NTP) explosive range 2.9 to 10.3% v/v in air
SYNONYMS: acetic acid anhydride; acetyl oxide
SAMPLER: LIQUID IN BUBBLER TECHNIQUE: VISIBLE ABSORPTION

(mixed bubbler with 10 mL alkaline SPECTROPHOTOMETRY
hydroxylamine)
ANALYTE: acetic anhydride-hydroxylamine-ferric
FLOW RATE: 0.2 to 1.0 L/min chloride complex
VOL-MIN: 25 L FINAL VOLUME: 50 mL

-MAX: 100 L
WAVELENGTH: 540 nm
SHIPMENT: hand delivery or special bubbler cases
CALIBRATION: complexed acetic anhydride
SAMPLE standards
STABILITY: > 4 days® 25 °C [1]
RANGE: 0.5 to 4 mg acetic anhydride
BLANKS: 2 to 10 field blanks per set per sample [2]
ESTIMATED LOD: 0.05 mg acetic anhydride per sample
ACCURACY PRECISION (Sr): 0.021 @ 1 to 4 mg acetic anhydride

per sample [1]
RANGE STUDIED: 9.35 to 37.4 mg/m3 [1]
(100-L samples)
BIAS: 4.9%
ACCURACY: ± 15.3%
APPLICABILITY: The working range is 1.2 to 10 ppm (5 to 40 mg/m3) for a 100-L air sample. The upper limit of the range may
be extended by diluting the sample with the collection medium prior to color development. The method is sensitive enough
for short-term (>5 min) determinations if a 5-cm or longer cuvette is used.
INTERFERENCES: Any substance containing a hydrolyzable carbonyl group, such as esters, acid chlorides, and aldehydes,
is an interference. The most likely interference to coexist with acetic anhydride in air is ketene [2,3].

ACETIC ANHYDRIDE: METHOD 3506, Issue 2, dated 15 August 1994 - Page 2 of 4
1. Hydroxylamine hydrochloride solution. Dilute 1. Sampler: bubbler, standard midget glass,

200 g (NH3OH)CI to 1 L with distilled water in stem containing fritted end with porosity ca.
a volumetric flask. Refrigerate in a light- 170 to 220 mm maximum pore diameter with
protected container. Discard after two weeks. hard, non-reactive stopper (PTFE or glass).
2. Sodium hydroxide solution. Dissolve 200 g in 2. Personal sampling pump, 0.2 to 1 L/min, with
distilled water. Cool and bring to volume in a flexible connecting tubing.
1-L volumetric flask with distilled water. Store 3. Splashovertube: glass tube, 5cm long, 8-mm
in a polyethylene bottle. OD, 6-mm ID, loosely packed with glass wool.
3. Absorbing solution (needed for sampler). Mix 4. Spectrophotometer reading at 540 nm with
equal volumes of the hydroxylamine 5-cm matched cuvettes.
hydrochloride and sodium hydroxide solutions 5. Flasks, volumetric, 1-L and 50- and 100-mL
just prior to use. Do not use after 2 h. 6. Pipets, graduated, 1-, 5- and 10-mL
4. HChwater, 1:1 (v/v). Mix equal volumes of 7. Micropipets, 10- to 100-//L
conc. HCI and distilled water. 8. Ice bath.
5. Ferric chloride solution. Dissolve 100 g
FeCI3-6H2O in a 1-L volumetric flask with 1:1
(v/v) HChwater. Dilute to volume with this
mixture.
6. Acetone.
7. Acetic anhydride calibration stock solution.
Pipet 10 mL acetic anhydride* into a 100-mL
volumetric flask. Make to volume with
acetone. The solution must be used within
2 h of preparation.
SPECIAL PRECAUTIONS: Acetic anhydride is readily combustible (flash point = 54 °C) and both the
liquid and vapor produce irritation and necrosis of tissues. It may produce allergic sensitization of the
skin [4].
SAMPLING:
1. Calibrate the personal sampling pump with a representative sampler in line.

2. Connect a splashover tube between the bubbler and the sampling pump with short pieces of flexible
tubing. Do not allow the air being sampled to pass through any tubing or other equipment before
entering the bubbler.
3. Pour 10 mL of absorbing solution into bubbler.
NOTE: Absorbing solution must be prepared just prior to use (see REAGENTS, 3).
4. Sample at an accurately known flow rate between 0.2 and 1 L/min for a sample size of 25 to 100 L
Change sampler every 2 hrs so that the absorbing solution is fresh.
5. After sampling, remove the bubbler stem and tap gently against the inside of the bubbler tube.
Wash the stem with 1 to 2 mL absorbing solution and add the wash to the bubbler.
6. Seal the bubbler tightly with a hard, non-reactive stopper and transport the samples by hand.
Alternatively, transfer contents of each bubbler to a glass vial, rinsing bubbler with 1 to 2 mL
absorbing solution. Cap the vial securely for shipment.

SAMPLE PREPARATION:
7. Transfer sample solution to a 50-mL volumetric flask.

8. Rinse bubbler twice with 1 mL distilled water. Add rinses to the flask.
NOTE: For samples containing > 4 mg acetic anhydride, dilute an aliquot of the bubbler solution to
50 ml_ at this step. Apply the appropriate dilution factor in calculations.
9. Pipet 5 mL ferric chloride solution into the flask.
10. In an ice bath, mix equal volumes of sodium hydroxide solution, hydroxylamine hydrochloride
solution and ferric chloride solution. Add this solution to bring the solution in the 50-mL volumetric
flask to the mark. The purple complex is formed rapidly.
1 1 . Calibrate daily with at least six working standards over the range 0.05 to 4 mg acetic anhydride per
sample.
a. Pipet 10 mL absorbing solution into each of six 50-mL volumetric flasks.
b. Transfer 0 (reagent blank), 10, 20, 40, 80 and 100 fjL acetic anhydride calibration stock solution
into the flasks.
c. Add reagents (steps 9 and 10).
d. Analyze with samples and blanks (steps 12 through 14).
e. Construct calibration graph (absorbance vs. mg acetic anhydride).
MEASUREMENT:
12. Set spectrophotometer to read at 540 nm.

13. Adjust the baseline to zero with distilled water in both cells.
14. Read absorbance of the sample vs. reagent blank in the reference cell.
CALCULATIONS:
15. Determine the mass, mg, of acetic anhydride in the bubbler, W, and in the average media blank, B,
from the calibration graph.
16. Calculate the concentration, C (mg/m3), of acetic anhydride in the air volume sampled, V (L):
C - - - mg/m3.
Method S170 was issued on August 1, 1975 [2], and validated using 100-L air samples over the range
9.35 to 37.4 mg/m3 at 22 °C and 761 mm Hg [1]. Overall precision, SrT, was 0.060, with a collection
efficiency of 1.00 ± 0.01. The average of concentrations obtained at 20 mg/m3 for the overall sampling
and measurement technique was 2.5% higher than the true concentrations representing a non-significant
bias for a limited number of experiments [1]. Sample atmospheres were generated using the apparatus
and procedure for epichlorohydrin [5] and a total hydrocarbon analyzer was used to monitor the
generated vapor concentrations [1].

REFERENCES:
[1] Documentation of the NIOSH Validation Tests, S170, U.S. Department of Health, Education, and
Welfare, Publ. (NIOSH) 77-185 (1977), available as GPO Stock #017-033-00231-2 from
Superintendent of Documents, Washington, DC 20402.
[2] NIOSH Manual of Analytical Methods, 2nd ed., Vol. 3, S170, U.S. Department of Health, Education,
and Welfare, Publ. (NIOSH) 77-157-C (1977).
[3] Diggle, W. M. and J. C. Gage. The Determination of Ketene and Acetic Anhydride in the
Atmosphere, Analyst. 78, 473 (1953).
[4] NIOSH/OSHA Occupational Health Guidelines for Chemical Hazards, U.S. Department of Health and
Human Services, Publ. (NIOSH) 81-123 (1981), available as GPO Stock #017-033-00337-8 from
[5] Documentation of the NIOSH Validation Tests, op. cit., S118.
METHOD REVISED BY:
Robert W. Kurimo, NIOSH/DPSE.

ACETONE
See KETONES I (Method 1300) for procedure

ACETONE CYANOHYDRIN 2506
(CH3)2C(OH)CN MW: 85.11 CAS: 75-86-5 RTECS: OD9275000
METHOD: 2506, Issue 2 EVALUATION: PARTIAL Issue 1: 15 May 1985

OSHA : no PEL PROPERTIES: liquid; d 0.932 g/mL @ 19 °C;

NIOSH: C 1 ppm/15 min BP95 °C; MP -19 °C
ACGIH: no TLV VP 1 10 Pa (0.8 mm Hg) @ 20 °C
(1 ppm = 3.48 mg/m3
SYNONYMS: 2-cyano-2-propanol; 2-methyllactonitrile; 2-hydroxy-2-methylpropanenitrile
SAMPLER: SOLID SORBENT TUBE TECHNIQUE: GAS CHROMATOGRAPH, NP

(Porapak OS, 100 mg/ 50 mg) (THERMIONIC) DETECTOR
FLOW RATE: 0.2 L/min ANALYTE: acetone cyanohydrin
VOL-MIN: 0.3 L @ 1 ppm DESORPTION: 1 mL ethyl acetate; ultrasonicate 60 min

-MAX: 12 L
INJECTION VOLUME: 5 //L, 1 fjL flush
SHIPMENT: in refrigerated container @ 0 °C
TEMPERATURE-INJECTOR: 100 °C
SAMPLE -DETECTOR: 100 °C
STABILITY: at least 5 days if stored at @ 0 °C -COLUMN: 70 °C
immediately following collection
CARRIER GASES: N2, 33 mL/min
COLUMN: PTFE, 2 m x 3.2-mm ID, packed with 5%
OV-17 on 40/60 mesh Chromosorb T
(APPENDIX)
ACCURACY
CALIBRATION: solutions of acetone cyanohydrin in
RANGE STUDIED: 0.33 to 16.7 mg/m3 [1] ethyl acetate
(3-L samples)
RANGE: 1 to 50 fjg per sample
BIAS: not determined
OVERALL PRECISION (SrT): 0.093 [1] ESTIMATED LOD: 0.1 fjg per sample [1]
ACCURACY: not determined
PRECISION (Sr): 0.042 [1]
APPLICABILITY: The working range is 0.1 to 4.8 ppm (0.33 to 17 mg/m3) for a 3-L air sample. However, coadsorbed water
vapor will decompose the analyte unless the samples are refrigerated immediately after collection.
INTERFERENCES: Acetone, methyl methacrylate and methanol do not interfere with the analysis. Methacrylamide does not
elute from the column under the conditions given above. The gas chromatograph must be modified to eliminate contact of
analyte with heated glass or metal surfaces.
OTHER METHODS: This method was originally designated P&CAM 340 [2].

ACETONE CYANOHYDRIN: METHOD 2506, Issue 2, dated 15 August 1994 - Page 2 of 5
1. Desiccant, bagged, for field use. 1. Sampler: glass tube, 7 cm long, 6-mm OD,
2. Acetone cyanohydrin, 98% or better.* 4-mm ID; two sections (front = 100 mg; back
3. Ethyl acetate, chromatographic quality. = 50 mg) of pre-extracted 50/80 mesh
4. Silicone oil (OV-17). Porapak OS held in place and separated by
5. Coated Chromosorb-T, 40/60 mesh, for GC silanized glass wool plugs. Tubes are
stationary phase (APPENDIX). commercially available (SKC, Inc. #226-59-09,
6. Calibration stock solution, ca. 1.8 mg/mL or equivalent).
Inject 2.0 fjL acetone cyanohydrin into 1.0 2. Personal sampling pump, 0.01 to 0.2 L/min,
mL ethyl acetate. Compute the actual with flexible connecting tubing.
concentration from analyte density. 3. Refrigerant, bagged ("Blue Ice," or equivalent).
7. Nitrogen, purified. 4. Gas chromatograph, NPD, integrator and
8. Hydrogen, purified. column (page 2506-1 and APPENDIX).
9. Air, filtered. 5. Vials, 2-mL, glass, PTFE-lined crimp caps.
6. Ultrasonic bath, water.
* See SPECIAL PRECAUTIONS. 7. Syringe, 10-//L, readable to 0.1 fjL.
8. Pipet, 1-mL, with pipet bulb.
9. Spatula.
SPECIAL PRECAUTIONS: Acetone cyanohydrin is extremely toxic; it is readily decomposed by water

to form hydrogen cyanide and acetone. Perform all work with the analyte in a hood. Avoid dermal
contact with acetone cyanohydrin. It is readily absorbed through the skin and will decompose in the
body, with release of HCN, to induce cyanosis [3].
SAMPLING:

2. Break ends of the sampler immediately before sampling. Attach sampler to personal sampling
pump with flexible tubing.
3. Sample at an accurately known flow rate between 0.1 and 0.2 L/min for a total sample size
between 0.3 and 12 L
4. Cap the samplers with PTFE tape and plastic (not rubber) caps. Pack the samplers in a plastic
bag containing bagged refrigerant. Ship in a refrigerated container at 0 °C.
SAMPLE PREPARATION:
5. Bring the samples to room temperature before uncapping. Remove the end caps from the
sorbent tube.
6. Remove the front glass wool plug. Place it in a vial along with the front (larger) sorbent section.
Transfer the separating glass wool plug along with the back sorbent section to a separate vial.
7. Add 1 .0 mL ethyl acetate to each vial. Attach crimp cap to each vial.
8. Agitate the samples in an ultrasonic waterbath for 60 min.
9. Calibrate daily with at least six working standards over the range 0.1 to 50 fJQ acetone
cyanohydrin per sample.
a. Add aliquots of calibration stock solution or a serial dilution thereof to 1.0 mL ethyl acetate
in 2-mL vials. Attach crimp cap to each vial.
c. Prepare calibration graph (peak area vs. //g acetone cyanohydrin).

10. Determine desorption efficiency (DE) at least once for each lot of samplers used for sampling in
the calibration range (step 9). Prepare three tubes at each of five levels plus three media blanks.
b. Inject a known amount of calibration stock solution or a serial dilution thereof directly onto
front sorbent section with a microliter syringe.
d. Desorb (steps 6 through 8) and analyze together with working standards and blanks (steps
12 and 13).
e. Prepare a graph of DE vs. //g acetone cyanohydrin recovered.
MEASUREMENT:
on page 2506-1. Inject sample aliquot manually using solvent flush technique, or auto sampler.
tr = 3.2 min under these conditions.
NOTE: If peak area is above the linear range of the working standards, dilute an aliquot of the
sample solution with ethyl acetate, reanalyze and apply the appropriate dilution factor in
calculations.
CALCULATIONS:
14. Determine the mass, fjg (corrected for DE) of acetone cyanohydrin found in the sample front
(Wf) and back (Wb) sorbent sections, and in the average media blank front (Bf) and back (Bb)
sorbent sections.
NOTE: If Wb > Wf/10, report breakthrough and possible sample loss.
15. Calculate concentration, C, of acetone cyanohydrin in the air volume sampled, V (L):
0 .
EVALUATION OF METHOD [1]:
Calibration curve: Over the range 2.5 to 250 ng acetone cyanohydrin injected (0.5 to 50 //g per sample),
the correlation coefficients of NPD response with mass injected ranged from 0.998 to 0.999 for peak
height and from 0.990 to 0.996 for peak area.
Recovery of spiked samples after storage for one week at room temperature was >98% over the range
0.5 to 50 //g per sample. Independent verification of sample concentrations generated dynamically was
not possible. The method was evaluated by evaporating 1, 10 or 50 //g of analyte from U-tubes onto the
sorbent tube. Three liters of humid air (RH = 80%) were then drawn through the tube at 0.2 L/min for
15 min. Two sets of six samples at each level were generated. One set of six samples at each level
were stored for one day at room temperature. The other sample sets were stored for five to seven days
at 0 °C. Recovery was > 89% (sr = 10.6%). Experiments also showed that storage of 1 or 10 //g
samples collected as above, but stored at ambient temperature for four days, gave recoveries of 62 to
80%.
A maximum of 2% mass breakthrough to the backup section was obtained when 10 to 100 //g aliquots
of analyte were evaporated from U-tubes into a stream of humidified air (RH = 80%) onto the sorbent at
0.2 L/min for 60 min. Recovery from the primary sorbent section for all samples was > 92%.

REFERENCES:
[1] Glaser, R. and P. Fey. Development of a Quantitative Sampling and Analytical Method for Acetone
Cyanohydrin in Air (1981), available as Order No. PB 83-139-444 from NTIS, Springfield, VA 22161.
[2] NIOSH Manual of Analytical Methods, 2nd. ed., V. 7, P&CAM 340, U.S. Department of Health and
Human Services, Publ. (NIOSH) 81-141 (1981).
[3] Criteria for a Recommended Standard. ..Occupational Exposure to NitriIes, U.S. Department of
Health, Education, and Welfare, Publ. (NIOSH) 78-212 (1978).
METHOD WRITTEN BY:
Robert Glaser, NIOSH/DPSE.
APPENDIX: COLUMN PREPARATION AND GC MODIFICATION
1. Stationary phase preparation:
Weigh 10 g Chromosorb T into a glass Petri dish or small bowl. Dissolve 0.5 g OV-17 in 50 ml_
acetone; pour this solution over the Chromosorb T. Using a small spatula, slowly stir the stationary
phase into the solution while evaporating the solvent away under a stream of nitrogen. Avoid
crushing the soft Chromosorb T. A portion of the coated Chromosorb T will adhere to the glass; do
not attempt to recover this material. Continue to stir the support into the solution until the solvent
has completely evaporated. After the solvent has evaporated, allow the coated Chromosorb T to dry
completely under the nitrogen stream. Refrigerate the coated Chromosorb T at 0 °C until it is
packed into the GC column.
2. Column preparation, GC modification:
Although the column dimensions are 2 m long x 3.2-mm ID, a longer piece of PTFE tubing (2.3 m)
should be used in order to allow fitting to the chromatograph. Measure the length of the injector
zone from the injector port to the point of column attachment in the oven. Push a plug of silanized
glass wool this distance (about 10 to 20 cm) into the front (injector) end of the column. Add the
packing material from the other end of the column under vacuum to a point about 1 cm before the
detector end of the column. A 2-m column requires ca. 5 g of packing material. Seal the detector
end of the column with a 0.5-cm plug of silanized glass wool. If it is necessary to replace transfer
lines (see below), do not fill the column completely; leave about 1 cm open at the detector end after
insertion of the glass wool. Use plastic (nylon, PTFE, etc.) compression fittings to connect the
column to the instrument. Slide the injection port compression fittings onto the column directly over
the silanized glass wool plug. Remove the septum retainer fitting, the septum, and the injector liner
from the GC injection port. Push the empty end of the column through the oven side of the
injection port to the point where it is just flush with the external port opening. If the column is made
from thin-walled PTFE tubing, do not tighten the compression fitting over the soft column packing;
otherwise, the Chromosorb T may be crushed and a plug may develop that will block carrier flow.
Trim any column overhang away from the outer edge of the injection port. It may be necessary to
slide a small piece of oversize glass or PTFE tubing over the column into the injection port in order
to center the column with the septum retainer fitting. Be careful not to block any holes drilled in the
port for carrier flow. Gently tighten the compression fitting around the column over the glass wool
plug. Replace the septum and septum retainer fitting.

ACETONE CYANOHYDRIN: METHOD 2506, Issue 2. dated 15 August 1994 - Page 5 of 5
Because the analyte is thermally labile, it must not contact hot metallic or glass surfaces in the gas
chromatograph. To eliminate this contact, push the end of the column into the detector port up to
the detector itself. If the design of the instrument does not permit the column to be pushed up to
the detector, the transfer line from the end of the column to the detector must be replaced with low
dead-volume PTFE tubing. Use a 1.6-mm ID x 3.2-mm OD x 1 cm long PTFE plug to seal the
detector end of the column. Determine the length of transfer line needed from the column end fitting
to the bottom of the detector jet. Force a piece of 1.6-mm OD PTFE tubing equal to this length plus
the length of the PTFE plug, through the center to the back end of the plug. Insert the PTFE plug,
back end first, into the opening at the detector end of the column. Push the compression fitting
over the column where the PTFE plug was inserted. Attach the column to the chromatograph,
pushing the transfer line as close as possible to the bottom of the detector jet. Gently tighten the
compression fitting around the column. Once the column has been installed in the instrument,
pressurize it with nitrogen. Check the column for a flow of 33 mL/min. Check the compression
fittings for leaks; gently tighten them as necessary. After it has been determined that there is flow
through the column, condition it at 125 °C for 1 to 2 hrs. A diagram of a column where the transfer
line has been replaced is shown in Figure 1.
3.2 MM COMPRESSION
FITTING
1.0 MM O.D. TEFLON

TRANSFER LIN
INJECTOR DETECTOR
Figure 1. AII-PTFE gas chromatograph system used for the determination of acetone cyanohydrin.
NIOSH Manual of Analytical Methods (NMAM), Fourth Edition. 8/15/94

ACETONITRILE 1606
CH3CN MW:41.06 CAS: 75-05-8 RTECS: AL7700000
METHOD: 1606, Issue 2 EVALUATION: PARTIAL Issue 1: 15 February 1984

OSHA : 40 ppm PROPERTIES: liquid; d 0.783 g/mL @ 20 °C; BP 82 °C;

NIOSH: 20 ppm VP 12 kPa (89 mm Hg; 12% v/v) @ 25 °C
ACGIH: 40 ppm, STEL 60 ppm explosive range 4.4 to 16% v/v in air
(1.0 ppm = 1.68 mg/m3 @ NTP)
SYNONYMS: methyl cyanide; cyanomethane; ACN.

(coconut shell charcoal,
400 mg/200 mg) ANALYTE: acetonitrile
FLOW RATE: 0.01 to 0.2 L/min EXTRACTION: 5 mL benzene; stand 30 min

-MAX: 25 L VOLUME: 5.0 pL
SHIPMENT: routine TEMPERATURE-INJECTOR: 270 °C

-DETECTOR: 285 °C
SAMPLE -COLUMN: 180 °C
STABILITY: not determined
CARRIER GAS: N2 or He, 50 mL/min
COLUMN: stainless steel, 1.2 m x 8-mm O.D.,
packed with 50/80 mesh Porapak Q
ACCURACY CALIBRATION: solutions of acetonitrile in benzene
RANGE STUDIED: 31.4 to 140.2 mg/m3 [1] RANGE: 0.2 to 2 mg per sample
(10-L samples)
BIAS: 4.0%
OVERALL PRECISION (SrT): 0.072 [1] PRECISION (gr): 0.047 [1]
ACCURACY: ± 15.4%
APPLICABILITY: The working range is 12 to 120 ppm (20 to 200 mg/m3) for a 10-L air sample. Large (400 mg/200 mg)
charcoal tubes are necessary for collection of the analyte since breakthrough volume is low with smaller charcoal tubes. The
method was used in a NIOSH health hazard evaluation where an estimated limit of detection of 0.01 mg per sample was
reported [2]. The capacity of the charcoal for the analyte has not been determined under conditions of high relative humidity
[1].
INTERFERENCES: None identified.
OTHER METHODS: This is Method S165 [3] in a revised format.

ACETONITRILE: METHOD 1606, Issue 2, dated 15 August 1994 - Page 2 of 3
1. Acetonitrile, chromatographic quality. 1. Sampler: glass tube, 9.0 cm long, 8 mm OD,

2. Benzene, chromatographic quality.* 6-mm ID; two sections of 20/40 mesh
3. Calibration stock solution, 70 mg/mL Add activated (600 °C) coconut charcoal (front =
700 mg (0.894 mL) acetonitrile to a 10-mL 400 mg, back = 200 mg), separated by a 3-
volumetric flask. Dilute to the mark with mm section of urethane foam and held in
benzene.* place with plugs of silanized glass wool, flame-
4. Nitrogen, purified. sealed at both ends; plastic caps for tube.
5. Hydrogen, pre-purified. Tubes are commercially available.
6. Air, filtered. 2. Personal sampling pump, 0.01 to 0.2 L/min,
with flexible connecting tubing.
3. Gas chromatograph, FID, integrator and
column (page 1606-1).
4. Vials, glass, 10-mL, PTFE-lined crimp caps.
* See Special Precautions 5. Syringes, 10- to 50-//L, readable to 0.1 fjL;
1.0-mL, readable to 0.01 mL.
7. Pipets, delivery-type, 5.0-mL, with pipet bulb.
SPECIAL PRECAUTIONS: Benzene is a suspected human carcinogen. Perform all work with this
solvent in a hood.
SAMPLING:

2. Break the ends of the sampler immediately before sampling. Attach sampler to personal sampling
3. Sample at an accurately known flow rate between 0.01 and 0.2 L/min for a total sample size of 3 to
25 L
4. Cap the samplers with plastic (not rubber) caps and pack securely for shipment.
SAMPLE PREPARATION:
5. Place the front and back sorbent sections of the sampler tube in separate vials. Discard the glass
wool and foam plugs.
6. Add 5.0 mL benzene to each vial. Attach crimp cap to each vial.
NOTE: If desorption efficiency is acceptable, toluene may be substituted for benzene.
8. Calibrate daily with at least six working standards over the range 0.01 to 2 mg acetonitrile per
sample.
a. Add known amounts of calibration stock solution to benzene in 10-mL volumetric flasks and
dilute to the mark.
c. Prepare calibration graph (peak area vs. mg acetonitrile).
9. Determine desorption efficiency (DE) at least once for each batch of charcoal used for sampling in

_ACETONITRILE: METHOD 1606, Issue 2, dated 15 August 1994 - Page 3 of 3
b. Inject a known amount of calibration stock solution directly onto front sorbent section with a
microliter syringe.
e. Prepare a graph of DE vs. mg acetonitrile recovered.
MEASUREMENT:
11. Set gas chromatograph according to manufacturer's recommendations and to conditions given on
page 1606-1. Inject sample aliquot manually using solvent flush technique or with autosampler.
NOTE: If peak area is above the linear range of the working standards, dilute with benzene,
CALCULATIONS:
13. Determine the mass, mg (corrected for DE) of acetonitrile found in the sample front (W,) and back
(Wb) sorbent sections, and in the average media blank front (Bf) and back (Bb) sorbent sections.
14. Calculate concentration, C, of acetonitrile in the air volume sampled, V (L):
C . (W.
Method S165 was issued on August 1, 1975 [3]. Synthetic atmospheres of the analyte in dry air were
generated dynamically at 22 °C and 762 torr by the vapor pressure saturation/air dilution technique [1].
The concentrations ranged from 31.4 to 140.2 mg/m3; these were verified by total hydrocarbon analyzer.
Mean recovery was 105%. Breakthrough of the 400-mg front sorbent section occurred after sampling
140 mg/m3 for 190 min at 0.196 L/min (37.2 L). The desorption efficiency, over the range 0.346 to 1.383
mg per sample, averaged 81%. A DE correction factor was used to compute the total recovery of the
collected samples. Recovery of the analyte after long-term storage on the sorbent was not evaluated.
REFERENCES:
Welfare, Publ. (NIOSH) 77-185 (1977).
[2] NIOSH Health Hazard Evaluation Report HHE 81-359-1058 (1981).
[3] NIOSH Manual of Analytical Methods, 2nd. ed., V. 3, S165, U.S. Department of Health, Education,
and Welfare, Publ. (NIOSH) 77-1 57-C (1977).
METHOD REVISED BY:
Robert Glaser, NIOSH/DPSE; S165 originally validated under NIOSH Contract CDC-99-74-45.

ACIDS, INORGANIC 7903
(1) HF; (2) HCI; (3) H3PO4; MW: Table 1 CAS: Table 1 RTECS: Table 1
(4) HBr; (5) HNO3; (6) H2SO4
METHOD: 7903, Issue 2 EVALUATION: FULL Issue 1: 15 February 1984

OSHA : Table 1 PROPERTIES: Table 1

NIOSH: Table 1
ACGIH: Table 1
SYNONYMS: (1) hydrofluoric acid; hydrogen fluoride (5) nitric acid; aqua fortis
(2) hydrochloric acid; hydrogen chloride (6) sulfuric acid; oil of vitriol
(3) phosphoric acid; ortho-phosphoric acid; meta-phosphoric acid
(4) hydrobromic acid; hydrogen bromide
SAMPLER: SOLID SORBENT TUBE TECHNIQUE: ION CHROMATOGRAPHY

(washed silica gel, 400 mg/200 mg with
glass fiber filter plug) ANALYTE: F-, cr, PO43~, er, NO3-, so42"
FLOW RATE: 0.2 to 0.5 L/min DESORPTION: 10 mL 1.7 mM NaHCO3/1.8 mM
Na2CO3
VOL-MIN: 3 L
-MAX: 100 L INJECTION
LOOP VOLUME: 50 fjL
SHIPMENT: routine
ELUENT: 1.7 mM NaHCO3/1.8 mM Na2C03;
SAMPLE 3 mL/min
STABILITY: stable at least 21 days @ 25 °C [1]
COLUMNS: HPIC-AS4A anion separator,
BLANKS: 2 to 10 field blanks per set HPIC-AG4A guard, anion micro
membrane suppressor [2]
CONDUCTIVITY
ACCURACY SETTING: 10 //S full scale
RANGE STUDIED: see EVALUATION OF METHOD RANGE: see EVALUATION OF METHOD
BIAS: see EVALUATION OF METHOD ESTIMATED LOD: see EVALUATION OF METHOD
OVERALL PRECISION (S^): see EVALUATION OF METHOD PRECISION (Sr): see EVALUATION OF METHOD
ACCURACY: ± 12 to ± 23%
APPLICABILITY: The working range is ca. 0.01 to 5 mg/m3 for a 50-L air sample (see EVALUATION OF METHOD). This method
measures the total concentration of six airborne anions. The corresponding acids may be collected on a single sampler and
determined simultaneously. Formic acid has been determined by this method [3].
INTERFERENCES: Paniculate salts of all the acids will give a positive interference. Chlorine or hypochlorite ion interfere with
chloride determination and bromine interferes with bromide. Silica gel will collect ca. 30% of the free CI2 and Br, in an
atmosphere [4]. Acetate, formate and propionate have elution times similar to F and Cl . If these anions are present, use a
weak eluent (e.g., 5 mM Na2B,O7) for greater resolution.
OTHER METHODS: This is P&CAM 339 in a revised format [5]. Alternate methods are 7902 for fluoride and P&CAM 266 for
sulfate [6].

ACIDS, INORGANIC: METHOD 7903, Issue 2, dated 15 August 1994 - Page 2 of 6
1. NaHCO3, reagent grade. 1. Sampler: glass tube, 11 cm x 7-mm OD,

2. NaaCOa, reagent grade. containing a 400-mg front section and 200-mg
3. Distilled, deionized water, filtered through backup section of washed silica gel, flame-
0.45-//m membrane filter. sealed ends with plastic caps. Front section is
4. Eluent: bicarbonate/carbonate buffer solution retained with a glass fiber filter plug. Urethane
(1 .7 mM NaHCO3/1 .8 mM NajCOa). Dissolve plugs separate and retain the backup section.
0.5712 g NaHCO3 and 0.7631 g N^COj in 4 L Tubes are commercially available (Supelco
filtered deionized water. ORBO 53 or equivalent) or may be prepared
5. Calibration stock solutions, 1 mg/mL (as the according to APPENDIX.
anion). Dissolve salt in filtered deionized 2. Personal sampling pump, 0.2 to 0.5 L/min,
water. with flexible connecting tubing.
a. Fluoride: 0.2210 g NaF/100 mL 3. Ion chromatograph, HPIC-AG4A anion
b. Chloride: 0.2103 g KCI/100 mL separator and HPIC-AG4A anion micro
c. Phosphate: 0.1433 g KH2PO4/100 mL membrane suppressor, conductivity detector,
d. Bromide: 0.1288 g NaBr/100 mL integrator and strip chart recorder.
e. Nitrate: 0.1371 g NaNO3/100 mL 4. Waterbath: hotplate with beaker of boiling
f. Sulfate: 0.1814 g Ks,SO4/100 mL water.
5. Centrifuge tubes, 15-mL, graduated, plastic,
with caps.*
6. Syringes, 10-mL, polyethylene with luer tip.
* See SPECIAL PRECAUTIONS. 7. Filters, luer tip, with membrane filter, 13-mm,
O.Q-fjm pore size.
8. Micropipettes. disposable tips.
9. Volumetric flasks, 50- and 100-mL*
10. Laboratory timer.
11. Bottles, polyethylene, 100-mL
12. Auto sampler vials (optional).
* Thoroughly clean glassware with mild

detergent, rinse thoroughly with deionized
water, to minimize anion blank values.
SPECIAL PRECAUTIONS: Acids, particularly HF, are extremely corrosive to skin, eyes, and mucous
membranes. HF will attack glass. Plastic labware is recommended.
SAMPLING:

2. Break ends of sampler immediately before sampling. Attach sampler to personal sampling
to 100 L
NOTE: Do not exceed 0.3 L/min when sampling for HF.
SAMPLE PREPARATION:
4. Score sampler with a file in front of primary sorbent section.

5. Break sampler at score line. Transfer glass fiber filter plug and front sorbent section to a 15-mL
graduated centrifuge tube.

_ACIDS, INORGANIC: METHOD 7903, Issue 2, dated 15 August 1994 - Page 3 of 6_
NOTE: Particulate salts of the volatile acids (HCI, HB, HF, and HNO3), if present in the air
sample, will collect on the glass fiber filter plug. To estimate the concentration these
salts, analyze the plug separately from the front sorbent section.
6. Place backup sorbent section in separate centrifuge tube. Discard urethane plugs.
7. Add 6 to 8 mL eluent to each centrifuge tube. Heat in boiling waterbath for 10 min.
NOTE: Eluent used for desorption should be from same batch as the eluent used in the
chromatograph to avoid carbonate/bicarbonate peaks near F and CI".
8. Allow to cool, dilute to 10.0-mL volume with eluent.
9. Cap the centrifuge tube and shake vigorously.
10. Pour sample into 10-mL plastic syringe fitted with in-line filter.
11. Calibrate daily with at least six working standards covering the range 0.001 to 0.3 mg of each
anion per sample.
a. Add known aliquots of calibration stock solution to eluent in 50-mL volumetric flasks and
dilute to the mark.
b. Store working standards in tightly-capped polyethylene bottles. Prepare fresh working
standards weekly.
c. Analyze working standards together with samples and blanks (steps 12 through 14).
d. Prepare a calibration graph for each anion [peak height (mm or fjS) vs. concentration (/ug
per sample)].
MEASUREMENT:
12. Set ion chromatograph to conditions given on page 7903-1, according to manufacturer's
instructions.
13. Inject 50-//L sample aliquot. For manual operation, inject 2 to 3 mL of sample from filter/syringe
to ensure complete rinse of sample loop.
NOTE: All samples, eluents and water flowing through the IC must be filtered to avoid plugging
system valves or columns.
14. Measure peak height.
NOTE: If sample peak height exceeds linear calibration range, dilute with eluent, reanalyze and
apply the appropriate dilution factor in calculations.
CALCULATIONS:
15. Determine the mass, //g, of anion found in the sample front (Wf) and back (Wb) sorbent sections,
and in the average media blank front (Bf) and back (Bb) sorbent sections.
16. Calculate concentration, C, of acid in the air volume sampled, V (L):
, mg/m*.
where: F (conversion factor from anion to acid) = 1.053 for HF; 1.028 for HCI;
1.032 for H3PO4; 1.012 for HBr;
1.016 for HNO3; and 1.021 for H2SO4.
The method was evaluated for hydrochloric, hydrobromic, nitric, phosphoric and sulfuric acids by
laboratory generation of mixed acids [1]. Data for the individual analytes are:

Measurement Overall
Range Studied Precision Precision Accuracy Estimated LOP [2]
Acid (mg/m3) (//g/sample) (Sr (%) dig per sample)
HF[7] 0.35 - 6 0.5 - 200 0.7 0.053 0.116 ±23.4 0.7
HCI [8] 0.14 - 14 0.5 - 200 0.3 0.025 0.059 ± 1 1 .9 0.6
H3PO4[1] 0.5-2 3 - 100 -0.9 0.029 0.096 ±19.7 2.0
HBr [1] 2-20 3-960 2.0 0.056 0.074 ±16.5 0.9
HNO3 [1] 1-10 3-500 2.0 0.018 0.085 ±18.7 0.7
H2SO4 [1] 0.5-2 3 - 100 2.4 0.028 0.087 ±19.4 0.9
The method was field-evaluated at two electroplating facilities using side-by-side silica gel tubes and
bubblers. The method was evaluated for hydrofluoric acid in 1983 using the silica gel tubes and
impingers [7]. Recovery based on impinger collection was 106% with SrT of 0.116. The capacity of the
silica gel sampler for HF was 820 fjg. This is equivalent to an 8-h sample at two to three times the
OSHA PEL Samples were stable for at least 21 days at 25 °C. Updated analytical columns have been
used by NIOSH for analytical sequences [2].
REFERENCES:
[1] Cassinelli, M. E. and D. G. Taylor. Airborne Inorganic Acids, ACS Symposium Series 149,
137-152 (1981).
[2] DataChem, Inc. NIOSH Analytical Sequences #7546, #7357, and #7594 (unpublished, 1992).
[3] DataChem Laboratories, NIOSH Sequence #7923-C,D (unpublished, Jan. 25, 1994).
[4] Cassinelli, M.E. "Development of a Solid Sorbent Monitoring Method for Chlorine and Bromine
in Air with Determination by Ion Chromatography." Appl. Occup. Environ. Hvg. 6:215-226 (1991)
[5] NIOSH Manual of Analytical Methods, 2nd. ed., V. 7, P&CAM 339, U.S. Department of Health
and Human Services, (NIOSH) Publication No. 82-100 (1982).
and Human Services, (NIOSH) Publication No. 82-100 (1982).
[7] Cassinelli, M. E. "Laboratory Evaluation of Silica Gel Sorbent Tubes for Sampling Hydrogen
Fluoride," Am. Ind. HVQ. Assoc. J_., 47(41:219-224 (1986).
[8] Cassinelli, M. E. and P. M. Eller. Ion Chromatographic Determination of Hydrogen Chloride,
Abstract No. 150, American Industrial Hygiene Conference, Chicago, IL (1979).
METHOD WRITTEN BY:
Mary Ellen Cassinelli, NIOSH/DPSE.
APPENDIX: SAMPLING TUBE PREPARATION
Silica gel cleaning procedure: Add 500 to 600 mL deionized water, slowly and with stirring, to ca. 200
mL volume of silica gel in 1-L beaker. When exothermal reaction has subsided, heat in boiling water-bath
for ca. 30 min with occasional stirring. Decant and rinse four to five times with deionized water. Repeat
cleaning procedure and dry overnight in 100 °C oven until free flowing. If blank of silica gel shows
impurities upon analysis by ion chromatography, repeat cleaning procedure.

Silica gel tubes: Pack glass tubes, 7-mm OD, 4.8-mm ID, 11 cm long, with 400 mg of 20/40 mesh
washed silica gel in front section and 200 mg backup section. Use urethane foam plugs between
sorbent sections and at back end. Hold front section in place with 6-mm diameter, 1 -mm thick glass
fiber filter plug (Gelman 66088).

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ACROLEIN 2501
H,C = CHCHO MW : 56.07 CAS: 107-02-8 RTECS: AS 1050000

OSHA : 0.1 ppm PROPERTIES: liquid; d 0.8389 g/mL @ 20 °C;

NIOSH: 0.1 ppm; STEL 0.3 ppm; Group I Pesticide BP 52.5 °C; MP -88 °C; VP 28.5 kPa
ACGIH: 0.1 ppm, STEL 0.3 ppm (214 mm Hg; 28% v/v) @ 20 °C;
(1 ppm = 2.29 mg/m3 @ NTP) explosive range 2.8 to 31% v/v in air
SYNONYMS: 2-propenal; acrylicaldehyde; acrylaldehyde; allylaldehyde.
SAMPLER: SOLID SORBENT TUBE TECHNIQUE: GAS CHROMATOGRAPHY, NITROGEN-

(2-(hydroxymethyl)piperidine on SPECIFIC DETECTOR
XAD-2, 120 mg/60 mg)
ANALYTE: 9-vinyl-1-aza-8-oxabicyclo[4.3.0]nonane
FLOW RATE: 0.01 to 0.1 L/min
DESORPTION: 2 mL toluene; ultrasonic bath for 30 min
VOL-MIN: 13 L @ 0.1 ppm

-DETECTOR: 250 °C
SAMPLE -COLUMN: 90 °C for 8 min;
STABILITY: at least 4 weeks @ 25 °C [1] 20°C/min; hold® 200 °C
for 11 min
BLANKS: 2 to 10 field blanks and 10 media
blanks per set CARRIER GAS: Helium, 30 mL/min
COLUMN: 2 m x 2-mm glass, 5% SP-2401-DB on

ACCURACY Supelcoport (100-120 mesh)
RANGE STUDIED: 0.1 2 to 1.50 mg/m3 CALIBRATION: acrolein spiked on coated sorbent
(24-L samples)
BIAS: 7.0% RANGE: 3 to 36 fjg per sample
OVERALL PRECISION (SrT): 0.111 [1] ESTIMATED LOD: 2 fjg per sample
ACCURACY: ± 29%
PRECISION (Sr): not determined
APPLICABILITY: The working range is 0.05 to 0.2 ppm (0.13 to 0.5 mg/m3) for a 24-L air sample. For STEL measurements,
the limit of the method is 0.9 ppm for a 15-min sample at 0.1 L/min.
INTERFERENCES: None known. Peaks for acetaldehyde and formaldehyde oxazolidines may be observed in the
chromatogram, but they are resolved from the acrolein peak. Capacity of the sampler is reduced if sampling in air containing
acids [1].
OTHER METHODS: This method was developed to give improved sample stability and to provide for ease of personal sampling
compared to P&CAM 118 [2] and P&CAM 211 [2], which have not been revised.

ACROLEIN: METHOD 2501, Issue 2, dated 15 August 1994 - Page 2 of 4
1. Toluene, chromatography quality. 1 . Sampling tube: glass tube, 10 cm x 4-mm ID,

2. Acrolein,* freshly distilled under N2 to remove containing a 120-mg front section and a 60-mg
stabilizer. Store at 0 °C. back-up section of the 2- (hydroxymethyl)
3. 2-(Hydroxymethyl)piperidine. Recrystallize piperidine-coated XAD-2 (see APPENDIX) with
several times from isooctane until pure by GC flame-sealed ends. Sorbent sections are
analysis. Store in dessicator. retained and separated by small plugs of
4. XAD-2 (Amberlite - Rohm and Haas) or silanized glass wool. Pressure drop ca. 2.2
equivalent. Extract 4 h in soxhlet with 50/50 inches of water (756 Pa) at 0.10 L/min. Tubes
(v/v) acetone/methylene chloride. Replace are commercially available (Supelco ORBO 23
with fresh solvent and repeat. Vacuum dry or equivalent).
overnight. 2. Sampling pump, 0.01 to 0.1 L/min, with
5. Calibration stock solution, 1.0 //g///L Add flexible connecting tubing.
11.9 fjL acrolein to a septum-capped 10-mL 3. Vials, 4-mL, with septum and plastic screw
volume of toluene. caps.
4. Ultrasonic bath.
5. Pipettes, volumetric, 1- and 2-mL, with pipet
See Special Precautions bulb.
6. Flasks, volumetric, 10-mL
7. Pipettes, disposable, 2-mL
8. Syringes, 10-//L (readable to 0.1 fjL) and 25-
and 50-//L
9. Gas chromatograph, nitrogen-specific
detector, integrator and column (page 2501-1).
10. File.
SPECIAL PRECAUTIONS: Acrolein is an acute irritant and a potential fire hazard (flash point =
-17.8 °C); work with this compound only in a hood.
SAMPLING:

2. Score with a file and break the ends of the sampler immediately before sampling. Attach sampler to
personal sampling pump with flexible tubing.
3. Sample at an accurately known flow rate between 0.01 and 0.1 L/min for a total sample size of 1.5
to 48 L
NOTE: Sampling rate is limited by the speed of reaction of acrolein with the sorbent coating.
Sampling at rates above 0.10 L/min could cause appreciable acrolein breakthrough,
possibly invalidating the sample.
SAMPLE PREPARATION:
4. Score each sampler with a file in back of the rear sorbent section.
5. Break sampler at score line. Remove and place glass wool plug and rear sorbent section in a 4-mL
vial.
6. Transfer front section with the remaining glass wool plugs to a second 4-mL vial.
7. Add 2.0 mL of toluene to each vial. Screw cap tightly onto each vial.
8. Agitate vials by placing them in an ultrasonic bath for 30 min.

9. Calibrate daily with at least six standards covering the range of the samples.
a. Weigh ten 120-mg portions of the coated sorbent into 4-mL vials with septum caps. If the bulk
coated sorbent is not available, remove the front section from 10 unused samplers (media
blanks).
b. Inject aliquots of the calibration stock solution into the vials at six different levels and allow to
stand overnight at room temperature. Prepare two standards at each level.
c. Desorb (steps 7 and 8) and analyze together with samples and blanks (steps 10 and 11).
d. Prepare calibration graph (peak area or height vs. concentration of acrolein, //g/mL).
NOTE: The calibration procedure used in this method does not require a desorption efficiency
(DE) correction to be made. If DE is needed, see the APPENDIX.
MEASUREMENT:
10. Set gas chromatograph to conditions given on page 2501- 1. Set air and hydrogen flows on the
nitrogen specific detector to manufacturer's specifications. Inject 1-//L sample aliquot.
11. Measure peak area or peak height. Acrolein derivative tr = 3.6 min and tr for
2-(hydroxymethyl)piperidine = 10.7 min for these conditions.
CALCULATIONS:
12. Read the //g/mL of acrolein found in the sample front (Wf) and back (Wb) sorbent sections from the
calibration graph and multiply by the desorption volume, 2 (mL). Calculate concentration, C
(mg/m3), of acrolein in the air volume sampled, V (L):
NOTE: Because the working standards are prepared on media blanks, no additional blank
correction is necessary.
„ (Wf + Wb) • 2 .
C = f *' , mg/m3.
The method was evaluated over the range of 0.12 to 1.5 mg/m3 using 24-L samples. Average
desorption efficiencies were ca. 1.0 for all levels studied. Mean recovery was 107%, representing an
insignificant bias in the method [1]. Concentration of the generated acrolein vapor was independently
verified by a modification of P&CAM 211 by Shell Development Co. [3]. No breakthrough was observed
for an 8-h sample at 0.10 L/min (48 L) of a 4.5 mg/m3 of acrolein at 80% RH. The method has been
used by three separate analysts at NIOSH and no intralaboratory bias was observed. Measurement
precision (Sr) was not determined. Overall accuracy was ± 29%; therefore, the method does not meet
the ± 25% criterion for a valid method.
REFERENCES:
[1] Kennedy, E.R., O'Connor, P.P., Gagnon, Y.T. "Determination of Acrolein in Air as an Oxazolidine
Derivative by Gas Chromatography," Anal. Chem. 56(1 2) :21 20-21 23 (1984).
[2] NIOSH Manual of Analytical Methods, 2nd ed., V. 1, P&CAM 118 and 211, U.S. Department of
Health, Education, and Welfare, Publ. (NIOSH) 77-1 57-A (1977).
[3] Shell Development Company Analytical Department. Determination of Acrolein in Air,
Bubbler/Colorimetric Method, SRC 11A11/79, Shell Development Company Westhollow Research
Center.
METHOD WRITTEN BY:
Eugene R. Kennedy, Ph.D. and Paula Fey O'Connor, NIOSH/DPSE.

APPENDIX:
SORBENT PREPARATION
Add 1 g of the purified 2-(hydroxymethyl)piperidine in 50 mL of toluene for each 9 g of extracted XAD-2
sorbent . Allow this mixture to stand for 1 h with occasional swirling. Remove the solvent by rotary
evaporation at 37 °C and dry at 130 Pa (1 mm Hg) at ambient temperature for approximately 1 h. To
determine the amount of background for each batch, desorb several 120-mg portions of the coated
sorbent with toluene and analyze using steps 6 through 11. No blank peak is expected for acrolein
although a blank for formaldehyde and acetaldehyde may be observed.
DESORPTION EFFICIENCY
The determination of desorption efficiency (DE) is not necessary when using the calibration procedure
outlined in this method. The following procedure can be used to determine DE, if necessary:
a. Using a 10-//L syringe and the calibration stock solution inject four sampling tubes at each of
five levels. Open several blank tubes but add no acrolein to them. Cap all the tubes.
b. Using the 10-//L syringe, spike the calibration stock solution into 4-mL vials containing 2 ml_ of
toluene and 10 mg of purified 2-(hydroxymethyl)piperidine. Prepare four replicate vials at each
of the five concentrations used in step a.
c. Allow the spiked tubes, spiked standard solutions and blank tubes to stand overnight at ambient
temperature to assure complete reaction. Desorb and analyze the spiked and blank tubes
according to steps 4 through 11. Analyze the spiked solutions according to steps 10 and 11.
d. To calculate the recovery, compare the blank-corrected peak areas or heights of the acrolein
peak found in the spiked tubes (Qr - B) to the peak area or height of the acrolein peak found in
the spiked solutions (Qa).
e. Prepare a graph of DE vs. mg acrolein recovered.

ACRYLONITRILE 1604
CH,=CHCN MW : 53.06 CAS: 107-13-1 RTECS: AT5250000

OSHA : 2 ppm; C 10 ppm (skin) PROPERTIES: liquid; d 0.806 g/mL @ 20 °C;

NIOSH: carcinogen; 1 ppm; C 10 ppm/15 min; BP 77.2 °C; VP 1 1 kPa (83 mm Hg 1 1 % v/v)
Group I Pesticide (skin) @ 20 °C; explosive range 3 to 17% v/v in air
ACGIH: carcinogen; 2 ppm (skin)
(1 ppm = 2.17 mg/m3 @ NTP)
SYNONYMS: 2-propenenitrile; vinyl cyanide; AN.

(coconut shell charcoal, 100 mg/50 mg)
ANALYTE: acrylonitrile
DESORPTION: 1 mL 2% (v/v) acetone in CS2;.
VOL-MIN: 3.5 L @ 2 ppm stand 30 min
-MAX: 20 L
INJECTION VOLUME: 2 fjL
SHIPMENT: routine
STABILITY: at least 7 days @ 25 °C [1,2] -COLUMN: 85 °C
BLANKS: 2 to 10 field blanks per set CARRIER GAS: N2 or He, 25 mL/min
COLUMN: 3-m x 3-mm stainless steel, 20% SP-1000

on 80/100 Chromosorb WHP
ACCURACY CALIBRATION: standard solutions of distilled

acrylonitrile in hexane
RANGE STUDIED: 1 to 100 mg/m3 [1,2]
(20-L samples) RANGE: 15 to 1000 fjg per sample [1]
BIAS: - 4.8%
ESTIMATED LOD: 1 //g per sample [1]
OVERALL PRECISION (SrT): 0.06 [1,2]
PRECISION (Sr): 0.06 @ 16 //g per sample [1]
ACCURACY: ± 14.1%
APPLICABILITY: The working range is 0.7 to 46 ppm (1.5 to 100 mg/m3) for a 10-L air sample. This method is applicable to
15-minute ceiling measurements. NIOSH has sampled for acrylonitrile at acrylic and electric plants.
INTERFERENCES: None known. An alternate chromatographic column is a fused silica capillary, 30 m x 0.32-mm, coated with
0.5 //m DB-WAX or 1 //m DB-5.
OTHER METHODS: This revises NIOSH Method S156 [1,3] and Method 1604 (dated 2/15/84). P&CAM 202 has been dropped
because of poor sensitivity (LOD 0.1 mg per sample) [4]. Marano et al. [5] have shown that the use of a nitrogen selective
detector (NPD) increases the sensitivity and specificity of the analysis.

ACRYLONITRILE: METHOD 1604, Issue 2, dated 15 August 1994 - Page 2 of 4
1. Carbon disulfide, chromatographic quality.* 1. Sampler: glass tube, 7 cm long, 6-mm OD, 4-
2. Acetone, chromatographic quality. mm ID, flame-sealed ends with plastic caps,
3. Hexane, reagent grade. containing two sections of activated (600 °C)
4. Eluent: 2% acetone (v/v) in carbon disulfide.* coconut shell charcoal (front = 100 mg, back
5. Acrylonitrile, stabilized.* Stable at least one = 50 mg) separated by a 2-mm urethane foam
month at 4 °C. plug. A silylated glass wool plug precedes the
6. Acrylonitrile, freshly distilled.* front section and a 3-mm urethane foam plug
7. Calibration stock solution, 4 fjg/fjL. follows the back section. Pressure drop
Add 50 //L freshly distilled acrylonitrile across the tube at 1 L/min airflow must be
to 10 mL hexane. Stable one week at 4 °C. less than 3.4 kPa. Tubes are commercially
8. Helium, purified. available.
9. Hydrogen, prepurified. 2. Personal sampling pump, 0.01 to 0.2 L/min,
10. Air, filtered. with flexible connecting tubing.
* See Special Precautions integrator and column (page 1604-1).
4. Micro-distillation apparatus for vacuum
distillation of acrylonitrile.
5. Vials, 2-mL, PTFE-lined crimp caps.
6. Syringe, 10-//L and other sizes as needed,
readable to 0.1 juL
8. Pipets, 1-mL, with pipet bulb.
SPECIAL PRECAUTIONS: Carbon disulfide is toxic and a severe fire and explosion hazard (flash point
= -30 °C). Acrylonitrile is explosive, flammable, toxic, and a suspect carcinogen [3]. Work with these
compounds only in a hood.
SAMPLING:

2. Break the ends of the sampler immediately before sampling. Attach sampler to personal sampling
3. Sample at an accurately known flow rate between 0.01 and 0.2 L/min for a total sample size of 3.5
to 20 L
4. Cap the samplers pack securely for shipment.
SAMPLE PREPARATION:
5. Place the front and back sorbent sections of the sampler tube in separate vials. Discard the glass
6. Add 1 .0 mL eluent to each vial. Attach crimp cap to each vial.
NOTE: An internal standard, e.g., 0.1% (v/v) benzene or n-hexane, may be added at this step.
8. Calibrate daily with at least five working standards over the range 1 to 1000 fjg acrylonitrile per
sample.
a. Add known amounts of calibration stock solution, or a serial dilution thereof, to eluent in 10-mL
volumetric flasks and dilute to the mark with eluent (2% acetone in CS2).


c. Prepare calibration graph (peak area vs. //g acrylonitrile).
NOTE: Compare the peak areas of the working standards with a 0.1 mg/mL reference standard
prepared from stabilized (undistilled) acrylonitrile in hexane. When the concentration of
the working standards starts to decrease, prepare new working standards.
9. Determine desorption efficiency (DE) at least once for each batch of charcoal used for sampling in
microliter syringe.
d. Desorb (steps 5 through 7) and analyze together with working standards (steps 1 1 and 12).
e. Prepare a graph of DE vs. IJQ acrylonitrile recovered.
MEASUREMENT:
11. Set gas chromatograph according to manufacturer's recommendations and to conditions given on
page 1604-1. Inject sample aliquot manually using solvent flush technique or with autosampler.
NOTE 1 : If peak area is above the linear range of the working standards, dilute with eluent,
NOTE 2: Under these conditions tr for acrylonitrile is ca. 8.5 min.
CALCULATIONS:
13. Determine the mass, fjg (corrected for DE) of acrylonitrile found in the sample front (Wf) and back
14. Calculate concentration, C, of acrylonitrile in the air volume sampled, V (L):
Method S156 [2] was validated at levels of 0.48, 0.95, and 1.91 mg per sample, using samples of
acrylonitrile prepared both by sampling standard atmospheres generated by calibrated syringe drive and
by spiking standard solutions in hexane on to the charcoal [6].
After the OSHA standard for acrylonitrile was lowered to 2 ppm, the method was evaluated by NIOSH at
levels of 8.6 and 16.6 //g per sample (desorption solvent 2% acetone in CS2), using samples from gas
bag atmospheres and by spiking the charcoal with standard solutions of acrylonitrile in hexane [1]. At
the higher levels (> 16 fjg), the recoveries of acrylonitrile averaged 94% and the Sr was 0.06. At the
lower level (8.6 //g), the recovery for the two sets of samples prepared from standard atmospheres
averaged 79% with a Sr of 0.14. The sample set prepared by spiking charcoal at the lower level had a
recovery of 94%. The parity between the recoveries of samples obtained from test atmospheres and
from liquid spikes at the lower level suggested a possible problem with accuracy at this level [1].
Samples were found to be stable for at least seven days at room temperature [1,6]. Several
breakthrough studies have been reported. At 80% relative humidity, breakthrough occurred after 184
minutes (36.7 L) sampling 8 mg/m3 at 0.2 L/min [7]. Breakthrough did not occur after sampling dry air
at 92 mg/m3 at 0.2 L/min for 4 hours [6].
NIOSh Manual of Analytical Metnods (NMAM), Fourth Edition, 8/15/94

REFERENCES:
[1] Gagnon, Y.T. and Posner, J.C. Recovery of Acrylonitrile from Charcoal Tubes at Low Levels, Am.
Ind. Hyg. Assoc. J., 40, 923-925 (1979).
and Welfare, Publ. (NIOSH) 77-157-C (1977).
[3] Criteria for a Recommended Standard. ..Occupational Exposure to Acrylonitrile, U.S. Department of
Health, Education, and Welfare, Publ. (NIOSH) 78-116 (1978); revised Mar, 1978 as part of NIOSH
testimony at OSHA hearing.
[4] NIOSH Manual of Analytical Methods, 2nd ed., V. 1, P&CAM 202, U.S. Department of Health,
Education, and Welfare, Publ. (NIOSH) 77-1 57-A (1977).
[5] Marano, R.S., Levine, S.P. and T.M. Harvey. Trace Determination of Subnanogram Amounts of
Acrylonitrile in Complex Matrices by Gas Chromatography with a Nitrogen Selective Detector. Anal.
Chem.. 50, 1948 (1978)
[7] OSHA Report, Acrylonitrile Method 37, Organic Methods Evaluation Branch, OSHA Analytical
Laboratory, Salt Lake City, UT (May, 1982).
METHOD REVISED BY:
Y.T. Gagnon, NIOSH/DPSE; S156 originally validated under NIOSH Contract CDC-99-74-45.

ALCOHOLS I 1400
Table 1 MW: Table 1 CAS: Table 2 RTECS: Table 2


NIOSH: Table 2
ACGIH: Table 2
COMPOUNDS AND SYNONYMS: (1) ethanol: ethyl alcohol.

(2) isopropyl alcohol: 2-propanol.
(3) tert-butyl alcohol: 2-methyl-2-propanol.

ANALYTE: compounds above
(<0.05 L/min for ethyl alcohol) DESORPTION: 1 mL 1% 2-butanol in CS2
(1) (2) (3) INJECTION

VOL-MIN: 0.1 L 0.3 L 1.0 L VOLUME: 5 //L
-MAX: 1 L 3 L 10 L
SHIPMENT: cooled -DETECTOR: 250-300 °C
-COLUMN: 65-70 °C
SAMPLE
STABILITY: unknown, store in freezer CARRIER GAS: N2 or He, 30 mL/min
BLANKS: 2 to 10 field blanks per set COLUMN: glass, 2 m x 4-mm ID, 0.2% Carbowax
1500 on 60/80 Carbopack C or
equivalent
ACCURACY
CALIBRATION: solutions of analyte in eluent (internal
RANGE STUDIED: see EVALUATION OF METHOD standard optional)
BIAS: not significant [1]
RANGE AND
OVERALL PRECISION (SrT): see EVALUATION OF METHOD PRECISION: see EVALUATION OF METHOD
ACCURACY: ± 14%
APPLICABILITY: The working ranges are 16 to 1000 ppm ethanol (30 to 1900 mg/m3) for a 1-L air sample; 4 to 400 ppm
isopropyl alcohol (10 to 1000 mg/m3) for a 3-L air sample; and 1 to 100 ppm t-butyl alcohol (3 to 300 mg/m3) for a 10-L air
sample. This method employs a simple desorption and may be used to determine two or more analytes simultaneously by
varying GO conditions (e.g., temperature programming).
INTERFERENCES: High humidity reduces sampling efficiency. The methods were validated using a 3 m x 3-mm stainless steel
column packed with 10% FFAP on Chromosorb W-AW; other columns with equal or better resolution (e.g., capillary) may be
used. Less volatile compounds may displace more volatile compounds on the charcoal.
OTHER METHODS: This method combines and replaces Methods S56, S65 and S63 [3].

ALCOHOLS I: METHOD 1400, Issue 2, dated 15 August 1994 - Page 2 of 4
1. Eluent: Carbon disulfide* (chromatographic 1. Sampler: glass tube, 7 cm long, 6-mm OD,
grade) with 1% (v/v) 2-butanol and 0.2% v/v 4-mm ID, flame-sealed ends, containing two
n-undecane, 0.1% v/v ethyl benzene, or other sections of activated (600 °C) coconut shell
suitable internal standard. charcoal (front = 100 mg; back = 50 mg)
2. Analyte, reagent grade. separated by a 2-mm urethane foam plug. A
3. Nitrogen, purified. silylated glass wool plug precedes the front
4. Hydrogen, prepurified. section and a 3-mm urethane foam plug
5. Air, compressed, filtered. follows the back section. Pressure drop
across the tube at 1 L/min airflow must be
less than 3.4 kPa. Tubes are commercially
available.
2. Personal sampling pump, 0.01 to 0.2 L/min,
* See SPECIAL PRECAUTIONS. with flexible connecting tubing.
3. Refrigerant, bagged (Blue Ice, or equivalent).
6. Syringe, 10-//L, readable to 0.1 fjL.
SPECIAL PRECAUTIONS: Carbon disulfide is toxic and an acute fire and explosion hazard (flash point
= -30 °C); all work with it must be done in a hood.
SAMPLING:

0.1 to 1 L (ethanol), 0.3 to 3 L (isopropyl alcohol) or 1.0 to 10 L (t-butyl alcohol).
4. Cap the samplers with plastic (not rubber) caps and pack securely with bagged refrigerant for
shipment.
SAMPLE PREPARATION:
6. Add 1.0 mL el uent to each vial. Attach crimp cap to each vial.
a. Add known amounts of analyte to eluent in 10-mL volumetric flasks and dilute to the mark.
b. Analyze together with samples and blanks (steps 1 1 and 12).
mg analyte).
blanks.


b. Inject a known amount of analyte directly onto front sorbent section with a microliter syringe.
e. Prepare a graph of DE vs. mg analyte recovered.
MEASUREMENT:
autosampler.
NOTE: If peak area is above the linear range of the working standards, dilute with eluent,
same chromatogram.
CALCULATIONS:
13. Determine the mass, mg (corrected for DE) of analyte found in the sample front (Wf) and back
14. Calculate concentration, C, of analyte in the air volume sampled, V (L):
C =
Methods S56, S65 and S63 were issued on January 17, 1975 [3], and validated using 1-, 3- and 10-L air
samples, respectively, of atmospheres generated in dry air by calibrated syringe drive from absolute
ethanol, 2-propanol and t-butyl alcohol [1]. No stability studies were done. Overall precision and
recovery were as shown below, representing non-significant bias in each method:
Overall Measurement
Precision Recovery Ranae Studied Breakthrough Avg. Precision
Method ma/m3 mg per sample © 2X OSHA DE &)
S56 0.065 103.6 900 to 3300 1 to 4 1.6 L 0.79* 0.027

S65 0.064 96.7 505 to 1890 1 to 5 6.0 L 0.93* 0.033
S63 0.075 100.3 165 to 600 1 5 to 6 17.0 L 0.91* 0.018
*Over the range studied. Each laboratory must do their own DE determinations.

REFERENCES:
[1] Documentation of the NIOSH Validation Tests, U.S. Department of Health, Education, and
Welfare, (NIOSH) Publication No. 77-185 (1977).
[2] User check, UBTL, NIOSH Sequence #3990-5 (unpublished, November 3, 1983).
[3] NIOSH Manual of Analytical Methods, 2nd ed., V. 2., S56, S65 and S63, U.S. Department of
Health, Education, and Welfare, Publ. (NIOSH) 77-1 57-B (1977).
METHOD REVISED BY:
George Williamson, NIOSH/DPSE; methods originally validated under NIOSH Contract 99-74-45.
TABLE 1. PROPERTIES
VP@
mg/m3 Density 20 °C,
= 1 ppm @20 °C BP kPa
Compound Formula & NTP M.W. (a/mU (mm Ha)
Ethanol CH3CH2OH; 1.883 46.07 0.789 78.5 5.6

C2H6O (42)
Isopropyl alcohol CH3CH(OH)CH3; 2.46 60.09 0.785 82.5 4.4

C3H8O (33)
tert-Butyl alcohol (CH3)3COH; 3.03 74.12 0.786 82.4; 4.1

C4H10O MP = (31)
25.6 °C
TABLE 2. GENERAL INFORMATION.
EXPOSURE LIMITS (ppm)

COMPOUND OSHA NIOSH ACGIH CAS# RTECS#
Ethanol TWA 1000 1000 1000 64-17-5 KQ6300000
Isopropyl alcohol TWA 400 400 400 67-63-0 NT8050000

500 STEL 500 STEL
tert-Butyl alcohol TWA 100 100 100 75-65-0 EO 1925000

150 STEL

ALCOHOLS II 1401


NIOSH: Table 2
ACGIH: Table 2
COMPOUNDS (1) n-butyl alcohol: 1-butanol; n-Butanol; Propyl carbinol

and (2) sec-butyl alcohol: 2-butanol; methyl ethyl carbinol; 2-hydroxybutane.
SYNONYMS: (3) isobutyl alcohol: 2-methyl-1-propanol; isopropyl carbinol; IBA.
(4) n-propyl alcohol: 1-propanol; ethyl carbinol.

DESORPTION: 1 mL 1% 2-propanol in CS2
(1) (2) (3) (4)
VOL-MIN: 2 L 2 L 2 L 1 L INJECTION
-MAX: 10 L 10 L 10 L 10 L VOLUME: 5 //L

-DETECTOR: 250-300 °C
STABILITY: unknown; store in freezer
COLUMN: glass, 3 m x 2-mm ID, 10% SP-1000 on
80/100 mesh Chromosorb WHP, or
equivalent
ACCURACY
CALIBRATION: solutions of analyte in eluent (internal
RANGE STUDIED: see EVALUATION OF METHOD standard optional)
BIAS: not significant [1]
RANGE AND
OVERALL PRECISION (SrT): see EVALUATION OF METHOD PRECISION: see EVALUATION OF METHOD
ACCURACY: ± 15%
APPLICABILITY: This method may be used to determine two or more analytes simultaneously by varying GC conditions (e.g.,
temperature programming).
INTERFERENCES: The methods were validated using a 3 m x 3-mm ID stainless steel column packed with 10% FFAP on
Chromosorb W-AW; other columns with equal or better resolution (e.g., capillary) may be used.
OTHER METHODS: This method combines and replaces Methods S66, S53, S64 and S62 [3].

ALCOHOLS II: METHOD 1401, Issue 2, dated 15 August 1994 - Page 2 of 4
1. Eluent: Carbon disulfide* (chromatographic 1. Sampler: glass tube, 7 cm long, 6-mm OD,
grade) with 1% (v/v) 2-propanol and 0.2% 4-mm ID, flame-sealed ends, containing two
(v/v) n-undecane, 0.1% (v/v) hexane or other sections of activated (600 °C) coconut shell
suitable standard. charcoal (front = 100 mg; back - 50 mg)
2. Analyte. separated by a 2-mm urethane foam plug. A
3. DE stock solution, 100 mg/mL Prepare silylated glass wool plug precedes the front
solutions of each analyte in heptane. section and a 3-mm urethane foam plug
4. Nitrogen, purified. follows the back section. Pressure drop
5. Hydrogen, prepurified. across the tube at 1 L/min airflow must be
6. Air, compressed, filtered. less than 3.4 kPa. Tubes are commercially
available.
* See SPECIAL PRECAUTIONS. 3. Gas chromatograph, FID, integrator and
SAMPLING:

to 10 L (2 to 10 L for sec-butanol and isobutyl alcohol).
SAMPLE PREPARATION:
mg analyte).
blanks.

b. Inject a known amount of DE stock solution directly onto front sorbent section with a
microliter syringe.
MEASUREMENT:
autosampler.
1 2. Measure peak area. Divide the peak area of analyte by the peak area of internal standard on the
same chromatogram.
CALCULATIONS:
C .
Methods S66 (n-butyl alcohol), S53 (sec-butyl alcohol), S64 (isobutyl alcohol), and S62 (n-propyl
alcohol) were issued on January 17, 1975, and validated using 10-L air samples of atmospheres
generated by injection of the pure alcohol into dry air using a calibrated syringe drive [1]. No stability
studies were done. Overall precision and recovery were as shown below, representing non-significant
bias in each method:
Overall Breakthrough Measurement

Precision Recovery Range Studied @ 2X OSHA Avg. Precision
Method _(S,T)_ (%) mq/m3 mg per sample in Dry Air DE
S66 0.065 100.0 170 to 610 1.5 to 6 35 L 0.89 0.021

S53 0.066 107.2 270 to 850 2.2 to 9 15 L 0.92 0.028
S64 0.073 100.0 180 to 620 1.5 to 6 31 L 0.85 0.023
S62 0.075 103.5 225 to 835 2.5 to 10 19 L 0.89 0.016
REFERENCES:
[2] User check, UBTL, NIOSH Sequence #3990-X (unpublished, November 3, 1983).

[3] NIOSH Manual of Analytical Methods, 2nd ed., V. 2., U.S. Department of Health, Education, and
Welfare, Publ. (NIOSH) 77-1 57-B (1977).
METHOD REVISED BY:
George Williamson, NIOSH/DPSE; S53, S62, S64 and S66 originally validated under NIOSH Contract
99-74-45.
TABLE 1. PROPERTIES
VP @
mg/m3 20 °C,
= 1 ppm Density BP kPa
Compound Formula @NTP M.W. (g/mL) (°C) (mm Hg)
n-Butyl alcohol CH3CH2CH2CH2OH; 3.03 74.12 0.810 117 0.56

C4H100 @20°C (4.2)
sec-Butyl alcohol CH3CH(OH)CH2CH3; 3.03 74.12 0.808 99.5 1.7

C4H100 @20°C (13)
108
Isobutyl alcohol (CH3)2CHCH2OH; 3.03 74.12 0.806 1.2
C4H100 @15°C (9)
97
n-Propyl alcohol CH3CH2CH2OH; 2.46 60.09 0.805 2.0
C3H80 @20°C (15)
TABLE 2. GENERAL INFORMATION
Exposure Limits (ppm)
COMPOUND CAS# RTECS# OSHA NIOSH ACGIH
n-Butyl alcohol 71-36-3 E0 1400000 100 TWA C 50 (skin) C 50 (skin)
sec-Butyl alcohol 78-92-2 E0 1750000 150 TWA 100 TWA; 150STEL 100 TWA
Isobutyl alcohol 78-83-1 NP9625000 100 TWA 50 TWA 50 TWA
n-Propyl alcohol 71-23-8 UH8225000 200 TWA 200 TWA; 250 STEL 200 TWA; 250 STEL
(skin) (skin)

ALCOHOLS 1402
Table 1 MW: Table CAS: Table 2 RTECS: Table 2


NIOSH: Table 2
ACGIH: Table 2
COMPOUNDS (1) allyl alcohol: 2-propen-1-ol; 2-propenol; vinyl carbinol.

and (2) diacetone alcohol: 4-hydroxy-4-methyl-2-pentanone; 2-methyl-2-pentanol-4-one.
SYNONYMS: (3) cyclohexanol: hexalin; hydralin; hydroxycyclohexane; anol.
(4) isoamyl alcohol: 3-methyl-1-butanol; isobutylcarbinol; isopentyl alcohol.
(5) methyl isobulyl carbinol: MIBC; 4-methyl-2-pentanol; methyl amyl alcohol.

DESORPTION: 1 mL 5% 2-propanol in CS2; 30 min
VOL-MIN: 1 L
VOLUME: 5 //L
SHIPMENT: routine
SAMPLE -DETECTOR: 250-300 °C
STABILITY: unknown; store in freezer -COLUMN: 80-120 °C

80/100 mesh Supelcoport or equivalent
ACCURACY CALIBRATION: solutions of analyte in eluent (internal

standard optional)
RANGE STUDIED: see EVALUATION OF METHOD
RANGE AND
BIAS: see EVALUATION OF METHOD PRECISION: see EVALUATION OF METHOD
OVERALL PRECISION (SrT): see EVALUATION OF METHOD ESTIMATED LOD: 0.01 mg per sample [2]
ACCURACY: ± 20%
APPLICABILITY: The working range is 1 to 10 mg/m3 for allyl alcohol (other analytes range from 45 to 140 mg/m3 at low end
and 175 to 680 mg/m3 at high end of working ranges) for a 10-L air sample. This method may be used to determine two or
more analytes simultaneously by varying GC conditions (e.g., temperature programming).
INTERFERENCES: High humidity reduces sampling capacity. The methods were validated using a 3 m x 3-mm stainless steel
column packed with 10% FFAP on Chromosorb W-AW; other columns with equal or better resolution (e.g., capillary) may be
used. Less volatile compounds may displace more volatile compounds on the charcoal.
OTHER METHODS: This method combines and replaces Methods S52, S55, S54, S58 and S60 [3].

ALCOHOLS III: METHOD 1402, Issue 2, dated 15 August 1994 - Page 2 of 4
1. Eluent: Carbon disulfide* (chromatographic) Sampler: glass tube, 7 cm long, 6-mm OD,
with 5% (v/v) 2-propanol and 0.1% (v/v) 4-mm ID, flame-sealed ends, containing two
hexane, 0.2% (v/v) n-pentadecane or other sections of activated (600 °C) coconut shell
suitable internal standard. charcoal (front = 100 mg; back - 50 mg)
3. n-Heptane. silylated glass wool plug precedes the front
4. DE stock solution, allyl alcohol, 12 mg/mL in section and a 3-mm urethane foam plug
n-heptane. follows the back section. Pressure drop
5. Nitrogen, purified. across the tube at 1 L/min airflow must be
6. Hydrogen, prepurified. less than 3.4 kPa. Tubes are commercially
7. Air, compressed, filtered. available.
See SPECIAL PRECAUTIONS. 3. Gas chromatograph, FID, integrator and
SAMPLING:

to 10 L
SAMPLE PREPARATION:
a. Add known amounts of analyte or calibration stock solution to eluent in 10-mL volumetric
flasks and dilute to the mark.
mg analyte).
blanks.

ALCOHOLS III: METHOD 1402, Issue 2, dated 15 August 1994 - Page 3 of 4

b. Inject a known amount of analyte or DE stock solution directly onto front sorbent section
with a microliter syringe.
MEASUREMENT:
autosampler.
same chromatogram.
CALCULATIONS:
C .
Methods S52 (allyl alcohol), S55 (diacetone alcohol), S54 (cyclohexanol), S58 (isoamyl alcohol) and S60
(methyl isobutyl carbinol) were issued on January 17, 1975 [3], and validated using 10-L air samples of
atmospheres generated in dry air by calibrated syringe drive from the pure substances [1]. No stability
studies were done. Precision and recovery were as shown below, representing non-significant bias in
each method:
Overall Measurement
Method Precision Recovery Range Studied Breakthrough Avg. Precision
[1.31 mg/nr mq per sample (5) 2X OSHA DE (S.)
S52 0.111 98.8 1.8 to 8.4 0.02 to 0.1 >48 L 0.90 0.023
S55 0.104 91.8 140 to 510 1.1 to 4.7 >48L 0.78 0.054
S54 0.080 98.9 95 to 380 1 to 4 >48 L 0.99 0.015
S58 0.077 107.6 195 to 680 1.8 to 7 34 L 0.99 0.020
S60 0.080 101.8 45 to 175 0.5 to 2 >48 L 0.99 0.035

ALCOHOLS lII: METHOD 1402, Issue 2, dated 15 August 1994 - Page 4 of 4
REFERENCES:
[2] User check, UBTL, NIOSH Sequence #3990-V (unpublished, November 4, 1983).
[3] NIOSH Manual of Analytical Methods, 2nd ed., V. 2., U.S. Department of Health, Education, and
METHOD REVISED BY:
George Williamson, NIOSH/DPSE; methods originally validated under NIOSH Contract 99-74-45.
TABLE 1. PROPERTIES
VP@
mg/m3 20 °C,
= 1 ppm Density BP kPa
Compound Formula @NTP MW (g/mL) (mm Hg)
Ally! alcohol CH2=CHCH2OH; 2.37 58.08 0.854 96-97 2.3 (17)

C3H60 @20°C
Diacetone alcohol (CH3)2C(OH)CH2COCH3; 4.75 116.16 0.931 167.9 0.1 (0.8)

C6H1202 @25°C
Cyclohexanol C6H120 4.09 100.16 0.962 161; 0.13 (1.0)

MP =
24
Isoamyl alcohol (CH3)2CHCH2CH2OH; 3.60 88.15 0.813 132 3.7 (28)

C5H120 @15°C
Methyl isobutyl (CH3)2CHCH2CH(OH)CH3; 4.18 102.18 0.802 132 0.4 (3)

carbinol C6HM0
EXPOSURE LIMITS (ppm)
COMPOUND CAS# RTECS# OSHA NIOSH ACGIH
Allyl alcohol 107-18-6 BA5075000 2 TWA; (skin) 2 TWA; 4 STEL (skin) 2 TWA; 4 STEL
(Group I Pesticide) (skin)
Diacetone alcohol 123-42-2 SA9 100000 50 TWA 50 TWA 50 TWA
Cyclohexanol 108-93-0 GV7875000 50 TWA 50 TWA (skin) 50 TWA (skin)
Isoamyl alcohol 123-51-3 EL5425000 100 TWA 100 TWA; 125 STEL 100 TWA; 125 STEL
(skin)
Methyl isobutyl 108-11-2 SA7350000 25 TWA; (skin) 25 TWA; 40 STEL 25 TWA; 40 STEL
carbinol (skin) (skin)

ALCOHOLS IV 1403


NIOSH: Table 1
ACGIH: Table 1
COMPOUNDS (1) 2-methoxyethanol: methyl cellosolve; ethylene glycol monomethylether; EGME

and (2) 2-ethoxyethanol: cellosolve; ethylene glycol monoethylether, EGEE
SYNONYMS: (3) 2-butoxyethanol: butyl cellosolve; ethylene glycol monobutylether, EGBE

DESORPTION: 1 mL 5% methanol in CH2Cl2
(1) (2) (3)
VOL-MIN: 6 L 1 L 2 L INJECTION
-MAX: 50 L 6 L 10 L VOLUME: 5 //L

-DETECTOR: 250-300 °C
SAMPLE -COLUMN: (1) 95 °C; (2) 140 °C
STABILITY: unknown; store in freezer (3) 145 °C

80/100 mesh Chromosorb WHP, or
ACCURACY equivalent
RANGE STUDIED: see EVALUATION OF METHOD CALIBRATION: solutions of analyte in eluent (internal
standard optional)
BIAS: see EVALUATION OF METHOD
OVERALL PRECISION (SrT): see EVALUATION OF METHOD RANGE AND
PRECISION: see EVALUATION OF METHOD
ACCURACY: ± 17%
ESTIMATED LOD: 0.01 to 0.02 mg per sample [1]
APPLICABILITY: This method may be used to determine two or more analytes simultaneously by varying GO conditions (e.g.,
temperature programming).
INTERFERENCES: High humidity may reduce sampling capacity. The methods were validated using a 3 m x 3-mm stainless
steel column packed with 10% FFAP on Chromosorb W-AW; other columns with equal or better resolution (e.g., capillary) may
be used. Less volatile compounds may displace more volatile compounds on the charcoal.
OTHER METHODS: This method combines and replaces Methods S79 [2], S361 [3], and S76 [2]. Butyl cellosolve and butyl
cellosolve acetate are included in OSHA Method 83. Cellosolve and cellosolve acetate are included in OSHA Method 79. Both
of these OSHA methods are very similar to Method 1403.

ALCOHOL IV: METHOD 1403, Issue 2, dated 15 August 1994 - Page 2 of 4
1. Eluent: methylene chloride with 5% (v/v) 1. Sampler: glass tube, 7 cm long, 6-mm OD,
methanol and 0.2% (v/v) 1-heptanol, 0.1% 4-mm ID, flame-sealed ends, containing two
(v/v) ethyl benzene or other suitable internal sections of activated (600 °C) coconut shell
standard. charcoal (front = 100 mg; back = 50 mg)
3. Nitrogen, purified. silylated glass wool plug precedes the front
4. Hydrogen, prepurified. section and a 3-mm urethane foam plug
5. Air, compressed, filtered. follows the back section. Pressure drop
across the tube at 1 L/min airflow must be
available.
5. Syringe, 10-//L, readable to 0.1 //L
SPECIAL PRECAUTIONS: Methylene chloride is a carcinogen [4].
SAMPLING:

6 to 50, 2-methoxyethanol; 1 to 6, 2-ethoxyethanol; 2 to 10, 2-butoxyethanol.
NOTE: Maximum flow rate for 2-methoxyethanol and 2-butoxyethanol is 0.2 L/min.
SAMPLE PREPARATION:
mg analyte).
blanks.
b. Inject a known amount of analyte directly onto front sorbent section with a microliter syringe.


MEASUREMENT:
autosampler.
same chromatogram.
CALCULATIONS:
c.
Methods S79 (2-methoxyethanol), S361 (2-ethoxyethanol) and S76 (2-butoxyethanol) were issued on
February 14, 1975 [2,5], March 17, 1978 [3,6,7], and February 14, 1975 [2,5], respectively, and validated
using, respectively, 50-, 6- and 10-L air samples of atmospheres generated by calibrated syringe drive.
Storage stability of these alcohols was not determined. Precision and recovery were as shown below,
representing non-significant bias in each method:
Overall Measurement
Precision Recovery Ranqe Studied Breakthrough Avg. Precision
Method mq/m3 mq oer sample & 2X OSHA DE
S79 [1,4] 0.068 93 44 to 160 2 to 8 128 L* 0.98 0.008

S361 [2,5,6] 0.059 107 340 to 1460 2 to 7 >10 L** 1.02 0.009
S76 [1,4] 0.060 92 124 to 490 1 to 5 >44 L* 0.99 0.009
*Dry air.
**90% RH.
The method was also successfully checked for spiked samples of 2-butoxyethyl acetate [8].
REFERENCES:
[1] User check, UBTL, NIOSH Sequence #3990-Z (unpublished, November 3, 1983).
[2] NIOSH Manual of Analytical Methods, 2nd ed., V. 2., S76 and S79, U.S. Department of Health,
Education, and Welfare, Publ. (NIOSH) 77-1 57-B (1977).

[3] Ibid, V. 5, S361, U.S. Department of Health, Education, and Welfare, Publ. (NIOSH) 79-141
(1979).
[4] NIOSH Recommendations for Occupational Safety and Health, U.S. Department of Health and
Human Services (NIOSH) Publ. 92-100 (January, 1992).
[5] Documentation of the NIOSH Validation Tests, S76 and S79, U.S. Department of Health,
[6] Backup Data, S361, available as "Ten NIOSH Analytical Methods, Set 6," Order No. PB 288-629
from NTIS, Springfield, VA 22161.
[7] NIOSH Research Report, Development and Validation of Methods for Sampling and Analysis of
Workplace Toxic Substances, U.S. Dept. of Health and Human Services Publ. (NIOSH) 80-133
(1980).
[8] User Check, DataChem Laboratories, NIOSH Sequence #6960-J,K (unpublished, August 15,
1990).
METHOD REVISED BY:
George Williamson, NIOSH/DPSE; methods originally validated under NIOSH Contracts 99-74-45 and
210-76-0123.
Compound mg/m3 Density

CAS# Exposure Limits (ppm) = 1 ppm @ 20 °C BP
RTECS# QSHA NIOSH ACGIH Formula @ NTP MW (g/mL) (°C)
2-Methoxyethanol 25 (skin) 0.1 (skin) 5 (skin) HOCH2CH2OCHj 3.11 76.09 0.966 124 0.8 (6)
109-86-4
KL5775000
2-ethoxyethanol 200 (skin) 0.5 (skin) 5 (skin) HOCH2CH2OCH2CH3 3.68 90.12 0.931 135 0.5 (4)
110-80-5
KK8050000
2-butoxyethanol 50 (skin) 5 (skin) 25 (skin) HOCH2CH2O(CH2)3CH3 4.83 118.17 0.902 171 0.11 (0.8)
111-76-2
KJ8575000

ALDEHYDES, SCREENING 2539


NIOSH: Table 1
ACGIH: Table 1
COMPOUNDS: acetaldehyde; acrolein; butyraldehyde; crotonaldehyde; formaldehyde; furfural; heptanal; hexanal;

isobutyraldehyde; isovaleraldehyde; propionaldehyde; valeraldehyde.
SYNONYMS: Table 1
SAMPLER: SOLID SORBENT TUBE TECHNIQUE: GAS CHROMATOGRAPHY, FID & GC/MS
(10% 2-(hydroxymethyl)piperidine on XAD-2,
120 mg/60 mg) ANALYTE: oxazolidine prepared from aldehyde
FLOW RATE: 0.01 to 0.05 L/min DESORPTION: 1 mL toluene; 60 min ultrasonic
VOLUME: 5 L INJECTION
VOLUME: 1 fjL splitless; split vent time 30 sec
SHIPMENT: @ 25 °C or lower
STABILITY: at least 1 week @ 25 °C -COLUMN: 1 min @ 70 °C; 6 °C/min
to 100 °C for 2 min;
FIELD BLANKS: 2 to 10 field blanks per set 30 °C/min to 260 °C
MEDIA BLANKS: 6 per set CARRIER GAS: He, 0.5 mL/min; makeup flow, 29
mL/min
COLUMN: capillary, 15 m x 0.32-mm, 1.0-//m film

ACCURACY 6% cyanopropyl-phenyl, DB-1301 or
equivalent
RANGE STUDIED: not studied
CALIBRATION: standard solutions of aldehydes spiked
on sorbent
OVERALL PRECISION (SrT): not determined
RANGE AND
PRECISION: not determined
ESTIMATED LOD: 2 fjg aldehyde per sample
APPLICABILITY: This is a screening technique to determine the presence of aldehydes and should not be used for quantitation.
Further confirmation of aldehyde identification should be performed by gas chromatography/mass spectrometry (See Table 2
for structural ion data). Methods for quantitation of some aldehydes listed in this method are available in the NIOSH Manual
of Analytical Methods (See OTHER METHODS). All aldehydes tested have been detected by this method in bulk field samples.
INTERFERENCES: High-boiling naphtha mixtures, such as kerosene and mineral spirits may have components with retention
times similiar to the oxazolidines and may be interferences in the gas chromatographic analysis. A second column (DB-5, DB-
WAX) may be needed to separate some of the earlier C3-C4 aldehydes from excess HMP reagent.
OTHER METHODS: This method incorporates sampling technology used in NIOSH methods 2501 (acrolein), 2541
(formaldehyde), 2529 (furfural), 2531 (glutaraldehyde) [1], and 2526 (valeraldehyde), and OSHA methods 68 (acetaldehyde) and
52 (acrolein/formaldehyde) [2].

ALDEHYDES, SCREENING: METHOD 2539, Issue 2, dated 15 August 1994 - Page 2 of 9
1. Toluene, chromatographic quality. 1. Sampler: glass tube, 10 cm long, 6-mm OD,

2. 2-(Hydroxymethyl)piperidine. Recrystallize 4-mm ID; flame-sealed ends and plastic caps,
several times from isooctane until there is one containing two sections of 40/60 mesh,
major peak (>95% of area) by GC analysis. 2-(hydroxymethyl)piperidine-coated XAD-2
Store in desiccator. (front = 120 mg; back = 60 mg: see
3. Amberlite XAD-2 (Rohm and Haas or APPENDIX A) retained and separated by small
equivalent). plugs of silanized glass wool. Pressure drop
4. Formaldehyde,* 37% (w/v) solution in water. across the tube at 0.10 L/min airflow must be
5. Formaldehyde stock solution, 1 fjg/fjL (see less than 760 kPa (5.7 mm Hg). Tubes are
APPENDIX A). commercially available (Supelco, Inc.
6. Acetaldehyde*. ORBO-23 or equivalent).
7. Acrolein*. 2. Personal sampling pump, 0.01 to 0.05 L/min,
8. Propionaldehyde*. with flexible connecting tubing.
9. Butyraldehyde*. 3. Gas chromatograph, flame ionization detector
10. Isobutyraldehyde*. (FID), integrator and column (page 2539-1).
11. Crotonaldehyde*. GO/MS system for confirmation.
12. Valeraldehyde*. 4. Ultrasonic bath.
13. Isovaleraldehyde*. 5. Vials, glass, 1-mL, with PTFE-lined crimp caps.
14. Hexanal*. 6. Flasks, volumetric, 10-mL
15. Heptanal*. 7. Pipets, volumetric, 1-mL with pipet bulb
16. Furfural*. 8. Syringes, 10-//L (readable to 0.1 -//L), 25-, and
17. Sulfuric acid, 0.02 N. 50-/YL
18. Sodium hydroxide, 0.01 N. 9. File.
19. Sodium sulfite, 1.13 M. 10. Beakers, 50-mL
20. Water, deionized, then distilled. 11. pH meter.
21. Hydrogen, prepurified. 12. Magnetic stirrer.
22. Air, filtered, compressed. 13. Burets, 50-mL
23. Helium, purified. 14. Flasks, round-bottomed, 100-mL
15. Soxhlet extraction apparatus.
* See SPECIAL PRECAUTIONS. 16. Vacuum oven.
1 7. Distillation apparatus.
SPECIAL PRECAUTIONS: Aldehydes can irritate the mucous membranes and act on the central
nervous system [3]. Certain aldehydes are also suspect carcinogens. Work with these compounds only
in a well-ventilated hood.
SAMPLING:

2. Break ends of the sampler immediately before sampling. Attach sampler to personal sampling
3. For general screening, sample at 0.01 to 0.05 L/min for a maximum sample volume of 5 L
NOTE: Aldehydes react with the 2-(hydroxymethyl)piperidine to form an oxazolidine derivative in
the sorbent bed during sampling. Sampling rate is limited by the speed of this reaction.
Owing to the lower reactivities of some aldehydes, sampling even at 0.02 L/min may
cause breakthrough because of incomplete reaction.
SAMPLE PREPARATION:
4. Score each sampler with a file in front of the first sorbent section.

5. Break sampler at score line. Remove and place front glass wool plug and front sorbent section
in a vial. Transfer back section with remaining glass wool plugs to a second vial.
6. Add 1 .0 mL toluene to each vial. Crimp cap tightly onto each vial.
7. Agitate vials in an ultrasonic bath for 60 min.
8. Prepare qualitative oxazolidine standard samples.

a. Prepare aldehyde standard stock solutions.
NOTE: Aldehydes can oxidize to other compounds on exposure to air. This will introduce
bias into the method, so use of freshly-opened bottles of aldehydes is
recommended.
(1) Inject an aliquot of formaldehyde stock solution directly onto the sorbent.
(2) Take special care with acetaldehyde because of its volatility. To prepare
acetaldehyde standard solutions, weigh a 10-mL capped volumetric flask containing
about 5 mL toluene. With a cooled pipette, transfer about 1 mL of acetaldehyde into
the weighed flask, recap and reweigh. Dilute to the mark.
(3) For the other aldehydes, add measured aliquots (ca. 12 fjL) of each to toluene in
10-mL volumetric flasks and dilute to the mark. From the density of each aldehyde,
determine the amount of each aldehyde present in each solution (ca. 1 fjg/fjL).
b. Inject 10 juL of the standard aldehyde solutions separately onto blank tubes from the same
lot as the field samples.
c. Analyze (steps 4 through 7 and 10 through 12) along with blanks for qualitative identification
of derivative peaks by retention times.
9. Determine limit of detection (LOD) for individual aldehydes by GC/FID with standards covering
the range 0.5 to 10 ^/g per sample. Do this once, when first setting up the method to determine
approximate sensitivities for the various aldehyde derivatives. Subsequently, analyze only
low-level formaldehyde standard samples with each set of samples as an internal check that the
analytical system is working.
a. Weigh 120-mg portions of unused sorbent from media blanks into vials. Keep at least three
120-mg portions of this sorbent for determination of the background levels of each aldehyde.
b. Add 0.5- to 10-//L aliquots of the individual aldehyde standard solutions to obtain standard
samples in the range 0.5 to 10 //g per 120 mg portion of sorbent. Cap vials and allow to
stand overnight at room temperature.
c. Desorb the standard samples of aldehydes (steps 6 and 7) and analyze (steps 10 through
12) along with blanks.
d. Determine lowest spike to be detected (peak area greater than three times the background
or lowest standard observable) to estimate LOD for each aldehyde.
NOTE: Because the working standards are prepared on media blanks, no additional blank
correction or desorption efficiency correction is necessary.
MEASUREMENT:
10. Set gas chromatograph to manufacturer's recommendations and to conditions given on page
2539-1. Inject 1-//L sample aliquot.
NOTE: If the amount of oxazolidine in the aliquot exceeds the capacity of the column, dilute the
sample with toluene.
1 1. Compare retention times of unknown peaks in samples to the retention times for the
oxazolidines as determined by the qualitative standard samples. (See Appendix B for sample
chromatogram).
a. Analyze samples with GC retention times matching any oxazolidine by GC/MS using the
same GC columns and conditions if possible. Alternate columns such as a DB-WAX
(formaldehyde, acetaldehyde, propanal) or DB-1 (remaining aldehydes) may also be used for
GC/MS confirmation depending on which aldehyde is suspected.

b. Determine the presence of oxazolidines by monitoring for specific ions known to be present
in the derivative spectra. See Table 2 for characteristic ion table and Appendix C for
reference mass spectra. Retention times by GC/MS must also match authentic oxazolidine
standards.
NOTE 1 : This method may also sample aldehydes other than those listed. The presence
of these other aldehydes can be confirmed by examination of the mass spectral
data and observation of peaks at m/e 126 and at the molecular ion minus one
mass unit. The molecular ion for a particular aldehyde is equal to the molecular
weight of the original aldehyde plus 97. Fragmentation patterns are also
important for the identification of the oxazolidines.
NOTE 2: The absence of some C3-C5 aldehydes, such as propionaldehyde,
isobutyraldehyde and crotonaldehyde, does not necessarily mean that these
compounds are not present in the air sampled. These compounds are not
efficiently trapped by the sorbent, and will readily breakthrough the sampler
sorbent beds.
NOTE 3: Higher molecular weight aldehydes, such as isovaleraldehyde, hexanal and
heptanal, probably will be more efficiently collected on the sorbent owing to
their lower vapor pressure. Thus, absence of these compounds in sample
results may be indicative of the absence of these compounds in the environment
sampled.
12. Report the presence of a particular aldehyde if:
a. There is a detectable peak by GC-FID at the correct retention time for that aldehyde
derivative.
b. The correct mass spectrum for the derivative is obtained by GC/MS at the proper retention
time.
REFERENCES:
[1] NIOSH Manual of Analytical Methods, 3rd ed., P.M. Eller, Ed., DHHS (NIOSH) Publication No.
84-100 (1984).
[2] Occupational Safety and Health Administration, "OSHA Analytical Method Manual," American
Conference of Governmental Industrial Hygienists, Cincinnati, OH (1985).
[3] Kennedy, E. R., P. F. O'Connor, Y. T. Gagnon. Determination of Acrolein in Air as an
Oxazolidine Derivative by Gas Chromatography. Anal. Chem.. 56, 2120-2123 (1984).
[4] Kennedy, E. R., Y. T. Gagnon, J. R. Okenfuss, A. W. Teass. The Determination in Air of Selected
Low-molecular Weight Aldehydes as Their Oxazolidines by Capillary Gas Chromatography.
Appl. Ind. Hva. 3, 274-279 (1988).
METHOD WRITTEN BY:
Ardith A. Grote and Eugene R. Kennedy, Ph.D., NIOSH/DPSE.

TABLE 2. MASS SPECTRAL DATA FOR ALDEHYDE DERIVATIVES OF 2-(HYDROXYMETHYL)PIPERIDINE (HMP)
HMP DERIVATIVE
Base Peak Other Characteristic
Aldehyde Formula m/z Ions m/z
Formaldehyde C,H13NO 97 126, 127*

Acetaldehyde C8H16NO 126 140, 141*
Propionaldehyde C9H,7NO 126 154, 155*
Acrolein C9H,5NO 126 152, 153*
Butyraldehyde C,0H,9NO 126 168, 169*
Isobutyraldehyde C10H19NO 126 168, 169*
Crotonaldehyde C,0H17NO 126 166, 167*
Valeraldehyde C,,H21NO 126 182, 183*
Isovaleraldehyde C,,H2,NO 126 182, 183*
Hexanal C,2H23NO 126 196, 197*
Heptanal C,3H25NO 126 210, 211*
Furfural C,,H15NO2 192 95, 163, 193*
* indicates molecular ion.
APPENDIX A:
SORBENT PREPARATION (optional if commercially prepared tubes are used):
Extract Amberlite XADS-2 for 4 h in Soxhlet with 50/50 (v/v) acetone/methylene chloride. Replace with fresh solvent and repeat.
Vacuum dry overnight. Add 1 g purified 2-(hydroxymethyl)piperidine in 50 mL toluene for each 9 g extracted XAD-2 sorbent.
Allow this mixture to stand 1 h with occasional swirling. Remove the solvent by rotary evaporation at 37 °C and dry at 130 kPa
(1 mm Hg) at ambient temperature for ca. 1 h. To determine the amount of background for each batch, extract several 120-mg
portions of the coated sorbent with toluene and analyze (steps 6 through 12). No blank peak is expected for any aldehydes
other than formaldehyde and possibly acetaldehyde.
SYNTHESIS OF ALDEHYDE OXAZOLIDINES:
Place a solution of purified 2-hydroxymethylpiperidine (0.57 g, 5 mmol) in 10 mL of toluene in

a 50-mL round-bottomed flask. Use several 20 mL portions of toluene to rinse residual 1-(hydroxymethyl)piperidine from the
container used for weighing. Add anhydrous magnesium sulfate (2.5 g) to the round-bottomed flask to dry the aldehyde
solution as it is added and to remove the water which forms during the reaction. Add a solution of 10 mole of aldehyde in 10
mL of toluene to the 2-hydroxymethylpiperidine solution dropwise with stirring over 1 h. Stir the solution overnight, then filter to
remove the magnesium sulfate. Remove the toluene and excess aldehyde from the solution at reduced pressure by rotary
evaporation.
PREPARATION AND STANDARDIZATION OF FORMALDEHYDE STOCK SOLUTION (ca. 1 mg/mL):
Dilute 2.7 mL 37% aqueous formalin solution to 1 L with distilled, deionized water. This solution is stable for at least three
months. Standardize by placing 5.0 mL of freshly prepared 1.13 M sodium sulfite solution in a 50-mL beaker and stir
magnetically. Adjust pH to between 8.5 and 10 with base or acid. Record the pH. Add 10.0 mL stock formaldehyde solution.
The pH should be greater than 11. Titrate the solution back to its original pH with 0.02 N sulfuric acid (1 mL acid = 0.600 mg
HCHO; about 17 mL acid needed). If the endpoint pH is overrun, back titrate to the endpoint with 0.01 N sodium hydroxide.
Calculate the concentration, C, (mg/mL), of the formaldehyde stock solution:
30.0 x N Va - Nb
where: 30.0 = 30.0 g/equivalent of formaldehyde

N, = normality of sulfuric acid
V, = volume of sulfuric acid (mL) used for titration
Nb = normality of NaOH
Vb = volume of NaOH (mL) used for back titration
V. = volume of formaldehyde stock solution (10.0 mL).

APPENDIX B: Sample chromatogram of aldehyde oxazolidines on DB-1301 column using conditions listed on page 2539-1.
S9. 64.
I
49.90 I
40.16.
30.42-
20.1
in
iO.i
UL 1 LLlk
i.BO 3.06 4.62 6.16 7.79 9.31 10.87 12.43 14.00
ALDEHYDE MIX ON ORBO-23
15M DB-1301 COLUMN

ALDEHYDES, SCREENING: METHOD 2539. Issue 2, dated 15 August 1994 - Page 8 of 9
APPENDIX C: Reference mass spectra of oxazolidines of aldehydes individually spiked onto ORBO-23 tubes. GC/MS
conditions: HP 5890 gas chromatograph interfaced (direct) to HP 5970 mass-selective detector (70eV); 30-m DB-1 column,
0.25-mm I.D., 1.0-p/m film; 70 °C for 1 min, 15 °C/min to 300 °C; interface temperature, 280 °C; injector, 250 °C, 1 pL splitless
injection; scan 20-400 amu.
row LDCHYDC 0XflZOLIDINE
4
}
ia
S V
//
V I ll IV ., [ r^l ..
„
KZT H_D£>rtDE OXRZOLIDINC
ta
i: A, 'V S^
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a
/ | iih i ' . I?
PROF IONft.DEHYDE OXRZOLIDINC
• in i»
HI , [."/ \
N
•
71
•
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4f •
a
a
^
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a
u
i Jil . . Jl.i 4 u
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a
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TI • « ia in ia » M • !• I71
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RCMOLEIN OXRZOLIDINE
tm
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" III '
IB OXflZOLlDJNE
\
/ *, W II
III
..ll,L ..1.1,,.. Y ..... L \1 .....1./ / \.
BUTYRW.3EHYDE OXBZOLIDINE
ia
"
!V V"
n B B w II1 ia La M
or
\ \

ALDEHYDES. SCREENING: METHOD 2539, Issue 2, dated 15 August 1994 - Page 9 of 9
APPENDIX C: (Continued)
- CROTtm.DEHYDC OXflZOLIDINE \
IS
«
a V «
'
* * '
M / 14
UB 19
\I 1,1, ,1, niiU i,jii, " 1 J,

Ut vnERflLDEHYDE oxnzouDi* \la
i ' ? V* aLv .JL

v *\\1f 1.y \>. L I41 I91 ••
JlL ..L Jlfc ...' I £
ISOVTLCRflLIICHYDe OXH20LIDINE
!•
\
a a V w ? _ „ * 1M
u la IB '«
f,i,, ,L Y j '' \... J" \
m HEXRNFL OXRZOLIDIME
*
«
>, 4I * / IU >47 ? 7
l ?l.il ,li V./.l .
at HCPTRLDCHYDC OXRZOLIDINE
I
1: "Z.i 1 l\ V/V. f \ T
ruRFURH. OXflZOLIOlNE
Ut
•
*
• X| /
4t ' 99 M
NJL JI ii.. -i. .JL .J* .i. i. jk- »/ i /7

9
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I91 IM I71 !• IN • III

ALDRIN 5502
C17HsClp MW: 364.93 CAS: 309-00-2 RTECS: IO21 00000

OSHA : 0.25 mg/m3 (skin) PROPERTIES: solid; MP 104 °C; VP 0.008 Pa (6 x 106
NIOSH: 0.25 mg/m3 (skin); carcinogen; mm Hg; 0.12 mg/m3) @ 20 °C;
Group I Pesticide
ACGIH: 0.25 mg/m3 (skin)
SYNONYMS: Aldrin: Octalene; aldrite; aldrosol; HHDN
SAMPLER: FILTER AND BUBBLER TECHNIQUE: GAS CHROMATOGRAPHY, ELECTROLYTIC

(glass fiber + 15 mL isooctane) CONDUCTIVITY DETECTOR
FLOW RATE: 0.2 to 1 L/min ANALYTE: Aldrin or Lindane
VOL-MIN: 18 L@ 0.25 mg/m3 FILTER

-MAX: 240 L EXTRACTION: isooctane
SHIPMENT: transfer bubbler solutions and filters in INJECTION

scintillation vials; pack carefully VOLUME: 15//L
SAMPLE TEMPERATURE-FURNACE: 750 to 770 °C

STABILITY: at least 1 week @ 25 °C -TRANSFER: 225 °C
-VENT: 205 to 260 °C
BLANKS: 2 to 10 field blanks per set -COLUMN: 160 to 190 °C
GASES-H2 (furnace): 150 to 160 mL/min

-N2 (carrier): 140 mL/min
ACCURACY COLUMN: glass, 1 .2 m x 3-mm OD; 5% SE-30 on 80/100

mesh acid-washed DMCS Chromosorb W or
RANGE STUDIED: 0.15 to 0.5 mg/m3 [1]; equivalent
BIAS: - 0.44% CALIBRATION: solution of analyte in isooctane
OVERALL PRECISION (SrT): 0.092 [1] RANGE: 5 to 135 //g per sample
ACCURACY: ± 16.9% ESTIMATED LOD: 3 fjg per sample
PRECISION (S,): 0.012 [1]
APPLICABILITY: The working range is 0.05 to 1.5 mg/m3 of Aldrin or Lindane for a 90-L air sample. Evaporation of isooctane
from the bubbler necessitates refilling the bubbler frequently.
OTHER METHODS: This method combines and replaces S275 [2] and S290 [2]. Lindane has also been sampled with a
filter-solid sorbent train [3].

ALDRIN and LINDANE: METHOD 5502, Issue 2, dated 15 August 1994 - Page 2 of 3
1. Aldrin, reagent grade.* 1 . Sampler: glass fiber filter, organic binder-free

2. Lindane, reagent grade.* (e.g., Gelman Type A/E), 37-mm, held without
3. Isooctane, chromatographic grade. backup pad in a two-piece polystyrene
NOTE: Needed for field use in sample cassette filter holder connected in series with
collection. a midget bubbler containing 15 mL of the
4. Benzene, reagent grade.* collection medium.
5. Calibration stock solution, 1 0 mg/mL Dissolve NOTE: a. Do not use filter holders made of
0.1 g accurately weighed Aldrin or Lindane in Tenite.
1:5 (v:v) benzene:isooctane; dilute to 10 mL b. Place glass tube, 5 cm x 6-mm
Stable at least one week. ID, plugged with glass wool
6. Hydrogen, prepurified. between the exit cover of the
7. Nitrogen, purified. bubbler and the inlet of the
personal sampling pump to avoid
splashover or solvent
condensation.
2. Personal sampling pump, 0.2 to 1 L/min, with
* See SPECIAL PRECAUTIONS. flexible connecting tubing.
3. Vial, scintillation, with PTFE-lined cap,
graduated at 15 mL
4. Gas chromatograph with electrolytic
conductivity detector, quartz reduction
furnace, in-line vent upstream of furnace,
integrator and column (page 5502-1).
5. Syringes, 5-, 10- and 25-//L, for making
standard solutions and GC injections.
6. Volumetric flasks.
7. Pipets, with pipet bulb.
8. Tweezers.
SPECIAL PRECAUTIONS: Benzene is a suspected human carcinogen; work with it only in a hood.
Aldrin and Lindane are toxic when absorbed through the skin [4].
SAMPLING:

2. Add 15 mL isooctane to the bubbler.
3. Sample at an accurately known flow rate of 0.2 to 1 L/min (e.g., 0.5 L/min for 1 to 6 h) for a
total volume of 18 to 240 L
NOTE: Check liquid level in the bubbler every 15 min. Maintain between 10 and 15 mL
isooctane in the bubbler throughout the sampling period with a volume at the end of
sampling of about 10 mL
4. Remove the bubbler stem and tap it gently against the inside wall of the bubbler to transfer
solvent from the stem to the bubbler.
5. Transfer contents of the bubbler to a vial. Rinse the bubbler with 2 mL isooctane. Add the rinse
to the vial.
6. Transfer the glass fiber filter to the same vial using tweezers.
7. Cap the vial and pack carefully for shipment.
SAMPLE PREPARATION:
8. Adjust the volume of solution in the vial to 15 mL

ALDRIN and LINDANE: METHOD 5502, Issue 2, dated 15 August 1994 - Page 3 of 3
9. Calibrate daily with at least six solutions covering the range 3 to 135 ^g Aldrin or Lindane per
sample.
a. Add calibration stock solution with a microliter syringe to 15 mL isooctane in a vial.
b. Analyze the working standards together with samples and blanks (steps 10 through 13).
c. Prepare calibration graph (peak area vs. //g Aldrin or Lindane). Analyze three additional
quality control blind spikes and three analyst spikes to ensure that the calibration graph is in
control.
MEASUREMENT:
1 0. Set gas chromatograph to manufacturer's specifications and to conditions given on

page 5502-1 .
11. Mix the contents of the scintillation vial thoroughly.
12. Inject 15 //L sample aliquot using solvent flush technique or autosampler.
NOTE: Open vent valve for 20 sec, beginning with time of injection, to prevent the solvent peak
from entering the furnace.
CALCULATIONS:
14. Determine the mass, //g, of Aldrin or Lindane found in the sample (filter plus bubbler), W, and
average media blank (filter plus bubbler), B, from the measured peak areas and the calibration
graph.
15. Calculate the concentration, C (mg/m3), of Aldrin or Lindane in the air volume sampled, V (L):
C . i«LlBl, mg/ms
Methods S275 (Aldrin) and S290 (Lindane) were issued on February 27, 1976, and March 26, 1976,
respectively [2]. The substances used to generate test atmospheres at 25 °C and 760 mm Hg in dry air
were Aldrite emulsifiable concentrate (64% Aldrin) and Ortho-Lindane Borer and Leaf Miner Spray [1].
Collection efficiencies and analytical method recoveries were 1 .00 for both substances in the range 22 to
90 fjg per sample. Sample filters extracted in isooctane immediately and stored one week at ambient
conditions gave recoveries of 103% and 102%, respectively. Overall precision, SrT, was 0.092 for Aldrin
and 0.086 for Lindane. No significant bias was found for either substance.
REFERENCES:
[2] NIOSH Manual of Analytical Methods, V. 3, S275 and S290, U.S. Department of Health,
Education, and Welfare, Publ. (NIOSH) 77-157-C (1977).
[3] Hill, R.H. and J.E. Arnold. Arch. Environ. Contam. Toxicol.. 8, 621-628 (1979).
[4] Criteria for a Recommended Standard. ..Occupational Exposure During the Manufacture and
Formulation of Pesticides, U.S. Department of Health, Education, and Welfare, Publ. (NIOSH)
78-174 (1978).
METHOD REVISED BY:
Gangadhar Choudhary, Ph.D., ATSDR; S275 and S290 originally validated under NIOSH Contract
CDC-99-74-45.

ALKALINE DUSTS 7401
NaOH, KOH, LiOH, MW: 40.00 (NaOH); CAS: 1310-73-2 RTECS: WB490000 (NaOH)
and basic salts 56.11 (KOH) 1310-58-3 TT2 100000 (KOH)
23.95 (LiOH) 1310-65-2 OJ6307070 (LiOH)

OSHA : 2 mg/m3 (NaOH) PROPERTIES: basic, hygroscopic, caustic solids and

NIOSH: C 2 mg/m3/15 min (NaOH); Group I Pesticide aerosols; VP not significant
ACGIH: C 2 mg/m3 (NaOH)
SYNONYMS: alkali; caustic soda; lye; sodium hydroxide; potassium hydroxide
SAMPLER: FILTER TECHNIQUE: ACID-BASE TITRATION

(1-//m PTFE membrane)
ANALYTE: OH (alkalinity)
FLOW RATE: 1 to 4 L/min
EXTRACTION: 5.00 mL 0.01 N HCI, 15 min under
VOL-MIN: 70 L @ 2 mg/m3 nitrogen with stirring
-MAX: 1000 L
TITRATION: 0.01 N NaOH under nitrogen, endpoint
SHIPMENT: routine by pH electrode
SAMPLE CALIBRATION: 0.01 N NaOH standardized with

STABILITY: at least 7 days @ 25 °C [1 ,2] 0.01 N HCI
BLANKS: 2 to 10 field blanks per set RANGE: 0.14 to 1.9 mg (as NaOH) per sample [1]
ESTIMATED LOD: 0.03 mg per sample (as NaOH) [1]

(7 x 10"4 moles of alkalinity)
ACCURACY PRECISION (Sr): 0.033 @ 0.38 to 1 .5 mg NaOH

per sample [1]
(360-L samples)
BIAS: 5.6%
ACCURACY: ± 16.2%
APPLICABILITY: The working range is 0.4 to 5.4 mg/m3 for a 360-L air sample. The method measures total alkalinity of alkali
hydroxides, carbonates, borates, silicates, phosphates, and other basic salts, expressed as equivalents of NaOH.
INTERFERENCES: Carbon dioxide in the air may react with alkali on the filter to produce carbonates but does not interfere
when titrated. The carbonates will produce the equivalent amount of strong alkali that was consumed on the filter [1]. Acid
aerosols may neutralize the sample, if present, producing a negative interference.
OTHER METHODS: This revises Methods S381 [2] and P&CAM 241 [3].

ALKALINE DUSTS: METHOD 7401, Issue 2, dated 15 August 1994 - Page 2 of 4
1. Sodium carbonate, primary standard grade. 1. Sampler: 37-mm diameter PTFE membrane
2. Hydrochloric acid stock solution, 0.1 N. filter (Millipore, Fluoropore or equivalent), 1.0-
Standardize with sodium carbonate primary fjm pore size, supported by a cellulose backup
standard. pad in a cassette filter holder.
3. Dilute hydrochloric acid, 0.01 N. Dilute 10.0 2. Personal sampling pump, 1 to 4 L/min, with
mL 0.1 N stock HCI to 100 mL in a volumetric flexible connecting tubing.
flask with distilled water. 3. pH meter with pH electrode and recorder.
4. Water, distilled, CO2-free. Boil and cool under 4. Titration vessel, 1 50 to 200 mL beaker, flask or
N2 or bubble nitrogen through distilled water jar with cover containing openings for the pH
for 30 min. Store with an Ascarite trap. electrode and N2 inlet and outlet.
5. Nitrogen, compressed. 5. Stirrer, magnetic, and stir bar.
6. Sodium hydroxide, 50% w/v.* Dissolve 50 g 6. Glass rod, ca. 5-mm diameter and 10 cm long
NaOH in CO2-free distilled water and dilute to to hold filter under liquid surface in titration
100 mL vessel.
7. Stock sodium hydroxide, 0.1 N. Dilute 8 mL 7. Pipets, 5- and 10-mL
50% NaOH to 1.0 L with CO2-free distilled 8. Volumetric flasks, 100-mLand 1-L
water. Store under Ascarite or other CO2- 9. Burets, 50-mL, readable to 0.1 mL.
absorbing trap. 10. Tweezers.
8. Working sodium hydroxide solution, 0.01 N.
Dilute 10 mL stock (0.1 N NaOH) to 100 mL
with CO2-free distilled water.
9. Standard buffer solutions, pH 4 and 7.
SPECIAL PRECAUTIONS: NaOH solutions are corrosive to tissue [4]. Handle with care.
SAMPLING:

2. Sample at an accurately known flow rate between 1 and 4 L/min for a sample size of 70 to 1000
L Do not exceed a filter loading of ca. 2 mg total dust.
SAMPLE PREPARATION:
3. Transfer the sample filter to a titration vessel with tweezers. Place the filter face down in the
titration vessel.
4. Place the end of a glass rod in the center of the filter to maintain the filter below the liquid
surface during the analysis.
5. Cover the titration vessel, add 5.00 mL 0.01 N HCI, start the magnetic stirrer and N2 purge (ca.
0.1 L/min).
6. Allow to stand 15 min (with stirring).
7. Calibrate the pH meter with pH 4 and pH 7 buffer solutions.

8. Standardize aliquots of the 0.1 N HCI stock solution with sodium carbonate in triplicate [3].
a. Dry 3 to 5 g primary standard grade Na2CO3 at 250 °C for 4 h. Cool in a desiccator.
b. Weigh ca. 2.5 g Na2CO3 to the nearest mg. Dissolve and dilute to exactly 1 L with CO2-free
distilled water. The concentration is ca. 0.05 N Na2CO3.
c. Place 5.00 mL 0.05 N Na2CO3 solution into a titration vessel and titrate potentiometrically to
a pH of 5.

d. Remove electrodes, rinse them into the titration vessel, and bubble N2 gas through contents
of the titration vessel for 3 to 5 min to remove dissolved CO2.
e. Proceed with the titration to the inflection point.
f. Calculate the normality of the stock HCI solution:
( g NajCOg weighed )( mL Na^CC^ solution used in titration )
HCI = ( 52.99 )( mL HCI used )
9. Standardize the working (ca. 0.01 N) NaOH solution against the standardized HCI solution by
following steps 8.c. and 8.e, substituting the standardized HCI stock solution for the Na2CO3
solution and the 0.01 N NaOH solution for the 0.1 N HCI solution. Calculate the normality of the
NaOH titrating solution.
NNa0H = (NHci)(mL HCI used)/(mL NaOH used)
10. Prepare at least three spiked media blank samples to check analytical recoveries at levels
expected on the field samples.
MEASUREMENT:
11. Back-titrate the excess HCI in the samples, blanks and spiked blank solutions with the
standardized NaOH solution while maintaining the N2 purge.
12. Observe the pH meter. Calculate the endpoint (mL of 0.01 N NaOH used).
CALCULATIONS:
13. Using the normality (N) and volumes of NaOH in the titration of the sample (VNaOH.s) and
average blank filter (VNaOH.b), and the volume of air sampled, V(L), calculate the concentration, C
(mg/m3), of alkalinity (as NaOH with equivalent weight = 40.0):
• N • 4 X
Method S381 [1] was issued on July 8, 1977, and was validated using generated atmospheres of NaOH
over the range 0.76 to 3.9 mg/m3 using a 360-L sample [1,6]. Overall precision, SrT, was 0.062 with an
average recovery of 105%, representing an insignificant bias. The NaOH concentration was
independently verified by analyzing additional samples for sodium by atomic absorption
spectrophotometry. An overall average collection efficiency of greater than 99% was found by sampling
1 to 360 L in an atmosphere of 7.50 mg/m3 (NaOH) using backup Fluoropore filters and also by
collecting two 615-L samples using backup impingers filled with water.
REFERENCES:
[1] Backup Data Report No. S381, Sodium Hydroxide, prepared under NIOSH Contract No.
210-76-0123, available as Order No. PB 275-838 from NTIS, Springfield, VA 22161
(Julys, 1977).
[2] NIOSH Manual of Analytical Methods, 2nd. ed., V. 4, S381, U.S. Department of Health,
[3] Ibid, V. 1, P&CAM 241, U.S. Department of Health, Education, and Welfare, Publ. (NIOSH)
77-1 57-A (1977).

[4] Criteria for a Recommended Standard. ..Occupational Exposure to Sodium Hydroxide, U.S.
[5] Standard Methods for the Examination of Water and Wastewater, 15th Edition, American Public
Health Association, American Water Works Association and Water Pollution Control Federation
(1981).
80-133 (1980).
METHOD REVISED BY:
Mary Ellen Cassinelli, NIOSH/DPSE; S381 originally validated under NIOSH Contract No. 210-76-0123.

ALLYL ALCOHOL
See ALCOHOLS III (METHOD 1402) for procedure

ALLYL CHLORIDE 1000
CH, = CHCHoCI MW : 76.53 CAS: 107-05-1 RTECS: UC7350000

OSHA : 1 ppm PROPERTIES: liquid; d 0.938 g/mL @ 20 °C; BP 45 °C;

NIOSH: 1 ppm; STEL 2 ppm MP - 135 °C; VP 39.3 kPA (295 mm Hg)
ACGIH: 1 ppm; STEL 2 ppm @25 °C; explosive range 3.3 to 11%v/v
(1 ppm = 3.13 mg/m3 @ NTP) in air
SYNONYMS: 3-chloro-1-propene; 1-chloro-2-propene.

ANALYTE: allyl chloride
FLOW RATE: 0.01 to 1 L/min
DESORPTION: 1 mL benzene; stand 30 min
VOL-MIN: 16L@1ppm
-MAX: 100 L INJECTION VOLUME: 5//L
SHIPMENT: routine TEMPERATURE-INJECTION: 185 to 200 °C

-DETECTOR: 250 °C
SAMPLE -COLUMN: 160 to 200 °C
STABILITY: at least 6 weeks @ 25 °C
CARRIER GAS: N2, 30 mL/min
COLUMN: stainless steel, 1.2 m x 6-mm OD;
50/80 mesh Porapak Q or equivalent
CALIBRATION: standard solutions of allyl chloride

ACCURACY in benzene
RANGE STUDIED: 1.8 to 7.2 mg/m3 [1] RANGE: 0.05 to 1.5 mg per sample
(100-L samples)
ESTIMATED LOD: 0.01 mg per sample
BIAS: 6.4%
OVERALL PRECISION (SrT): 0.071 [1] PRECISION (§r): 0.023 [1]
ACCURACY: ± 16.6%
APPLICABILITY: The working range is 0.16 to 3 ppm (0.5 to 10 mg/m3) for a 100-L air sample. The method is applicable to
short term samples taken at 1 L/min. The upper limit of loading depends on the concentrations of allyl chloride and other
substances in the air, including water vapor.
OTHER METHODS: This is Method S116 in a revised format [2].

ALLYL CHLORIDE: METHOD 1000, Issue 2. dated 15 August 1994 - Page 2 of 3
1. Benzene, chromatographic quality.* 1. Sampler: glass tube, 7 cm long, 6-mm OD, 4-

2. Allyl chloride. mm ID, flame-sealed ends, containing two
3. Hexane. sections of activated (600 °C) coconut shell
4. Calibration stock solution, 7.5 //g///L Dilute charcoal (front = 100 mg, back = 50 mg)
75 mg allyl chloride (80.0 //L at 20 °C) to separated by a 2-mm urethane foam plug. A
10 mL with hexane. silylated glass wool plug precedes the front
5. Nitrogen, purified. section and a 3-mm urethane foam plug
6. Hydrogen, prepurified. follows the back section. Pressure drop
7. Air. across the tube at 1 L/min airflow must be
* See Special Precautions available.
flexible connecting tubing.
5. Syringe, W-fjL, readable to 0.1 fjL.
SPECIAL PRECAUTIONS: Benzene is a suspected human carcinogen. All work should be performed
in a hood.
SAMPLING:

to 100 L
SAMPLE PREPARATION:
6. Add 1.0 mL benzene to each vial. Attach crimp cap to each vial.
8. Calibrate daily with at least six working standards over the range 0.01 to 1.5 mg allyl chloride
per sample.
a. Add known amounts of calibration stock solution to benzene in 10-mL volumetric flasks and
dilute to the mark.
c. Prepare calibration graph (peak area vs. mg allyl chloride).
blanks.

ALLYL CHLORIDE: METHOD 1000, Issue 2, dated 15 August 1994 - Page 3 of 3

microliter syringe.
e. Prepare a graph of DE vs. mg allyl chloride recovered.
MEASUREMENT:
autosampler.
NOTE: If peak area is above the linear range of the working standards, dilute with benzene,
CALCULATIONS:
13. Determine the mass, mg (corrected for DE) of allyl chloride found in the sample front (Wf) and
sections.
14. Calculate concentration, C, of allyl chloride in the air volume sampled, V (L):
C - W - Wt - B, - Bt) •
Method S116 was issued on May 9, 1975 [2], and validated over the range 1.8 to 7.2 mg/m3 at 25 °C
and 759 mm Hg using a 100-L sample [1]. Overall precision, SrT, was 0.071 with average recovery
105.5%, representing a non-significant bias. The concentration of allyl chloride was independently
verified by direct gas chromatography. Desorption efficiency was 0.943 in the range 0.15 mg to 0.6 mg
allyl chloride per sample. Breakthrough (5% on back section) occurred between 210 and 240 min when
sampling an atmosphere containing 7.56 mg/m3 allyl chloride at 0.94 L/min at 0% RH.
REFERENCES:
[1] Documentation of the NIOSH Validation Tests, NIOSH, S116, U.S. Department of Health,
and Welfare, Publ. (NIOSH) 77-1 57-B (1977).
METHOD REVISED BY:
G. David Foley, NIOSH/DPSE; originally validated under NIOSH Contract CDC-99-74-45.

ALLYL GLYCIDYL ETHER 2545
CH2 = CHCH2OCH2CH(O)CH2 MW: 114.14 CAS: 106-92-3 RTECS: RR0875000
OSHA : C 10 ppm PROPERTIES: liquid; d 0.970 g/mL @ 20 °C; BP 154 °C;

NIOSH: 5 ppm; STEL 10 ppm (skin) VP 0.63 kPa (4.7 mm Hg, 0.62%) @ 25 °C
ACGIH: 5 ppm; STEL 10 ppm (skin)
(1 ppm = 4.67 mg/m3 @ NTP)
SYNONYMS: 1-allyloxy-2,3-epoxypropane; ((2-propenyloxy)methyl)oxirane; AGE

(Tenax GC; 100 mg/50 mg)
ANALYTE: allyl glycidyl ether
DESORPTION: 2 mL diethyl ether, 30 min
VOL-MIN: 1.5L@5ppm
-MAX: 8 L TEMPERATURE-INJECTION: 200 °C
-DETECTOR: 280 °C
SHIPMENT: routine -COLUMN: 150 °C
SAMPLE INJECTION
STABILITY: at least 7 days @ 25 °C VOLUME: 2 //L
BLANKS: 2 to 10 field blanks per set CARRIER GAS: N2, 30 mL/min
COLUMN: stainless steel, 3.2-mm ID x 6.1 m,

packed with 10% FFAP on 100/120 mesh
Supelcoport
CALIBRATION: standard solutions of allyl glycidyl ether

ACCURACY and internal standard in diethyl ether
RANGE STUDIED: 19 to 87 mg/m3 [1] RANGE: 30 to 300 fjg per sample

(3-L samples)
ESTIMATED LOD: 10 fjg per sample
BIAS: -1.3%[1]
OVERALL PRECISION (SrT): 0.057 [1] PRECISION (Sr): 0.034 [1]
ACCURACY: ±12.5%
APPLICABILITY: The working range is 2 to 20 ppm (10 to 100 mg/m3) for a 3-L air sample. An appropriate capillary column
may be used for better resolution and sensitivity.

ALLYL GLYCIDYL ETHER: METHOD 2545, Issue 1, dated 15 August 1994 - Page 2 of 4
1. Allyl glycidyl ether*, reagent grade. 1. Sampler: borosilicate tubes, 10 cm long,

2. Diethyl ether*, anhydrous, containing 8-mm OD, 6-mm ID; flame-sealed ends with
approximately 0.1 mg/mL isoamyl alcohol or plastic caps, containing two sections of 35/60
other suitable internal standard. mesh Tenax GC (front = 100 mg; back = 50
3. Hexane. mg) separated by a urethane foam plug. A
4. Nitrogen, purified. silanized glass wool plug held in place with a
5. Hydrogen, prepurified. metal spring precedes the front section and a
6. Air, compressed, filtered. urethane foam plug follows the back section.
Pressure drop across the tube at 1 .0 L/min air
flow must be less than 3.4 kPa. Tubes are
* See SPECIAL PRECAUTIONS. commercially available.
3. Gas chromatograph, FID, integrator, and
4. Vials, 5-mL, with PTFE-lined crimp caps.
5. Microliter syringes, 1 0-fjL and convenient sizes
for making dilutions.
7. Pipets, 2-mL
SPECIAL PRECAUTIONS: Allyl glycidyl ether is flammable (flash point = 57 °C) and a moderate skin
and severe eye irritant [3]. Diethyl ether is a serious fire and explosion hazard (flash point = -45 °C)
and may form explosive peroxides during storage. All work with these compounds must be done in a
hood.
SAMPLING:

1 .5 to 8 L
SAMPLE PREPARATION:
6. Add 2.0 mL diethyl ether to each vial. Cap each vial.
8. Calibrate daily with at least six working standards over the range 10 to 800 fjg allyl glycidyl ether
per sample.
a. Add a known amount of allyl glycidyl ether to diethyl ether in 10-mL volumetric flask and
dilute to the mark. Use serial dilutions as needed for smaller concentrations.

ALLYL GLYCIDYL ETHER: METHOD 2545, Issue 1, dated 15 August 1994 - Page 3 of 4
b. Analyze with samples and blanks (steps 11 and 12).

c. Prepare calibration graph (ratio of allyl glycidyl ether peak area to internal standard peak
area vs. //g allyl glycidyl ether per 2 mL).
9. Determine desorption efficiency (DE) at least once per year for each lot of Tenax GC used for
sampling in the range of interest. Determine for three samplers at each of five concentrations
plus three media blanks.
a. Transfer front sorbent section of media blank sampler to a 5-mL vial.
b. Inject known amount (1 to 10 //L) of allyl glycidyl ether or standard solution of allyl glycidyl
ether in hexane directly into sorbent in vial with a microliter syringe.
NOTE: Standard solutions for DE determination should not contain internal standard.
d. Desorb (steps 5 through 7) and analyze with working standards (steps 11 and 12).
e. Prepare a graph of DE vs. //g allyl glycidyl ether recovered.
MEASUREMENT:
on page 2545-1 . Inject sample aliquot manually using solvent flush technique or with
autosampler.
desorbed liquid with diethyl ether, reanalyze, and apply the appropriate dilution factor in
calculations.
12. Measure peak areas. Divide peak area of allyl glycidyl ether by peak area of internal standard
for each chromatogram.
CALCULATIONS:
13. Determine the mass, ;/g (corrected for DE) of allyl glycidyl ether found in the sample front (Wf)
and back (Wb) sorbent sections, and in the average media blank front (Bf) and back (Bb) sorbent
sections.
Note: If Wb > W,/10, report breakthrough and possible sample loss.
14. Calculate concentration, C, of allyl glycidyl ether in the air volume sampled, V (L):
C . ' > ' mg/m*.
Method S346 was issued on January 21, 1977 [2] and was validated over the range 19 to 87 mg/m3 for
3-L air samples from dynamically generated test atmospheres [1]. The average recoveries ranged from
98.2 to 99.5%. The allyl glycidyl ether concentrations were independently calculated from analyte
delivery rate and air dilution ratios. Breakthrough was observed after sampling 12 L from a test
atmosphere containing 87 mg/m3 of allyl glycidyl ether at 90% relative humidity. Desorption efficiency
ranged from 101% to 89.8% for loadings of 67 to 269 //g allyl glycidyl ether per sample. A storage
stability study gave average recoveries of 96.9% for 7-day storage versus 98.1% for 1-day storage.

ALLYL GLYCIDYL ETHER: METHOD 2545. Issue 1, dated 15 August 1994 - Page 4 of 4
REFERENCES:
[1] Backup Data Report for Allyl Glycidyl Ether, No. S346, prepared under NIOSH Contract No.
210-76-0123.
[3] NIOSH/OSHA Occupational Health Guidelines for Chemical Hazards, U.S. Department of Health
and Human Services, Publ. (NIOSH) 81-123, available as GPO Stock #17-033-00337-8 from
Superintendent of Documents, Washington, D.C. 20402.
METHOD REVISED BY:
R. Alan Lunsford, Ph.D., NIOSH/DPSE. Method S346 was originally validated under NIOSH Contract
No. 210-76-0123.

ALUMINUM and compounds, as Al 7013
Al MW: 26.98 (Al); CAS: 7429-90-5 (Al); RTECS: BD0330000

101.96(AI203) 1344-28-1 (AI203) BD1 200000

OSHA: no PEL PROPERTIES: ductile metal; valence 3; MP 660 "C

NIOSH: see table 1
ACGIH: see table 1
SYNONYMS: vary depending upon the compound; alumina (AI2O3)
SAMPLER: FILTER TECHNIQUE: ATOMIC ABSORPTION, FLAME

(0.8-//m cellulose ester membrane)
ANALYTE: aluminum
ASHING: conc. HNO3, 6 mL; 140 °C
VOL-MIN: 10 L @ 5 mg/m3
-MAX: 400 L FINAL SOLUTION: 10% HNO3, 10 mL
1000//g/mLCs
SHIPMENT: routine
FLAME: nitrous oxide-acetylene, reducing
SAMPLE
STABILITY: stable WAVELENGTH: 309.3 nm
BLANKS: 2 to 10 field blanks per set BACKGROUND CORRECTION: none used
CALIBRATION: Al3* in 10% HNO3
RANGE: 50 to 5000 fjg per sample [1]

ACCURACY
ESTIMATED LOD: 2 fjg per sample [2]
PRECISION (Sr): 0.03 [1,2]
BIAS: none identified
OVERALL PRECISION (£„): not evaluated
ACCURACY: not evaluated
APPLICABILITY: The working range is 0.5 to 10 mg/m3 for a 100-L sample. This is an elemental analysis, not compound
specifie. Verify that the types of compounds in the samples are soluble with this ashing procedure. AJiquots of the samples
can be analyzed separately for approximately four additional metals.
INTERFERENCES: Cesium at 1000 Aig/mL controls ionization in the nitrous oxide-acetylene flame [3]. Iron and HCI at greater
than 0.2% (w/w) decrease the sensitivity. Vanadium or H2SO4 require 1% (w/w) La as a releasing agent [4].
OTHER METHODS: This is Method P&CAM 173 for Al [1] in a revised format. Method 7300 (ICP-AES) is an alternate analytical
method.

ALUMINUM and compounds, as Al: METHOD 7013, Issue 2, dated 15 August 1994 - Page 2 of 3
1. Nitric acid, conc. 1. Sampler: cellulose ester membrane filter,

2. Nitric acid, 10% (v/v). Add 100 mL conc. 0.8-//m pore size, 37-mm diameter; in cassette
HNO3 to 500 mL water; dilute to 1 L filter holder.
3. Calibration stock solution, 1000 fjg AI/mL 2. Personal sampling pump, 1 to 3 L/min, with
Commercially available or dissolve 1.000 g Al flexible connecting tubing.
wire in minimum volume of (1+1) HCI using 3. Atomic absorption spectrophotometer with a
small drop of Hg as catalyst. Dilute to 1 L nitrous oxide-acetylene burner head and
with 1% (v/v) HCI. aluminum hollow cathode lamp.
4. Cs solution, 50 mg/mL Dissolve 73.40 g 4. Regulators, two-stage, for N2O and acetylene.
CsNO3 in 100 mL water; dilute to 1 L 5. Beakers, Phillips, 125-mL, or Griffin, 50-mL,
5. Nitrous oxide. with watchglass covers.*
6. Acetylene. 6. Volumetric flasks, 10- and 100-mL*
7. Distilled or deionized water. 7. Micropipets, 5 to 500 fjL*
8. Hotplate, surface temperature 100 to 140 °C.
* Clean with conc, nitric acid and rinse

thoroughly with distilled or deionized water
before use.
SPECIAL PRECAUTIONS: Perform all acid digestions in a fume hood.
SAMPLING:

2. Sample at an accurately known flow rate between 1 and 3 L/min for a total sample size of 10 to
400 L Do not exceed 2 mg total dust loading on the filter.
SAMPLE PREPARATION:
NOTE: Alumina (AI2O3) will not be dissolved by this procedure. Lithium borate fusion is necessary to
dissolve alumina. The following sample preparation gave quantitative recovery for soluble
aluminum compounds (see EVALUATION OF METHOD). Steps 4 through 9 of Method 7300 or
other quantitative ashing techniques may be substituted, especially if several metals are to be
determined on a single filter.
3. Open the cassettes and transfer the samples and blanks to separate clean beakers.
4. Add 6 mL conc. HNO3 and cover with a watchglass. Start reagent blanks at this point.
5. Heat on hotplate (140 °C) until sample dissolves and a slightly yellow solution is produced. Add
acid as needed to completely destroy organic material.
6. When the sample solution is clear, remove watchglass and rinse into the beaker with 10% HNO3.
7. Place the beakers on a hotplate and allow to go to a small liquid volume (ca. 0.5 mL).
8. When sample is dry, rinse walls of beaker with 3 to 5 mL 10% HNO3. Reheat for 5 min to
dissolve the residue, then allow to air cool.
9. Transfer the solution quantitatively to a 10-mL volumetric flask containing 0.2 mL 50 mg/mL Cs
solution. Dilute to volume with 10% HNO3.
NOTE: If vanadium or sulfuric acid are present, add 1% (w/w) La as a releasing agent [1,3].
10. Add known amounts, covering the range 0 to 500 mg Al per sample, of calibration stock solution
to 100-mL volumetric flasks containing 2.0 mL 50 mg/mL Cs solution and dilute to volume with
10% HNO3.

ALUMINUM and compounds, as Al: METHOD 7013, Issue 2, dated 15 August 1994 - Page 3 of 3
11. Analyze the working standards together with the samples and blanks (steps 16 and 17).
12. Prepare a calibration graph of absorbance vs. solution concentration (/ug/mL).
13. Aspirate a standard for every 10 samples to check instrument drift.
14. Check recoveries with at least one spiked media blank per 10 samples.
15. Use method of additions occasionally to check for interferences.
MEASUREMENT:
16. Set spectrophotometer according to manufacturer's instructions and to conditions on

page 7013-1.
17. Aspirate standards and samples. Record absorbance readings.
NOTE: If the absorbance values for the samples are above the linear range of the standards,
dilute the solutions with 10% HNO3 and an appropriate amount of the 50 mg/mL Cs
solution, reanalyze, and apply the appropriate dilution factor in the calculations.
CALCULATIONS:
18. Using the measured absorbances, calculate the corresponding concentrations (/ug/mL) of
aluminum in the sample, Cs, and average media blank, Cb, from the calibration graph.
19. Using the solution volumes (mL) of the sample, Vs, and media blanks, Vb, calculate the
concentration, C (mg/m ), of aluminum in the volume of air sampled, V (L):
(c.v. -
mg/m:
V
Estimated LOD was 2 //g Al per sample [2]. Only the analytical procedure was evaluated for this
method.
REFERENCES:
[2] User check, UBTL, NIOSH Seq. #3990-0 (unpublished, November 29, 1983).
[3] Winefordner, J. D., Ed., Spectrochemical Methods of Analysis, John Wiley & Sons (1971).
[4] Analytical Methods for Atomic Absorption Spectrophotometrv, Perkin-Elmer (1976).
METHOD REVISED BY:
Mark Millson, NIOSH/DPSE and R. DeLon Hull, Ph.D., NIOSH/DBBS.
TABLE 1 - ALUMINUM EXPOSURE LIMITS
OSHA NIOSH ACGIH

mg/m3 mg/m3 mg/m3
Total Dust no PEL 10 10

Respirable Fraction no PEL 5
Pyro powders no PEL 5 5
Welding fumes no PEL 5 5
Soluble salts no PEL 2 2
Alkyls no PEL 2 2

AMINES, ALIPHATIC 2010
(1) Diethylamine: (C2H5)2NH MW: 73.14 CAS: 109-89-7 RTECS: HZ8750000

(2) Dimethylamine: (CH3)2NH 45.08 124-40-3 IP8750000

OSHA : See Table 1 PROPERTIES: See Table 1

NIOSH: See Table 1
ACGIH: See Table 1
SYNONYMS: (1) DEA; N,N-diethamine; N-ethylethanamine;

(2) N-methylmethanamine; DMA

(silica gel, 150 mg / 75 mg)
ANALYTE: amines listed above
FLOW RATE: 0.01 to 1 .0 L/min
DESORPTION: 1 mL dilute H2SO4 in 10% (v/v) aqueous
VOL-MIN: 3 L @ OSHA standards (Table 1) methanol, 3 h ultrasonic
-MAX: 3OL
INJECTION
SHIPMENT: refrigerated VOLUME: 1 fjL
SAMPLE COLUMN: 1.8 m x 4-mm ID glass, 4% Carbowax

STABILITY: not determined 20M + 0.8% KOH on Carbosieve B
(60/80 mesh)
FIELD BLANKS: 2 to 10 field blanks per set
CARRIER GAS: nitrogen, 30 mL/min
CALIBRATION: standard solutions of analyte in dilute

sulfuric acid
ACCURACY
RANGE: (1) 0.5 to 11 mg per sample [1]
RANGE STUDIED: see EVALUATION OF METHOD (2) 0.15 to 2.6 mg per sample [1]
BIAS: (1) -5.0%; (2) 0.8% ESTIMATED LOD: 0.02 mg per sample
OVERALL PRECISION (SrT): see EVALUATION OF METHOD PRECISION (Sr): see EVALUATION OF METHOD
ACCURACY: (1) ±16.0%; (2) ±12.5%
APPLICABILITY: The working ranges for 20-L air samples are 8 to 183 ppm (25 to 550 mg/m3) for diethylamine and 4 to 71
ppm (7.5 to 130 mg/m3) for dimethylamine. A nitrogen-specific detector instead of an FID will greatly increase sensitivity. This
alternative detector has been used for amines with a 30 m x 0.25-mm x 0.25-//m film DB-5 fused-silica capillary column, with
column temperature 60 °C for 1 min, programmed to 300 °C at 10°/min; detector, 300 °C and injector, 250 °C.
INTERFERENCES: This method has been evaluated only in dry air [1]. Silica gel may have a reduced capacity at high
humidity. The methanol peak could interfere in low-level analyses.
OTHER METHODS: This revises and combines Methods S139 and S142[2]. The methods for other aliphatic amines are similar
[3,4,5,6]. To avoid possible sample instability on silica gel, OSHA developed a method (OSHA 34) which employs XAD-7 coated
with 7-chloro-4-nitrobenzo-2-oxa-1,3-diazole for sampling followed by HPLC of the derivative [7].

AMINES, ALIPHATIC: METHOD 2010, Issue 2, dated 15 August 1994 - Page 2 of 4
1. Sulfuric acid, 0.1 M, in 10% (v/v) aqueous 1. Sampler: glass tube flame-sealed ends, with
methanol (90% H2O + 10% methanol).* plastic caps, 7 cm x 6-mm OD x 4-mm ID,
2. Potassium hydroxide (KOH) solution, 0.3 M.* containing two sections of 20/40 mesh silica
3. Amines, highest purity available.* gel (front = 150 mg; back = 75 mg).
NOTE: Dimethylamine is commercially Silanized glass wool plug precedes front.
available as a 40% aqueous solution Urethane foam plugs, separate and retain the
(Aldrich Co. or equivalent). back section. Tubes are commercially
4. Calibration stock solution.* Dilute 1 mL of available.
amine to 10 mL with deionized water. Check 2. Personal sampling pump, 0.01 to 1 L/min, with
concentration by titrating with standard sulfuric flexible connecting tubing.
acid. 3. Refrigerated, bagged ("Blue-Ice," or
5. Hydrogen, prepurified. equivalent).
6. Nitrogen, purified. 4. Gas chromatograph, FID, integrator, and
7. Air, compressed and filtered. column (page 2010-1).
5. Vials, glass, 2-mL, with PTFE-lined caps.
6. Ultrasonic bath.
7. Syringes, 20-//L, 10-//L, 1-//L
See SPECIAL PRECAUTIONS. 8. Pipets, 0.5-, 1-, 2-, and 10-mL
10-File.
1 1 Tweezers.
SPECIAL PRECAUTIONS: The amines are highly flammable and have strong ammoniacal odors. They
can cause severe eye damage and can easily be absorbed through the skin [8]. Sulfuric acid is highly
corrosive, and potassium hydroxide is caustic. All work with these compounds should be performed in
a hood. Use proper protective clothing including gloves, safety glasses, and laboratory coat.
SAMPLING:

2. Break the ends of the samplers immediately prior to sampling. Attach sampler to pump with
flexible tubing.
to 30 L
4. Cap the samplers and pack securely for shipment with bagged refrigerant.
SAMPLE PREPARATION:
5. Place the front and back sorbent sections of the sampler tube in separate vials. Add the glass
wool plug to the front sorbent section vial. Discard the foam plugs.
6. Add 1.0 mL 0.1 M H2SO4 in aqueous methanol. Tightly cap the vial.
7. Agitate the vials in ultrasonic water bath for 3 h.
NOTE: The water in the ultrasonic bath can get hot (ca. 50-60 °C) during the desorption period.
Therefore, all vials must be tightly capped to minimize evaporation losses.
8. Neutralize the sample solution as follows: let silica gel particles settle for a few minutes.
Transfer a 500-/7L aliquot of the supernatant liquid to a clean vial. Add 500 //L 0.3 M KOH. (The
pH of the solution should be greater than 10). Analyze the solutions immediately (steps 12
through 14).
NOTE: Ensure that no silica gel is present when adding KOH to prevent loss of analyte [1].

9. Calibrate daily with at least six working standards covering the range of interest.
a. Add aliquots of the calibration stock solutions to 10-mL volumetric flasks and dilute to the
mark with 0.1 M sulfuric acid in aqueous methanol.
b. Neutralize the standards as in step 8.
c. Analyze with samples and blanks (steps 12 through 14).
d. Prepare a calibration graph (peak area or peak height vs. mg of amine per sample).
10. Determine desorption (DE) at least once for each lot of silica gel used for sampling in the
concentration range of interest. Prepare four tubes at each of five levels plus media blanks.
a. Measure the amount of silica gel used in the front sorbent section into a vial.
b. Inject a known amount (1 to 20 fjL) of calibration stock solution, or a dilution there of
directly onto the silica gel.
c. Cap vial. Allow to stand overnight.
d. Desorb and neutralize as in steps 6 through 8.
e. Analyze together with working standards and blanks (steps 12 through 14).
f. Prepare a graph of DE vs. mg analyte recovered.
MEASUREMENT:
on page 2010-1. Use the following conditions as a guide.
Temperature (°C)
Compound Injection Column Detector
Diethylamine 160 70 200

Dimethylamine 155 60 200
NOTE: Use a removable glass liner at the inlet to the GC column. Remove the glass liner from
the gas chromatograph and clean it with water and acetone rinses at the end of each
day. In order to prevent salt buildup, the glass GC liner was soaked in a saturated KOH
solution and packed with KOH-coated glass wool [9].
13. Inject sample aliquot manually using solvent flush technique or with autosampler.
14. Measure peak area or peak height.
CALCULATIONS:
15. Determine the mass, mg (corrected for DE), of analytes found in sample front (Wf) and back
(Wb) sorbent sections and in the media blank front (Bf) and blank back (Bb) sorbent sections
from the calibration graph.
16. Calculate concentration of analyte, C (mg/m3), in the air volume sampled, V (L):
C . W - Wb - B, -
Precisions, biases, and recoveries listed below were determined by analyzing generated atmospheres
containing one-half, one, and two times the OSHA standard [1,2,3]. Generated concentrations were
independently verified. Breakthrough of the front section of the silica gel tube was not observed after
sampling a dry test atmosphere. Sample stability was not determined.

SAMPLING MEASUREMENT OVERALL
Substance BTa Conc. Range Range Precision Bias Precision Accuracy

Vol. (mg/m3) (mg/m3) (mg/sample) A) DE (%) (S,T)
(L)
Diethylamine >46 160 36-165 1.8-7.1 0.02 0.82 5 0.07 18.7
Dimethylamine >45.6 42.5 7.02-29.5 0.4-1.7 0.03 0.92 1.1 0.062 13.2
aBreakthrough (BT) experiments performed at flow rate of 0.2 L/min.
REFERENCES:
Education, and Welfare, Publ. (NIOSH) 77-185 (1977), available as Stock No. PB 274-248 from
NTIS, Springfield, VA 22161.
[2] NIOSH Manual of Analytical Methods, 2nd. ed., Vol. 3, S139 and S142, U.S. Department of
Health, Education, and Welfare, Publ. (NIOSH) 77-157-C (1977).
[3] Ibid., Vol. 1, P&CAM 221, U.S. Department of Health, Education, and Welfare, Publ. (NIOSH) 77-
157-A (1977).
[4] Ibid., S144, S146, and S150.
[5] Campbell, Evan E., G.O. Wood, and R.G. Anderson. "Development of Air Sampling Techniques,"
Los Alamos Scientific Laboratory, Progress Reports (unpublished) LA-5634-PR (June 1974), LA-
5973-PR (July 1975), and LA-6057-PR (September 1975).
[6] Wood, G.O. and R.G. Anderson. "Development of Air Monitoring Techniques Using Solid
Sorbents," Los Alamos Scientific Laboratory, Progress Reports (unpublished) LA-6216-PR
(February 1976) and LA-6513-PR (September 1976).
[7] OSHA Manual of Analytical Methods, USDOL OSHA Salt Lake City Technical Center, Salt Lake
City, UT. Available from ACGIH, Cincinnati, OH (1991).
and Human Services, Publ. (NIOSH) 81-123 (1981).
[9] Andre, C.E. and A.R. Mosier. "Precolumn Inlet System for the Gas Chromatographic Analysis of
Trace Quantities of Short-Chain Aliphatic Amines," Anal. Chem., 45. 1971 (1973).
METHOD REVISED BY:
Paula Fey O'Connor, NIOSH/DPSE.
Table 1. Exposure Limits and Properties.
Compound Exposure Limits, ppm mg/m3/ppm Properties

OSHA NIOSH ACGIH @ NTP
Diethylamine 25 10; 5 (skin) 2.99 Liquid; d 0.708 g/mL @ 20 °C;

STEL 25 STEL 15 MP -50 °C; BP 55.5 °C; vapor density
(air = 1) 2.5; VP 25.9 kPa (195 mm Hg)
@ 20 °C; explosive limits in air 1.8 to
10.1% (v/v)
Dimethylamine 10 10 5; 1.84 Gas; MP -92.2 °C; BP 6.88 °C; vapor

STEL 5 density (air = 1) 1.6; VP 173.9 kPa
(1307.2 mm Hg) @ 20 °C; explosive
limits in air 2.8 to 14% (v/v)

AMINES, AROMATIC 2002
METHOD: 2002, Issue 2 EVALUATION: FULL (1-3); PARTIAL (4,5) Issue 1: 15 May 1985

NIOSH: Table 2
ACGIH: Table 2
SYNONYMS: (1) aniline: benzenamine; aminobenzene; phenylamine

(2) o-toluidine: 2-aminotoluene
(3) 2,4-xylidine: 2,4-dimethylaniline; dimethylaminobenzene
(4) N,N-dimethyl-g-toluidine: g-dimethylaminotoluene
(5) N,N-dimethylaniline: N.N-dimethylbenzeneamine

(silica gel, 150 mg/75 mg)
ANALYTE: amines listed above
FLOW RATE: Table 2
DESORPTION: 1 mL95% ethanol; 1 h in ultrasonic bath
VOL-MIN: Table 2
-MAX: Table 2 INJECTION
VOLUME: 5 M-
SHIPMENT: routine
SAMPLE
STABILITY: (1), (2), and (3) stable for > 7 days [1]; COLUMN: stainless steel, 0.6 m x 3-mm OD, packed
stability data not available for (4) and (5) with 80/100 mesh Chromosorb 103
BLANKS: 2 to 10 field blanks per set CALIBRATION: standard solutions of analytes in 95%
ethanol
RANGE: 0.1 to 3 mg per sample

ACCURACY
ESTIMATED LOD: 0.01 mg per sample [2]; not determined
RANGE STUDIED: see EVALUATION OF METHOD for (3)
PRECISION (§r): see EVALUATION OF METHOD
OVERALL PRECISION (SrT): see EVALUATION OF METHOD
ACCURACY: see EVALUATION OF METHOD
APPLICABILITY: See Table 2 for working ranges. A modification of this method has been used for aniline and o-toluidine at
a vulcanized rubber manufacturing plant [2]. Applicability of this method for simultaneous determination of the analytes has
not been investigated. A nitrogen-specific GC detector instead of an FID will greatly increase sensitivity.
INTERFERENCES: None known. Silica gel has reduced capacity for organic compounds at high humidity.
OTHER METHODS: This combines Methods S162 (xylidine) [3], S164 (dimethylaniline) [3], S168 (o-toluidine) [3], S310 (aniline)
[3], P&CAM 280 (N,N-dimethyl-p-toluidine) [4], and P&CAM 168 (aromatic amines) [5,6].

AMINES, AROMATIC: METHOD 2002, Issue 2, dated 15 August 1994 - Page 2 of 6
1. Ethanol, 95%, non-denatured, 1. Sampler: glass tube, 7 cm long, 6-mm OD,

chromatographic quality. 4-mm ID; with plastic caps; containing two
2. n-Hexane. sections of 20/40 mesh silica gel separated
3. Benzene.* by a 2-mm portion of urethane foam (front =
4. Analytes, reagent grade.* 150 mg; back = 75 mg). For
5. Aniline calibration stock solution, 102.2 N,N-dimethyl-p-toluidine, a front section of
mg/mL* Dissolve 1 mL aniline in 2 mL 100 mg and back section of 50 mg may be
benzene; dilute to 10 mL with hexane. used. A silylated glass wool plug precedes
NOTE: Benzene possibly could be replaced the front section and a 3-mm urethane foam
with toluene, alcohol, or acetone to plug follows the back section. Pressure
minimize the analyst's exposure to drop across the tube at 1 L/min airflow must
suspect carcinogens. Effects of this be less than 3.4 kPa. Tubes are
substitution are not known and commercially available.
should be tested. 2. Personal sampling pump, 0.02 to 1 L/min,
6. o-Toluidine calibration stock solution, 100.6 with flexible connecting tubing.
mg/mL* Dilute 1 mL o-toluidine to 10 mL 3. Gas chromatograph, FID, integrator and
with n-hexane. column (page 2002-1).
7. 2,4-Xylidine calibration stock solution, 97.8 4. Vials, glass, 2-mL, PTFE-lined crimp caps.
mg/mL* Dilute 1 mL 2,4-xylidine to 10 mL 5. Syringes, 10-, 25-, 50- and 100-//L
with n-hexane. 6. Pipets, 1 - and 2-mL
8. N,N-Dimethyl-p_-toluidine calibration stock 7. Ultrasonic bath.
solution, 93.5 mg/mL* Dilute 1 mL 8. File.
N,N-dimethyl-p.-toluidine to 10 mL with 9. Tweezers.
n-hexane. 10. Flasks, volumetric, 10-mL
9. N,N-Dimethylaniline calibration stock
solution, 95.6 mg/mL* Dilute 1 mL
N,N-dimethylaniline to 10 mL with hexane.
10. Hydrogen, prepurified.
11. Helium, purified.
12. Nitrogen, purified.
13. Air, filtered, compressed.
SPECIAL PRECAUTIONS: n-Hexane and ethanol are flammable. Aniline, o-toluidine, 2,4-xylidine, and
benzene are suspect carcinogens [7,8]. Absorption through skin is a potential hazard. All work with
these chemicals should be performed in a hood. Use proper protective clothing including gloves.
Analytes (1), (2), (3), and (5) are severe poisons.
SAMPLING:

3. Sample at an accurately known flow rate for a total sample size according to Table 3.

SAMPLE PREPARATION:
wool plug to the front sorbent section vial. Discard the foam plugs.
6. Add 1.0 mL 95% ethanol to each vial. Attach crimp cap to each vial.
7. Agitate 1 h in an ultrasonic bath.
8. Calibrate daily with at least six working standards over the range 0.01 to 3 mg analyte per
sample.
a. Add known amounts of calibration stock solution, or a dilution thereof, in n-hexane to 95%
ethanol in 10-mL volumetric flasks and dilute to the mark.
c. Prepare calibration graph (peak area or height vs. mg analyte).
9. Determine desorption efficiency (DE) at least once for each lot of silica gel used for sampling in
the calibration range. Prepare three tubes at each of five levels plus three media blanks.
b. Inject a known amount (1 to 20 fjL) of calibration stock solution, or a dilution thereof, in
hexane directly onto front sorbent section with a microliter syringe.
MEASUREMENT:
autosampler. Use the following conditions as a guide (these were used in development of the
methods [1]):
TEMPERATURES. °C
COMPOUND Injection Column Detector
Aniline 230 165 245

o-Toluidine 240 180 265
2,4-Xylidine 230 170 235
N,N-Dimethyl-p.-toluidine 250 180 250
N,N-Dimethylaniline 150 100for4min, 250
then 8°C/min
to 225
NOTE: If peak response is above the linear range of the working standards, dilute with 95%
ethanol, reanalyze, and apply the appropriate dilution factor in calculations.
12. Measure peak area or height.

_AMINES, AROMATIC: METHOD 2002, Issue 2, dated 15 August 1994 - Page 4 of 6_
CALCULATIONS:
(Wb) sorbent sections, and in the average media blank front (B() and back (Bb) sorbent sections.
NOTE: If Wb > W,/I0, report breakthrough and possible sample loss.
C . mg/m
Precisions, biases and recoveries listed below were determined by analyzing generated atmospheres
containing one-half, one and two times the OSHA standard [1]. Generated concentrations were
independently verified. Breakthrough of the front section of the silica gel tube was not observed after
sampling a dry test atmosphere. The first three analytes were stable on silica gel for at least one week.
Method S164 using collection on activated charcoal was also developed for N,N-dimethylaniline [3].
Sampling
Breakthrough
volume in dry air Range Overall Measurement
at concentration mg/m3 Bias Precision Accuracy Range Precision Desorption
Substance (L) (mg/m3) (volume) (%) (S,T) (%) (mg) (S,) efficiency
Aniline >44.4 38 9.5-38.2 -4.9 0.060 ±15.1 0.20-0.82 0.013 0.980-1.00

(20 L)
o-Toluidine >221.3 47 11.7-46.9 -1.5 0.060 ±12.0 0.55-2.2 0.032 0.970-0.983

(50 L)
2,4-Xylidine >44.4 50 12.5-50.0 -1.2 0.057 ±11.2 0.25-1.01 0.021 0.959-1.015

(20 L)
N,N-Dimethyl-e- * * 9.4-30.0 * * * 0.47 0.035 0.88

toluidine (100 L)
N,N-Dimethyl- * * * -7.9 0.090 ±16.0 0.05-3.0 * 0.997

aniline (1.9-mg
samples)
*Not determined
REFERENCES:
[1] Documentation of the NIOSH Validation Tests, S162, S164, S168, S310, U.S. Department of
Health, Education, and Welfare, Publ. (NIOSH) 77-185 (1977), available as GPO Stock
#017-033-00231-2 from Superintendent of Documents, Washington, DC 20402.
[2] UBTL, Inc., Sequence #2300-8, Aniline (May 15, 1980), and Sequence #2551 -M, o-Toluidine
(August 28, 1980) (NIOSH, unpublished).
[3] NIOSH Manual of Analytical Methods, 2nd ed., Vol. 3, S162, S164, S168, S310, U.S. Department
of Health, Education, and Welfare, Publ. (NIOSH) 77-1 57-C (1977).
[4] Ibid., Vol. 4, P&CAM 280, U.S. Department of Health, Education, and Welfare, Publ. (NIOSH)
78-175 (1978).
77-1 57-A (1977).

[6] Campbell, E. E., G. O. Wood and R. G. Anderson. Los Alamos Scientific Laboratory Progress
Reports LA-5104-PR, LA-5164-PR, LA-5308-PR, LA-5389-PR, LA-5484-PR and LA-5634-PR, Los
Alamos, NM (November, 1972; January, 1973; June, 1973; August, 1973; December, 1973; and
June, 1974).
[7] Registry of Toxic Effects of Chemical Substances, 1979 eds., Vols. 1 and 2, U.S. Department of
Health and Human Services, Publ. (NIOSH) 80-111 (1980).
[8] NIOSH/OSHA Occupational Health Guidelines for Chemical Hazards, Aniline and o-Toluidine,
U.S. Department of Health and Human Services, Publ. (NIOSH) 81-123 (1981), available as GPO
Stock #017-033-00337-8 from Superintendent of Documents, Washington, DC 20402.
METHOD WRITTEN BY:
Paula Fey O'Connor, Julie R. Okenfuss and George Williamson, NIOSH/DPSE.
TABLE 1. PHYSICAL PROPERTIES AND PERSONAL EXPOSURE LIMITS
VP Conversion
5) 20 °C factor
Substance BP MP d, g/mL kPa (ppm to mg/m3
Formula MW @20 °C (mm Hg) @ NTP)
Aniline; 93.13 184 -6 1.022 0.089 3.81

C6H7N (0.3)
o-Toluidine; 107.16 200 -15 1.006 0.043 4.38

C7H9N (0.32)
2,4-Xylidine; 121.18 214 -14 0.9723 <0.1 4.95

C8HHN
N,N-Dimethyl-p_-toluidine; 135.21 211 NA 0.935 NA 5.53

C9H13N
N.N-Dimethylaniline; 121.18 192 2 0.956 <0.1 4.95

CeH^N (0.5)
NA = not available.

TABLE 2. GENERAL INFORMATION.

Exposure Limits (ppm)
Substance CAS RTECS OSHA NIOSH ACGIH
Aniline 62-53-3 BW6650000 5 (skin) lowest feasible 2 (skin)

(carcinogen)
o-Toluidine 95-53-4 XU2975000 5 (skin) lowest feasible 2 (skin)

(carcinogen; skin) (carcinogen)
2,4-Xylidine 1300-73-8 ZE8575000 5 (skin) 2 (skin) 0.5 (skin)
N,N-Dimethyl-p_-toluidine 99-97-8 XU5803000 —
N,N-Dimethylaniline 121-69-7 BX4275000 5 (skin) 5 TWA; 5 TWA;

10 STEL 10 STEL
(skin) (skin)
TABLE 3. SAMPLING FLOW RATES AND VOLUMES.
SAMPLING
Flow Rate Volume (L)
Substance (L/min) MIN MAX Working Range (mg/m3
Aniline 0.02 - 0.2 5 30 5 - 60 (20-L samples)
o-Toluidine 0.02- 1.0 10 150 5 - 60 (55-L samples)
2,4-Xylidine 0.02 - 0.2 3 20 3 - 75 (20-L samples)
N,N-Dimethyl-p_-toluidine 0.02- 1.0 * 9 - 30 (100-L samples)
N,N-Dimethylaniline 0.02 - 1.0 30 1 .3 - 79 (38-L samples)
"Not determined.

AMINOETHANOL COMPOUNDS I 2007


NIOSH: Table 1
ACGIH: Table 1
COMPOUNDS 2-aminoethanol: ethanolamine; 2-hydroxyethylamine

and 2-dibutylaminoethanol: 2-n-dibutylaminoethanol; DBAE
SYNONYMS: 2-diethylaminoethanol: 2-hydroxytriethylamine

DESORPTION: 2 mL 4:1 (v/v) methanol: water; stand 2 h
VOL-MIN: 4L with occasional shaking
-MAX: 24 L
INJECTION
FIELD TREATMENT: add 20 fjL conc. HCI to silica VOLUME: 3fJL
gel immediately after sampling
-COLUMN: 90 °C, 3 min; 90 to 225
SAMPLE °C @ 16°/min, hold 6
STABILITY: at least 4 weeks @ 25 °C [1] min
COLUMN: 1.8 m x 2-mm ID silanized glass, 10%

Carbowax 20 M + 2% KOH on 80/100
mesh Chromosorb WAW
ACCURACY
CALIBRATION: solutions of analyte in 4: 1 methanol:water
RANGE STUDIED: see EVALUATION OF METHOD [1,2] containing 0.12 N HCI
BIAS: - 2.9% RANGE: 0.1 to 6 mg per sample [2]
OVERALL PRECISION (SrT): 0.056 [2] ESTIMATED LOD : 0.005 mg per sample [2]
ACCURACY: ± 12.1% PRECISION (§,): 0.026 @ 0.6 to 2.7 mg per sample [2]
APPLICABILITY: The working range is 5 to 300 mg/m3 for each compound in a 20-L air sample. Water vapor does not
significantly affect collection efficiency [3]. Sensitivity may be improved at least ten-fold by using a photoionization or
nitrogen-selective detector.
INTERFERENCES: None identified [3]. The chromatographic column or separation conditions may be changed to circumvent
interference problems. A DB-5 fused silica capillary column may be used.
OTHER METHODS: This revises P&CAM 270 [3], S140 [4], and Method 2007 (dated 5/15/85).

AMINOETHANOL COMPOUNDS I: METHOD 2007, Issue 2, dated 15 August 1994 - Page 2 of 5
1. Eluent: Four parts methanol to one part 1. Sampler: glass tube, 7-cm long, 8-mm OD,
distilled water (v/v). 6-mm ID, flame-sealed ends with plastic caps,
NOTE: Do not use deionized water which containing two sections of 45/60 mesh
may contain formaldehyde. chromatographic grade silica gel (front = 300
2. Analyte, reagent grade.* mg; back = 150 mg) separated by a plug of
3. Alkalinizing solution: 0.20 N NaOH (8.0 g silylated glass wool. A silylated plug of glass
NaOH/L) in eluent. wool is at each end of the tube. Pressure
4. HCI, conc. (38%, 12 N) (needed for field use).* drop across the tube at 0.2 L/min airflow must
5. HCI, 0.12 N, in eluent. Dilute 10.0 mL conc. be less than 3.2 kPa. Tubes are commercially
HCI with eluent to make 1 L solution. available. Do not use sampling tubes
6. Benzaldehyde. constructed with metal parts or urethane foam
7. Calibration stock solutions, 10 mg/mL, in 0.12 plugs. Conc. HCI will react with these
N HCI in eluent for each analyte. materials.
8. Nitrogen or helium, purified. 2. Personal sampling pump, 0.01 to 0.2 L/min,
9. Hydrogen, prepurified. with flexible connecting tubing.
10. Air, filtered. 3. Syringe for dispensing HCI, 50-//L with glass
1 1 . pH paper. barrel, PTFE-tipped plunger and inert (platinum
12. KOH, saturated solution. or PTFE) needle (for field use).
13. Glass wool. 4. Gas chromatograph, FID, integrator and
5. Coated capillary injection port liner: Soak liner
See SPECIAL PRECAUTIONS. and small quantity of glass wool in saturated
KOH. Air-dry liner and glass wool. Loosely
pack glass wool in liner.
6. Vials, 2-mL, glass, PTFE-lined crimp caps.
9. Micropipets, 10- to 100-//L
10. Pipets, 0.5- and 2-mL, with pipet bulb.
SPECIAL PRECAUTIONS: The analytes are eye irritants [5]. Avoid skin contact or inhalation of conc.
HCI.
SAMPLING:

to 24 L
NOTE: If samples are to be eluted immediately or will be stored in a freezer for less than 14
days, the following step may be eliminated.
4. Immediately after sampling, stabilize the samples by adding exactly 20 //L conc. HCI to each
section of silica gel in each sampler using a syringe.
NOTE 1 : The amount of HCI added must be measured carefully because the sample will be
neutralized and made alkaline (step 9) for proper chromatography.
NOTE 2: Iron impurities in silica gel will turn yellow upon addition of acid.

SAMPLE PREPARATION:
6. Place the first glass wool plug and the front section of the sampler in a vial. Place the second
plug and backup section in a separate vial.
7. Add 2.0 mL eluent to each vial. Attach cap to each vial.
NOTE: If conc. HCI was not added to the silica gel after sampling, desorb the samples in
2.0 mL 0.12 N HCI in eluent. The acid increases desorption efficiency.
8. Allow to stand 2 h with occasional agitation.
9. Transfer a 0.5-mL aliquot of each sample to another vial. Add 0.5 mL alkalinizing solution and
attach cap. Mix thoroughly. Check the solution pH with pH paper. If the solution pH is <9 add
alkalinizing solution until solution pH is >9.
10. If 2-aminoethanol is present, repeat step 9 with another 0.5-mL aliquot. Add 10 fjL
benzaldehyde to the basic solution, mix thoroughly and let stand 20 min.
NOTE: Benzaldehyde derivatizes 2-aminoethanol to 2-benzylideneaminoethanol which has a
higher molecular weight, thereby decreasing the GC detection limit. Underivatized
2-aminoethanol can be determined by this method if the sample size is large.
11. Calibrate daily with at least six working standards over the range 0.005 to 6 mg of each analyte.
a. Add known amounts of analyte or calibration stock solution to 0.12 N HCI in eluent in 10-mL
volumetric flasks and dilute to the mark.
b. Treat the working standards with base and benzaldehyde as needed (steps 9 and 10).
c. Analyze together with samples and blanks (steps 14 and 15).
d. Prepare calibration graph (peak area vs. mg analyte).
12. Determine desorption efficiency (DE) at least once for each lot of silica gel used for sampling.
Prepare three tubes at each of five levels plus three media blanks.
b. Inject a known amount of analyte or calibration stock solution directly onto front sorbent
section with a microliter syringe.
c. Add 20.0 fjL conc. HCI.
d. Cap the tube. Allow to stand overnight.
e. Desorb (steps 6 through 10) and analyze with working standards (steps 14 and 15).
f. Prepare a graph of DE vs. mg analyte recovered.
MEASUREMENT:
autosampler.
NOTE 1: The temperature program separates all three compounds. Isothermal column
conditions are 225, 150, and 90 °C for 2-aminoethanol, 2-dibutylaminoethanol and
2-diethylaminoethanol, respectively. The column packing degrades rapidly at
225 °C; keep operating time at a minimum near this temperature.
NOTE 2: If peak area is above the linear range of the working standards, dilute with eluent,
reanalyze, and apply the appropriate dilution factor in calculations.
NOTE 3: When using a capillary column system, use the split injection port liner coated with
KOH to improve amine peak shape.

AMINOETHANOL COMPOUNDS I: METHOD 2007. Issue 2, dated 15 August 1994 - Page 4 of 5
CALCULATIONS:
NOTE: If Wb > Wt/10, report breakthrough and possible sample loss.
c-
All three compounds were evaluated under Method P&CAM 270 using a smaller bed of silica gel (front =
150 mg; back = 150 mg) than given above [3]. Desorption efficiencies for 0.1 mg analyte were found to
be 0.97 for 2-aminoethanol, 0.85 for 2-diethylaminoethanol, and 0.93 for 2-dibutylaminoethanol [3]. Only
2-diethylaminoethanol was evaluated under Method S140 using the suggested sorbent tube. In all
cases, laboratory testing was performed with spiked samples and generated atmosphere [1,2,6]. All
analytes were stable on silica gel up to four weeks when stabilized with acid. Results were:
Range Studied Sample Precision

Compound Method (mg/m3) size (L) Measurement (Sr) Overall (SrT)
2-aminoethanol P&CAM 270 [3] 30.4 to 63.6 30 < 0.070 0.057

2-dibutylaminoethanol P&CAM 270 [3] unknown unknown unknown unknown
2-diethylaminoethanol S140 [4] 25 to 113 24 0.026 0.056
Method S140 [4] was issued on January 19, 1979, and validated over the range 25 to 113 mg/m3
at 23 °C and 762 mm Hg using 24-L samples [2,7]. Coast Engineering Laboratory 40/60 mesh silica
gel was the collecting medium. Average recovery was 97.1%, representing a non-significant bias.
The concentration of 2-diethylaminoethanol was independently verified using midget bubblers con
taining 15 mL 2% HCI. Desorption efficiency was 0.964 in the range 0.6 to 2.3 mg per sample.
Breakthrough (5% on back section) was not achieved after 5.3 h when sampling an atmosphere
containing 88 mg/m3 2-diethylaminoethanol at 0.2 L/min at 82% relative humidity.
REFERENCES:
[1] Wood, G. O. and J. W. Nickols. Development of Air-Monitoring Techniques Using Solid

Sorbents, October 1, 1976 - December 31, 1977, Progress Report LA-7295-PR, Los Alamos
Scientific Laboratory, Los Alamos, NM, NIOSH IA-77-12 (1978).
[2] Backup Data Report No. S140, prepared under NIOSH Contract 210-76-0123 (NIOSH,
unpublished, 1979); Report on NIOSH Sequence #5162 (unpublished, April 2, 1986).
[3] NIOSH Manual of Analytical Methods, 2nd ed., Vol. 4, P&CAM 270, U.S. Department of Health,
[4] Ibid., Vol. 5, S140, U.S. Department of Health, Education, and Welfare, Publ. (NIOSH) 79-141
(1979).
[5] NIOSH/OSHA Occupational Health Guidelines for Chemical Hazards, Diethylaminoethanol and
Ethanolamine, U.S. Department of Health and Human Services, Publ. (NIOSH) 81-123 (1981),
available as GPO Stock #017-033-00337-8 from Superintendent of Documents, Washington, DC
20402.
[6] Wood, G. O., R. G. Anderson and J. W. Nickols. Sampling and Analysis of Aminoethanols in Air,
Report LA-UR-77-1398, Industrial Hygiene Group, Los Alamos Scientific Laboratory, Los Alamos,

NM (1977) (presented at the 1977 American Industrial Hygiene Conference, May 1977, New
Orleans, LA).
[7] NIOSH Research Report - Development and Validation of Methods for Sampling and Analysis of
80-133 (1980).
METHOD REVISED BY:
Ardith A. Grote, NIOSH/DPSE.
TABLE 1. STRUCTURAL FORMULAS, MOLECULAR WEIGHTS, PERMISSIBLE EXPOSURE LIMITS

AND PROPERTIES.
mg/m3 = OSHA Density

CAS 1 ppm NIOSH BP VP @ (g/mL @
Compound RTECS Formula MW @NTP ACGIH (ppm) (°C) 20 °C 20 °C)
2-aminoethanol 141-43-5 HOCH2CH2NH2 61.08 2.50 3 TWA 171 48 kPa 1.0180

KJ5775000 3 TWA; 6 STEL (470 ppm)
3 TWA; 6 STEL
2-dibutylamino- 102-81-8 (C4H9)2N(CH2)2OH 173.30 7.09 no standard 228 not 0.859

ethanol KK3850000 2 TWA (skin) available
2 TWA (skin)
2-diethylamino- 100-37-8 (C2H5)2N(CH2)2OH 117.19 4.79 10 TWA (skin) 163 130 kPa 0.8921
ethanol KK5075000 10 TWA (skin) (1300 ppm)
10 TWA (skin)

AMINOETHANOL COMPOUNDS II 3509
(1) HOCH2CH2NH2 MW: 61.10 CAS: 141-43-5 RTECS: KJ5775000

(2) (HOCH2CH2)2NH 105.14 111-42-2 KL2975000
(3) (HOCH2CH2)3N 149.19 102-71-6 KL9275000


NIOSH: Table 1
ACGIH: Table 1
SYNONYMS: (1) 2-aminoethanol; monoethanolamine; MEA

(2) 2,2'-iminodlethanol; diethanolamine; DEA
(3) 2,2',2"- nitrilotriethanol; triethanolamine; TEA
SAMPLER: IMPINGER TECHNIQUE: ION CHROMATOGRAPHY, ion pairing

(15 mL 2 mM hexanesulfonic acid) [2,3]
FLOW RATE: 0.5 to 1 L/min ANALYTE: MEA, DEA, TEA
VOL-MIN: 5 L INJECTION
-MAX: 300 L LOOP VOLUME: 50 fj\.
SHIPMENT: routine ELUENT: 2 mM hexanesulfonic acid (HSA), 1

mL/min (2 mM HSA/0.5% v/v acetonltrile
SAMPLE may also be used to reduce run time)
STABILITY: stable at least 3 weeks @ 20 °C [1]
COLUMNS: Ion-pairing guard and cation separator,
BLANKS: 2 to 10 field blanks per set Dionex MPIC-NG1.MPIC-NS1, and cation
suppressor
CONDUCTIVITY
SETTING: 3 A/S full scale
ACCURACY
RANGE: see EVALUATION OF METHOD [1] and
RANGE STUDIED: see EVALUATION OF METHOD [1] and Table 2
Table 2
ESTIMATED LOD: 7 to 20 //g per sample (Table 2)
OVERALL PRECISION (SrT): not determined PRECISION (5r): see EVALUATION OF METHOD [1] and
Table 2
APPLICABILITY: The working ranges for MEA, DEA, and TEA are 0.08 to 12 ppm (0.2 to 30 mg/m3), 0.09 to 7 ppm (0.4 to 30
mg/m3) and 0.1 to 5 ppm (0.6 to 30 mg/m3), respectively, for a 100-L air sample. The method is better suited to area sampling
than personal sampling because it uses an impinger for sample collection.
INTERFERENCES: Larger amines such as cocomorpholine, triethylenediamine, 4-ethylmorpholine,

2-oxybis(N,N-dimethyl)ethylamine, n-cetyl-N,N-dimethylamine do notelute under these analytical conditions and do not interfere.
Other low molecular weight amines may interfere. Sodium and ammonium ions can interfere with MEA.
OTHER METHODS: This is adapted from the method of Bouyoucos and Melcher [2,3]. There are no other NIOSH methods
for DEA or TEA. MEA can be determined by method 2007, using silica gel collection and gas chromatographic analysis.

AMINOETHANOL COMPOUNDS II: METHOD 3509, Issue 2, dated 15 August 1994 - Page 2 of 5
1. Hexanesulfonic acid (HSA), 2 mM (diluted 1. Sampler: midget impinger containing 15 mL of

from 0.1M solution obtained from Dionex 2 mM HSA.
Corp.). 2. Personal sampling pump, 0.5 to 1 L/min, with
2. Acetonitrile, reagent grade. flexible connecting tubing and glass wool trap.
3. Ethanolamine*, high purity. 3. Ion chromatograph, with ion-pairing guard and
4. Diethanolamine*, high purity. separator columns, cation suppressor (fiber
5. Triethanolamine*, high purity. suppressor or micromembrane suppressor),
6. Water, distilled. integrator and strip chart recorder (page
7. Regenerant for IC suppressor. For fiber 3509-1).
suppressor use 40 mM tetramethylammonium 4. Marker, China.
hydroxide (TMAOH) at 2 mL/min. For cation 5. Vials, scintillation, plastic, 20-mL, for shipping
micromembrane suppressor use 2 mM and storage of samples.
TMAOH at 4 mL/min. Prepare fresh weekly 6. Syringes, 10-mL, polypropylene, with luer tip.
and protect from atmospheric CO2 (which can 7. Filters, luer tip, with membrane filter,
lead to high background). 13- or 25-mm, 0.45-//m pore size.
8. Calibration stock solution, 1 fjg/fjL Weigh 8. Micropipets (or microliter syringes), 1- to
0.10 g of each amine into 100-mL volumetric 500-M-.
flask and dilute to mark with 2 mM 9. Flasks, volumetric, 50-, and 100-mL
hexanesulfonic acid. Store in a polyethylene 10. Bottles, polyethylene, 100-mL
bottle. 11. Pipet, 15-mL
SPECIAL PRECAUTIONS: Ethanolamines can cause skin and eye irritation [4]. Usual laboratory safety
procedures should be exercised.
SAMPLING:

2. Fill the impinger with 15 mL of 2 mM HSA. Mark the initial liquid level.
3. Attach impinger to sampling pump with flexible tubing. Insert a glass wool trap between the
impinger and sampling pump to prevent splashover.
4. Sample at an accurately known flow rate between 0.5 and 1 L/min for a total sample size of 5 to
300 L
5. Fill the sample solution in the impinger to the 15-mL mark with distilled water.
6. Transfer each impinger solution to a vial for shipment. Pack securely to avoid spillage during
transit.
7. Calibrate daily with at least six working standards over the range of interest.
a. Add known aliquots of calibration stock solution to 50-mL volumetric flasks and dilute to the
mark with eluent.
b. Store working standards in tightly-capped polyethylene bottles (glass may introduce sodium
ions, a chromatographic interference). Prepare fresh weekly.
c. Analyze working standards together with samples and blanks (steps 8 through 11).
d. Prepare a calibration graph for each analyte (peak height vs. //g analyte).

MEASUREMENT:
8. Set the ion chromatograph to manufacturer's recommendations and to conditions given on page
3509-1. When using fiber or micromembrane suppression, if the background level is high, make
several injections of acetonitrile through the sample loop to lower the background level.
NOTE: Filter all samples, eluents, and water flowing through the ion chromatograph to avoid
plugging system valves or columns.
9. Transfer a portion of sample solution to a syringe fitted with an inline membrane filter, for direct
injection or for transfer to autosampler vials.
10. Inject 50-fjL sample aliquot. For manual operation, inject 2 to 3 mL of sample from syringe
(through inline filter) to ensure complete rinse of the sample loop.
11. Measure peak height. If sample peak height exceeds the linear calibration range, dilute with
eluent, reanalyze, and apply the appropriate dilution factor in calculations.
CALCULATIONS:
12. Determine the mass, //g, of analyte in the impinger (W) and in the average media blank (B) from
the calibration graph.
13. Calculate the concentration, C, of analyte in the air volume sampled, V (L):
C . IW^ll. mg/m°.
This method was evaluated for DEA with generated air samples and for all three specified amines with
liquid spiked samples [5]. Samples for DEA were generated from methanol solution delivered by a
syringe pump to an ultrasonic nebulizer producing a mist which was mixed with dry, heated air in the
initial mixing chamber to evaporate the methanol. The flow passed into a sampling manifold where it
was mixed with humidified air to maintain a relative humidity of 73-78%. The system was monitored by
measuring the level of methanol in the sampling manifold with a Miran 1A infrared analyzer. The
recovery of DEA calculated from the methanol concentration varied from 70-95% in different generation
runs. After studies were complete, the initial mixing chamber was rinsed with 2 mM. HSA and was found
to contain 52 mg DEA, and a rinse of the sampling chamber contained 23 mg DEA, indicating that DEA
was lost in the generator during sample generation, and explaining the variation in recovery vs. that
calculated from the methanol concentration. In the first run, four samples were generated to test the
generation system. These samples were expected to contain 1305 //g DEA based on monitoring of the
methanol concentration. They were found to have 1237 ± 56 //g DEA, giving a recovery of 94.8%.
Next, twelve samples at each of two levels were generated for storage studies. All samples were
collected at 0.75 L/min and stored at room temperature (20 °C). Finally, six samples including backup
impingers were generated for breakthrough studies. The results of the storage and breakthrough studies
are given below:
Storage studies: 2-Day Storage 21 -Day Storage Recovery

N Found, //g RSD N Found, //g RSD after 21 days
Low level 5 226 4.9 5 215 13.4 95.1%

High level 6 885 3.3 4 865 3.0 97.7%
Breakthrough studies (stored 39 days at 20 °C):

N Found, //g RSD Breakthrough (average)
Front section 6 4433 7.2
Back section 6 137 N/A 2.68% (range 1.0-5.4%)
Total 6 4570 8.2

The method was further evaluated by spiking 2 mM hexanesulfonic acid impinger solutions with all three
ethanolamines, at 2, 10, and 20 times the estimated LOQ, six spikes per analyte at each level, and
analyzing them after storage at room temperature (20 °C) either for 2 days or for 21 days. Recovery of
all analytes and at all levels tested (42 to 409 fjg MEA, 79 to 712 //g DEA, and 1 17 to 1 161 //g TEA) was
between 94 and 1 06% after 3 weeks storage.
REFERENCES:
[1] Bolyard, Michele and George Williamson, Method Development Efforts for Ethanolamine
Compounds, NIOSH/MRSB, Unpubl. (NIOSH) 1988.
[2] Determination of Ethanolamines in Refinery Water, Application Note #39, Dionex Corporation,
Sunnyvale, CA, (February, 1982).
[3] Bouyoucos, Spiros A. and Richard G. Melcher., Collection of ethanolamines in air and
determination by mobile phase ion chromatography, Am. Ind. Hyg. Assoc. J. 47(3), 185-188
(1986).
[4] NIOSH Pocket Guide to Chemical Hazards, U.S. Dept. of Health and Human Services, Publ.
(NIOSH) 90-117, National Institute for Occupational Safety and Health, Cincinnati, OH 45226
(1990).
[5] Foley, G. D., Bolyard, M. L and L Blade. Sampling and Determination of Six Specific Amines,
presented at the American Industrial Hygiene Conference, San Francisco, CA (1988).
METHOD REVISED BY:
George Williamson, NIOSH/DPSE.
TABLE 1. EXPOSURE LIMITS AND PROPERTIES.
Exposure limits, ppm

Compounds OSHA NIOSH ACGIH Properties
Monoethanolamine 3 3;* 3; liquid; d 1.02 g/mL @ 20 °C;

(MEA) STEL 6 STEL 6 BP 170 5 °C; VP <0.13 kPa
(<1 mm Hg); flash point 152 °C
Diethanolamine No PEL 3 3 crystals or liquid; d 1.088 g/mL @

(DEA) 30 °C; MP 28 °C; BP 269 °C;
VP < 0.001 kPa (0.01 mm Hg); flash point
152 °C
Triethanolamine No PEL No REL 5 mg/m3 liquid; d 1.124 g/mL @ 20 °C;

(TEA) MP 21.2
kPa (<0.01
°C;mm
BP Hg);
335 °C
flash(decomp.);
point 191 VP
°C 0.001
* Group III Pesticide

TABLE 2. RANGE, LOD, AND LOQ.

Measurement
Range Studied mg/m3 = 1ppm LOD LOQ precision
(ma/sample) (5) NTP (UQ /sample) (ua /sample) (Sr)
Monoethanolamine
(MEA) 0.04 to 0.4 2.50 20 0.028
Diethanolamine
(DEA) 0.07 to 4.5 4.30 13 40 0.064
Triethanolamine
(TEA) 0.12 to 1.16 6.10 20 60 0.079

AMMONIA 6015
NH, MW: 17.03 CAS: 7664-41-7 RTECS: B00875000
METHOD: 6015, Issue 2 EVALUATION: PARTIAL Issue 1: 15 August 1994
OSHA : 50 ppm PROPERTIES: gas; MP -77.7 °C; BP -33.4 °C; explosive

NIOSH: 25 ppm; STEL 35 ppm; Group III pesticide range 16 to 25% v/v in air; vapor density
ACGIH: 25 ppm; STEL 35 ppm 0.6 (air = 1)
(1 ppm - 0.697 mg/m3 @ NTP)
SYNONYMS: none
SAMPLER: SOLID SORBENT TUBE TECHNIQUE: VISIBLE ABSORPTION

(sulfuric acid-treated silica gel) SPECTROPHOTOMETRY
A 0.8-micron MCE prefilter may be used to
remove particulate interferences. ANALYTE: indophenol blue
FLOW RATE: 0.1 to 0.2 L/min EXTRACTION: 20 mL deionized water
VOL-MIN: 0.1 L @ 50 ppm COLOR

-MAX: 96 L DEVELOPMENT: EDTA antiprecipitant, phenolate coupling
agent, nitroprusside intensifier,
SHIPMENT: routine hypochlorite.
SAMPLE WAVELENGTH: 630 or 660 nm

CALIBRATION: standard solutions of ammonium chloride
BLANKS: 2 to 10 field blanks per set in deionized water
RANGE: 1 .5 to 20 fjg per sample [1 ]

ACCURACY
ESTIMATED LOD: 0.5 fjg per sample [1]
PRECISION (Sr): not determined
APPLICABILITY: The working range is 0.2 to 400 ppm (0.15 to 300 mg/m3) for a 10-L air sample. This method is applicable
to STEL measurements.
OTHER METHODS: This method is based on the sampling procedure of Method S347 [2], the automated analytical procedure
of EPA Method 350.1 [3], and Standard Methods 417G [4]. NIOSH Method 6701 [5] was less sensitive, employing a passive
liquid sorbent badge for collection followed by ion chromatography. NIOSH Method P&CAM 205 [6] used impinger collection
and Nessler's reagent for manual colorimetric analysis. OSHA has both impinger collection with ion specific electrode analysis
(lD-164) [7] and sulfuric acid-impregnated beaded carbon collection followed by ion chromatography analysis (ID-188) [8].

AMMONIA: METHOD 6015, Issue 2, dated 15 August 1994 - Page 2 of 7
1. Water, distilled and deionized. Special 1 . Sampler:

precaution must be taken to ensure that a. Prefilter (to remove paniculate
distilled water is free of ammonia, by passing interferences): 37-mm cellulose ester
it through an ion exchange column comprised membrane filter (0.8-//m pore size)
of a mixture of both strongly acidic cation and supported by stainless steel screen in two
strongly basic anion exchange resins. piece cassette filter holder.
Regenerate the ion exchange column b. Sulfuric acid-treated silica gel sampling
according to the instructions of the tubes. Glass tube with both ends
manufacturer. unsealed and fire-polished, 6.0 cm long
NOTE: All solutions must be made using with a 6-mm O.D. and a 4-mm I.D.
ammonia-free water. containing two sections of 20/40 mesh
2. Sulfuric acid, conc., reagent grade. sulfuric acid-treated silica gel (200 mg
3. Phenol. front/100 mg back) separated by a 2-mm
4. Sodium hydroxide, reagent grade. portion of glass wool. Plugs of silylated
5. Brij-35. glass wool are placed at the ends of the
6. Ammonium chloride. tube. The pressure drop across the tube
7. Chloroform. must be < 1 3 inches of water at a flow rate
8. Sulfuric acid 5N. Air scrubber solution (AAII). of 0.2 L/min (see APPENDIX). The glass
Carefully add 140 mL of concentrated sulfuric tubes should be rinsed and dried with
acid to approximately 500 mL of ammonia-free acetone before packing. The tubes are
distilled water. Cool to room temperature and capped with plastic caps. Tubes are
dilute to 1 L with ammonia-free water. commercially available.
9. Sodium phenolate. In a 1 -liter flask, dissolve 2. Personal sampling pump calibrated, 0.1 to
83 g phenol (or 80 mL 90% liquid phenol) in 0.2 L/min, with flexible tubing.
500 mL distilled water. In small increments, 3. Technicon AutoAnalyzer Unit (AAII) (or
cautiously add with agitation, 32 g NaOH (96 TRAACS 800 equivalent) consisting of an
g 50% NaOH for TRAACS). Periodically cool autosampler, and analytical cartridge
flask under water faucet. When cool, dilute to (AAII), proportioning pump, colorimeter
1 L with distilled water. Filter if necessary. equipped with 15-mm, 30-mm, or 50-mm
Store in amber glass bottle. For AAII add 0.5 tubular flow cell and 630- to 660-nm filters,
mL Brij-35. a data collection system, and recorder.
10. Sodium hypochlorite solution: Dilute one 4. pH Meter and pH electrode.
volume of a bleach solution containing 5.25% 5. Plastic vials, 80-mL or 50-mL
NaOCI (such as "CIorox") with an equal 6. Polyethylene centrifuge tubes.
volume of deionized water. Available chlorine 7. Magnetic stirrer and stirring bars.
level should approximate 2 to 3%. 8. Pipets: delivery type of convenient sizes.
1 1 . Disodium ethylenediamine-tetraacetate (EDTA) 9. Volumetric flasks: 1-L and 50-mL and
(5%): Dissolve 50 g EDTA (disodium salt) and other convenient sizes for preparing
six pellets NaOH in 1 L of deionized water. standard solutions.
(For TRAACS, dissolve 41 g EDTA, 1 g 50% 1 0. Stopwatch.
NaOH, and 3-6 mL Brij-35.) 11. Manometer.
12. Sodium nitroprusside (0.05% Na2Fe(CN)5NO •
2H2O): Dissolve 0.5 g sodium nitroprusside in
1 L deionized water (or 1.1 g for TRAACS).
NOTE: Sodium nitroprusside solution is light-
sensitive. Store in and use from a
brown bottle.
13. Calibration stock solution (100 mg NH3/L):
Dissolve 0.3144 g anhydrous ammonium
chloride, NH4CI, dried at 105 °C, in deionized
water, and dilute to 1 L Add 1 mL chloroform
as a preservative.

SPECIAL PRECAUTIONS: Phenol is both corrosive and poisonous from ingestion, inhalation, or
absorption through the skin [10]. Avoid skin contact and inhalation of vapors. Sodium hydroxide,
sulfuric acid, and sodium hypochlorite (bleach) are all corrosive. Avoid contact with skin or inhalation
of vapors. Chloroform is believed to be carcinogenic [10], with reports of mutagenic and teratogenic
effects in animals. Handle in a hood and avoid skin contact. Sodium nitroprusside (sodium
nitroferricyanide) is highly toxic. Use extreme caution to avoid ingestion or inhalation of dust.
SAMPLING:

2. Sample at an accurately known flow rate between 0.1 and 0.2 liter/minute for a total sample size
of 0.1 to 96 L
3. Cap the sampling tubes with plastic (not rubber) caps immediately after sampling.
4. Pack securely for shipment.
SAMPLE PREPARATION:
5. Remove the plastic caps. Transfer the front and back sections of sulfuric acid-treated silica gel
to separate 80-mL vials. Discard glass wool plugs. Analyze the two sections separately.
NOTE: Firm tapping of the tube may be necessary to effect complete transfer of the sulfuric
acid-treated silica gel.
6. Add 20 mL of ammonia-free deionized water to each vial. Cap and shake vigorously.
Desorption is complete in 45 minutes. Adjust the pH of each sample to 5.0 to 6.5 with sodium
hydroxide.
NOTE: Analyses should be completed within one day after the ammonia is desorbed.
7. Calibrate daily with at least six working standards over the range 0.05 to 1 //g/mL Using the
stock solution, prepare standards such as the following in 100-mL volumetric flasks (prepare
fresh daily):
a. Add known amounts of calibration stock solution to deionized water in 100-mL volumetric
flasks and dilute to the mark. Prepare fresh daily.
NH3, fjg/mL mL Stock Solution/100 mL
0.05 0.05
0.10 0.10
0.20 0.20
0.40 0.40
0.80 0.80
1.00 1.00
b. Analyze working standards together with samples and blanks (steps 9 through 12).
c. The instrument automatically generates calibration graph (peak height versus concentration).
Sample concentrations will be printed out directly from this graph.
8. Analyze three quality control blind spikes and three analyst spikes to ensure that the calibrating

MEASUREMENT:
9. For a working range of 0.05 to 1.0 //g NH3/ml_, set up the manifold as shown in Figure 1 for Mil
and as shown in Figure 2 for TRAACS. Higher concentrations may be accommodated by
sample dilution.
10. Allow both the colorimeter and the recorder to warm up for 30 minutes. Obtain a stable
baseline with all reagents, feeding deionized water through the sample line.
11. For normal conditions use a 30 or 40/hour 2:1 cam with a common wash for the AAII. For the
TRAACS use a sampling rate between 90 and 120/hour with a 3:1, 4:1, or 5:1 sample/wash
ratio.
12. Arrange ammonia standards in sampler in order of decreasing concentration of nitrogen.
Complete loading of sampler tray with unknown samples. Begin analysis.
CALCULATIONS:
13. Read NH3 concentration (//g/mL) found in sample front (Wf) and back (Wb) sorbent sections
directly from the instrument printout.
14. Calculate the concentration (C) of NH3 in the volume, V (L), of air sampled from the sample
solution concentrations, W, and Wb (^g/mL), multiplied by the appropriate solution volumes, V,
and Vb (mL):
C =
REFERENCES:
[1] DataChem Laboratories report for NIOSH Seq. 7482-L (NIOSH/DPSE, unpublished, May 20,
1992).
[2] NIOSH Manual of Analytical Methods, 2nd ed., Volume 5, S347, U.S. Department of Health,
[3] Methods for Chemical Analysis of Water and Wastes, EPA-600/4-79-020 Revised March 1983,
U.S. Environmental Protection Agency, Environmental Monitoring and Support Laboratory,
Cincinnati, Ohio.
[4] Standard Methods for the Examination of Water and Wastewater, 16th ed., 1985, APHA, AWWA,
WPCF.
[5] NIOSH Manual of Analytical Methods, 3rd ed., Method 6701, U.S. Department of Health,
Education, and Welfare, Publ. (NIOSH) 84-100, February 1984.
[6] NIOSH Manual of Analytical Methods, 2nd ed., Volume 1, P&CAM 205, U.S. Department of
Health, Education, and Welfare, Publ. (NIOSH) 77-1 57-A (1977).
[7] "Ammonia in Workplace Atmosphere" Method ID-164, Inorganic Methods Evaluation Branch,
OSHA Analytical Laboratory, Salt Lake City, Utah.
[8] "Ammonia in Workplace Atmosphere" Method ID-188, Inorganic Methods Evaluation Branch,
OSHA Analytical Laboratory, Salt Lake City, Utah, (April, 1988).
[9] The Merck Index, 11th Edition, 7206 Phenol, 2141 Chloroform, Merck & Co., Inc., Rahway, NJ
(1989).
and Human Services Publ. (NIOSH) 81-123 (1981), available as GPO Stock #17-033-00337-8
from Superintendent of Documents, Washington, D.C. 20402.
METHOD WRITTEN BY:
Norman K. Christensen, DataChem Laboratories, Salt Lake City, Utah.

APPENDIX: PREPARATION OF SULFURIC ACID-TREATED SILICA GEL
1. Place 6 g of 20/40 mesh silica gel in 250-mL beaker.
2. Add 15 mL 0.4 N sulfuric acid to the beaker. Stir the mixture, and cover the beaker with a watch
glass.
3. Heat the silica gel-acid mixture in a fume hood with a Bunsen burner to a very gentle boil.
Evaporate approximately one-half of the liquid.
4. Place the covered beaker in a drying oven at 120 °C until the remainder of the water has been
evaporated.
5. The prepared acid-treated silica gel should flow freely and not adhere to the beaker. Store in silica
gel in a desiccator until ready for use.

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AMMONIA by 1C 6016
NH, MW: 17.03 CAS: 7664-41-7 RTECS: BO0875000
OSHA : 50 ppm PROPERTIES: gas; MP -77.7 °C; BP -33.4 °C; VP 888

NIOSH: 25 ppm; STEL 35 ppm; Group III Pesticide kPa (8.76 atm) @ 21 .1 °C; vapor density
ACGIH: 25 ppm; STEL 35 ppm 0.6 (air = 1); explosive range 16 to 25%
(1 ppm = 0.697 mg/m3 @ NTP) v/v in air
SYNONYMS: none
SAMPLER: SOLID SORBENT TUBE TECHNIQUE: ION CHROMATOGRAPHY,

(sulfuric acid-treated silica gel) CONDUCTIVITY DETECTION
a O.JH/m MCE prefilter may be used to
remove particulate interferences. ANALYTE: ammonium ion (NH,*)
EXTRACTION: 10 mLdeionized water
FLOW RATE: 0.1 to 0.5 L/min INJECTION

VOLUME: 50 pL
VOL-MIN: 0.1 L@ 50 ppm
-MAX: 96L@50ppm[1] ELUENT: 48 mM_HCI/4 mM DAP-HCI/4 mM L-histidine-HCI;
1 mL/min
SHIPMENT: routine alternate: 12 mM HCI/0.25 mM DAP-HCI/
0.25 mM L-histidine-HCI; 1 mL/min
SAMPLE
STABILITY: at least 35 days @ 5 °C [2] COLUMNS: HPIC-CS3 cation separator; HPIC-CG3
cation guard; CMMS-1 cation
BLANKS: 2 to 1 0 field blanks per set micromembrane suppressor
CONDUCTIVITY
SETTING: 30 pS full scale
ACCURACY
CALIBRATION: standard solutions of NH,, ' in deionized
RANGE STUDIED: 17 to 68 mg/m3 [1] water
(30-L samples)
RANGE: 4 to 100 /jg per sample [3]
BIAS: -2.4%[1]
ESTIMATED LOD: 2/jg per sample [3]
PRECISION (St): 0.038 [2]
ACCURACY: ± 14.5%
APPLICABILITY: The working range is 24 to 98 ppm (17 to 68 mg/m3) for a 30-L sample. This method is applicable to STEL
measurements when sampled at 20.2 L/min.
INTERFERENCES: Ethanolamines (monoethanolamine, isopropanolamine, and propanolamine) have retention times similar to
NH4.*
The use of the alternate (weak) eluent will aid in separating these peaks.
OTHER METHODS: This method combines the sampling procedure of methods S347 [4] and 6015 with an ion chromatographic
analytical procedure similar to Method 6701 [5] and OSHA Method ID-188 [3].

AMMONIA by lC: METHOD 601 6, Issue 1, dated 15 May 1996 - Page 2 of 4
1. Water, deionized, filtered. 1. Sampler:

2. Sulfuric acid (H2SO4), 0.01 N,* a. Prefilter: 37-mm mixed cellulose ester
Add 0.28 mL conc. H2SO4 to 500 mL deionized membrane filter, 0.8-;um pore size, stainless
water in 1-L volumetric flask. Dilute to 1 L with steel or porous plastic screen in two piece
deionized water.
cassette filter holder.
3. Hydrochloric acid (HCI), 1 N:*
b. Sulfuric acid-treated silica gel, glass tube,
Add 82.5 mL conc. HCI to 500 mL deionized
water in 1-L volumetric flask. Dilute to 1 L with unsealed and fire-polished, 6.0 cm long, 6-
deionized water. mm OD, 4-mm ID, containing two sections
4. 2,3-diaminopropionic acid monohydrochloride of 20/40 mesh sulfuric acid-treated silica gel
(DAP-HCI) (200 mg front/100 mg back) separated and
5. L-histidine monohydrochloride monohydrate (L- held in place with plugs of silylated glass
nistidine-HCI) wool, and capped with plastic caps. Tubes
6. Eluent (48 mM HCI/4 mM DAP-HCI/4 mM are commercially available.
L-histidine-HCI): Place 0.560 g DAP-HCI and 2. Personal sampling pump, 0.1 to 0.5 L/min, with
0.840 g L-histidine-HCI in a 1-L volumetric flask. flexible tubing.
Add 48 mL of 1 N HCI, dilute to volume with 3. Ion Chromatograph with conductivity detector,
deionized water. Prepare monthly. cation column and guard, and cation
7. Alternate eluent (12 mM HCI/0.25 mM micromembrane suppressor (see p 6016-1).
DAP-HCI/0.25 mM L-histidine-HCI): Dilute 4. Syringes, 10-mL, polyethylene, Luertip.
252 mL strong eluent and 36 mL 1 N HCI to 4 L 5. Centrifuge tubes, 15-mL, graduated, plastic with
with deionized water. Prepare fresh for each screw caps.
use. 6. Volumetric flasks, 10-, 50-, 100-mL, and 1-L.
8. Tetramethylammonium hydroxide (TMAOH), 7. Syringe filters, 13-mm, 0.8-um, membrane filter.
25%, (Aldrich Chemical Co. Milwaukee, Wl). 8. Micropipets, disposable tips.
9. Regenerant solution: Dilute 57.4 mL of 25% 9. Analytical balance (sensitivity to 0.01 mg).
TMAOH to 4 L with deionized water.
10. Ammonia stock solution, 1000 ug/mL as
NH3 (1059 ug/mL as NH4+): Dissolve
3.1409 g ammonium chloride in deionized
water. Dilute to 1 L.
See SPECIAL PRECAUTIONS
SPECIAL PRECAUTIONS: Concentrated acids are corrosive to skin. Handle acid in a fume hood. Wear
protective gloves.
SAMPLING:
1 . Calibrate each personal sampling pump with a representative sampler in line.

2. Sample at an accurately known flow rate between 0.1 and 0.5 L/min for a total sample size of 0.1 to 96 L
3. Cap the sampling tubes with plastic (not rubber) caps immediately after sampling.
4. Pack securely for shipment.
SAMPLE PREPARATION:
5. Remove caps from sampling tubes. Transfer the front and back sections of sulfuric acid-treated silica gel
to separate 15-mL graduated centrifuge tubes.
NOTE: Firm tapping of the tube may be necessary to effect complete transfer of the sulfuric acid-treated
silica gel.

AMMONIA by IC: METHOD 6016, Issue 1, dated 15 May 1996 - Page 3 of 4
6. Add 10 mL of deionized water to each centrifuge tube. Cap and shake vigorously. Allow to stand
45 minutes with occasional shaking. (Desorption is complete in 45 minutes.)
NOTE: Analyses should be completed within one day after the ammonia is desorbed.
7. Transfer samples to 10-mL syringes fitted with inline syringe filters for manual injection or transfer to
autosampler vials.
8. Calibrate daily with at least six working standards over the range of 1 to 110 ug NH3 per sample (about
0.11 to 12 ug/mL NH4+).
a. Add known aliquots of ammonia stock solution to 0.01 N. H2SO4 in 10-mL volumetric flasks.
NOTE: Prepare standards just before use.
b. Analyze working standards together with samples and blanks (steps 9 through 1 1 ).
c. Prepare calibration graph (peak height vs. ug NH3).
MEASUREMENT:
9. Set ion chromatograph to conditions given on page 6016-1, according to manufacturer's instructions.
10. Inject 50-uL sample aliquot manually or with autosampler. For manual operation, inject 2 to 3 mL of
sample from filter/syringe to ensure complete rinse of sample loop.
1 1 . Measure peak height.
NOTE: If peak height exceeds linear calibration range, dilute with 0.01 N H2SO4, reanalyze and apply
the appropriate dilution factor in calculations.
CALCULATIONS:
12. Determine the mass, ug, of ammonia found in the sample front (Wf) and back (Wb) sorbent sections,
and in the average media blank front (Bf) and back (Bb) sorbent sections.
13. Calculate concentration, C, of NH3 in the air volume sampled, V (L):
(W.- + Whb- - B.! - BJ

C = —' £, mg/m
V
This method combines the sampling procedure of NIOSH Methods S347 [4] and 6015 with the ion
chromatographic analytical procedure of NIOSH Method 6701 [5] and OSHA Method ID-188 [3]. This method
will serve as an alternate analytical procedure to the automated spectrophotometric procedure of method
6015. Although the methods from which this method is derived are fully evaluated methods, the combination
of the sulfuric acid-treated silica gel sampler and IC analysis has not received a full evaluation as such.
During the development of the passive monitor method for ammonia (6701), sulfuric acid-treated silica gel
tubes were used as one of the reference methods [5]. The silica gel samples with IC analysis showed good
agreement with the other reference methods, bubbler collection with colorimetric analysis using Nessler's
Reagent, and bubbler collection with IC analysis.
A storage stability study compared the sulfuric acid-treated silica gel tube and sulfuric acid-treated carbon
beads used in OSHA Method ID-188. When stored at room temperature for five days and then refrigerated
for 21 days, silica gel samples had a mean recovery of 102 ± 3.8% (n = 8), while carbon beads had a mean
recovery of 95 ± 1.6% (n = 8). The samples stored on carbon beads for 35 days showed significantly lower
(although still acceptable) recovery compared to samples stored for 14 days: 103 ± 3.8% for silica gel (n =
12), and 108 ± 7.0% for carbon beads (n = 12) [2].

AMMONIA by IC: METHOD 601 6, Issue 1, dated 15 May 1996 - Page 4 of 4
REFERENCES:
[1] NIOSH [1977]. Ammonia: Backup data report No. S347. Ten NIOSH analytical methods, set 6. SRI
International Contract No. 210-76-0123. Available NTIS PB-288629.
[2] DataChem [1995]. User check of method 6015 for ammonia. Sequence 8321-J, K, L, M. Unpublished
report.
[3] OSHA [1991]. Ammonia in workplace atmospheres - solid sorbent: Method ID-188, OSHA analytical
methods manual, 2nd ed., Part 2, Inorganic substances.
[4] NIOSH [1979]. Ammonia: Method S347. In: Taylor DG, Ed. NIOSH manual of analytical methods, 2nd
ed., volume 5. Cincinnati, OH: National Institute for Occupational Safety and Health, DHEW (NIOSH)
Publication No. 79-141.
[5] NIOSH [1984]. Ammonia: Method 6701. In: Eller PM, Ed. NIOSH manual of analytical methods, 3rd
ed. Cincinnati, OH: National Institute for Occupational Safety and Health, DHHS (NIOSH) Publication
No. 84-100.
METHOD WRITTEN BY:
Mary Ellen Cassinelli, NIOSH/DPSE/QASA

sec-AMYL ACETATE
See ESTERS I (Method 1450) for procedure

SGC-AMYL ACETATE

ANILINE
See AMINES, AROMATIC (Method 2002) for procedure

ANISIDINE 2514
CH,OCKHdNH, MW: 123.16 CAS: (0-) 90-04-0 RTECS: (O-) BZ54 10000
(B-) 104-94-9 (p-) BZ5450000

OSHA : 0.5 mg/m3 (skin) PROPERTIES: o-isomer: liquid; d 1.092 g/mL@ 15 °C;
NIOSH: 0.5 mg/m3 (skin); o-isomer suspect carcinogen BP 225 °C; MP 5 °C; VP 0.1 mm
ACGIH: 0.1 ppm (skin) (0.5 mg/m3) Hg @ 27 °C
(1 ppm = 5.03 mg/m3 @ NTP) g-isomer: solid; MP 57 °C; BP 246 °C
SYNONYMS: o-isomer: 2-aminoanisole; 2-methoxybenzenamine; o-methoxyaniline

g-isomer: 4-aminoanisole; 4-methoxybenzenamine; p_-methoxyaniline
SAMPLER: SOLID SORBENT TUBE TECHNIQUE: HPLC, UV DETECTION

(XAD-2, 150 mg/75 mg)
ANALYTE: o-anisidine and g-anisidine
DESORPTION: 5 mL methanol; stand 15 min
VOL-MIN: 24 L
VOLUME: 10 fJL
SHIPMENT: routine
MOBILE PHASE: 35% acetonitrile/65% water
SAMPLE @ 1.2 mL/min; ambient temperature
STABILITY: at least 1 week @ 25 C
COLUMN: 50 cm x 2-mm ID stainless steel packed
BLANKS: 2 to 10 field blanks per set with //-Bondapak C18 or equivalent
DETECTOR: UV absorption @ 254 nm
ACCURACY CALIBRATION: analytes dissolved in methanol
RANGE STUDIED: 0.13 to 0.58 mg/m3 [1] RANGE: 12 to 360 //g per sample
(225-L samples) (each isomer) [2]
BIAS: 0.12%
ESTIMATED LOD : 0.35 //g per sample [2]
PRECISION (Sr): 0.029 @ 30 to 240 fjg per sample [1 ]
ACCURACY: ± 13.3%
APPLICABILITY: The working range is 0.06 to 0.8 mg/m3 (0.012 to 0.16 ppm) for a 200-L air sample.
OTHER METHODS: This revises Method S163 [2]. This method replaces P&CAM 168 [3] because XAD-2 has a much greater
capacity than silica gel for o-anisidine at high humidity [1].

ANISIDINE: METHOD 2514, Issue 2, dated 15 August 1994 - Page 2 of 4
1. p_-Anisidine, reagent grade.* 1. Sampler: glass tube, 7 cm long, 8-mm OD,
2. o-Anisidine, reagent grade.* 6-mm ID, with plastic caps, containing two
3. Methanol, HPLC grade.* sections of 20/50 mesh XAD-2 (front =
4. Acetonitrile, HPLC grade.* 150 mg; back = 75 mg) separated and held in
5. Water, distilled, deionized. place by plugs of silylated glass wool.
6. Methylene chloride. Pressure drop across the tube must be
7. Calibration stock solution, 15.0 mg/mL <3.4 kPa (2.5 cm Hg) at 1 L/min airflow.
jD-anisidine and 15.3 mg/mL o-anisidine. Tubes are commercially available, (SKC Cat.
Dissolve 750 mg p_-anisidine and 700 fjL No. 226-30-05, or equivalent).
o-anisidine in methanol to make 50 mL 2. Personal sampling pump, 0.5 to 1 L/min, with
solution. flexible connecting tubing.
8. HPLC mobile phase: 3. HPLC with UV absorption detector at
35% acetonitrile/65% water. Filter (5-//m 254 nm, integrator and column
PTFE) and degas prior to use. (page 2514-1).
4. Vials, 20-mL, scintillation.
* See SPECIAL PRECAUTIONS. 5. Pipet, 5-mL
6. Syringes, 10-juL, readable to 0.1 //L
7. Volumetric flasks, 5- and 50-mL
SPECIAL PRECAUTIONS: Anisidine can irritate the skin. Methanol and anisidine can be absorbed
through the skin. Avoid inhalation of vapors of these compounds and of acetonitrile [4].
SAMPLING:

2. Uncap the sampler immediately before sampling. Attach sampler to personal sampling pump
with flexible tubing.
3. Sample at an accurately known flow rate between 0.5 and 1 .0 L/min for a total sample size of 24
to 320 L Do not sample at less than 0.5 L/min.
SAMPLE PREPARATION:
5. Place the front and back sections of the sampler in separate vials. Discard the glass wool plugs.
6. Add 5.0 mL methanol to each vial. Cap each vial and swirl vigorously.
7. Allow to stand for 15 min. Analyze within one day.
8. Calibrate daily with at least six working standards over the range 0.4 to 360 //g anisidine per
sample for each isomer.
a. Add a known volume of calibration stock solution, or a dilution thereof in methanol, to a
5-mL volumetric flask and dilute to the mark with methanol.
c. Prepare calibration graph (peak area vs. //g analyte) for each isomer.
9. Determine desorption efficiency (DE) at least once for each lot of XAD-2 used for sampling in the
concentration range of interest. Prepare four tubes at each of five levels.
a. Remove and discard the back sorbent section of a media blank sampler.

b. Inject a known amount (e.g., 1 to 20 fjL) of calibration stock solution, or a dilution thereof in
methanol, directly onto the front section with a microliter syringe.
e. Prepare graphs of DE vs. //g isomer recovered.
10. Analyze three quality control blind spikes and three analyst spikes with each subsequent set
from the same lot to ensure that the calibration graph and DE graph are in control.
MEASUREMENT:
11. Set HPLC to conditions given on page 2514-1. Inject sample aliquot.
NOTE: Sensitivity is ca. 0.083 absorbance unit/mg of either isomer in a 10-mL injection volume
with a 1-cm flow cell. Approximate retention times are 7.5 min for rj-anisidine and 12
min for o-anisidine.
CALCULATIONS:
13. Determine the quantities (sum of quantities of the o- and the rj-isomers corrected for DE), mg of
analytes found in the sample front (Wf) and back (Wb) sorbent sections, and in the average
media blank front (Bf) and back (Bb) sorbent sections.
14. Calculate the sum of the concentrations, C, of the isomers in the air volume sampled, V (L):
c . (W-*w»-B'-tH m/m3.
Method S163 was issued on February 16, 1979 [2], and was validated over the range 0.13 to
0.58 mg/m for the o-isomer and 0.12 to 0.58 mg/m for the p_-isomer using 225-L air samples [1,5].
The generation system was constructed so that samples were generated for both isomers at the same
time. Concentrations were verified by an independent method using bubblers containing methanol and
HPLC analysis [1]. The overall precision, SrT, for the combined sampling and measurement of both
isomers was 0.068 with an average recovery of 100.7% for the o-isomer and 99.7% for the rj-isomer [1],
which represent non-significant biases for the isomers. A separate breakthrough test was conducted for
each isomer with XAD-2. Samples were taken at ca. 1 .0 L/min. o-Anisidine was generated at 1 .03
mg/m3 with a relative humidity of 81% at 21 °C. Breakthrough (3%) from 150 mg XAD-2 occurred after
236 min, but did not increase above this amount up to 479 min. rj-Anisidine was generated at 1 .04
mg/m with a relative humidity of 82% at 20 °C. Breakthrough did not occur during the 361 -min test.
Samples containing both isomers were stored for one week at room temperature and found to be stable.
Desorption efficiencies averaged 0.95 and 0.91 for o- and rj-anisidine, respectively, in the range 30 to
240 fjQ per sample.
REFERENCES:
[1] NIOSH Backup Data Report S163 (unpublished, February, 1979).

[3] Ibid., Vol. 1, P&CAM 168, U.S. Department of Health, Education, and Welfare, Publ.
(NIOSH) 77-1 57-A (1977).

Health and Human Services, Publ. (NIOSH) 81-123 (1981), available as GPO Stock
#01 7-033-00337-8 from Superintendent of Documents, Washington, DC 20402.
Workplace Toxic Substances, U.S. Department of Health and Human Services, Publ.
(NIOSH) 80-133 (1980).
METHOD REVISED BY:
Edward Slick, NIOSH/DPSE; S163 originally validated under NIOSH Contract 210-76-0123.

ARSENIC and compounds, as As 7900
(except AsH3 and As2O3)
As MW: 74.92 CAS: 7440-38-2 RTECS: CG525000

OSHA : 0.01 mg/m3 PROPERTIES: soft, reactive metalloid; MP 848 °C;

NIOSH: C 0.002 mg/m3/15 min; carcinogen valence ± 3, 5 in salts
ACGIH: 0.01 mg/m3; carcinogen
SYNONYMS: vary depending upon the compound
SAMPLER: FILTER TECHNIQUE: ATOMIC ABSORPTION, FLAME ARSINE

cellulose ester membrane) GENERATION
FLOW RATE: 1 to 3 L/min ANALYTE: arsenic
VOL-MIN: 30 L @ 0.002 mg/m3 ASHING: conc. HNO3, 3 mL; conc. H2S04, 1 mL;
-MAX: 1000 L conc. HCI04, 1 mL; 140 °C
SHIPMENT: routine FINAL

SOLUTION: 4% H2SO4, 25 mL
SAMPLE
STABILITY: stable if refrigerated FLAME: hydrogen-argon
BLANKS: 2 to 10 field blanks per set WAVELENGTH: 193.7 nm
BACKGROUND
CORRECTION: D2 or H2 c
ACCURACY CALIBRATION: As in 4% H2SO4
RANGE STUDIED: not studied RANGE: 0.05 to 2.0 fjg per sample [1]
BIAS: see APPLICABILITY
OVERALL PRECISION (SrT): not evaluated
APPLICABILITY: The working range is 0.00025 to 0.01 mg/m3 for a 200-L air sample and 0.002 to 0.07 mg/m3 for a 30-L air
sample. This method collects participate arsenic only; if arsenic trioxide vapor Is present, use the sampler in Method
7901. This is an elemental analysis, not compound specific. Volatile organic arsenic compounds, As2O3 vapor, and arsine are
not collected efficiently by this sampling method.
INTERFERENCES: Background absorption is overcome by the use of D2 or H2 continuum.
OTHER METHODS: This revises P&CAM 139 [1]); a similar method appears in the criteria document [2]. Method 7901 uses
a sampler designed to collect As2O3 vapor and an alternate measurement technique (graphite furnace-AAS). Method 7300
(ICP-AES) also gives an alternate measurement technique.

ARSENIC and compounds, as As: METHOD 7900, Issue 2, dated 15 August 1994 - Page 2 of 3
1. Nitric acid, conc. 1. Sampler: cellulose ester filter, 0.8-/mi pore

2. Hydrochloric acid, conc. size, 37-mm diameter; in cassette filter holder.
3. Sulfuric acid, conc. 2. Personal sampling pump, 1 to 3 L/min, with
4. Perchloric acid, conc.* flexible connecting tubing.
5. Calibration stock solution, 1000 mg/mL* 3. Atomic absorption spectrophotometer with
Commercially available or dissolve 1.320 g appropriate hydrogen burner head or quartz
primary standard As2O3 in 25 mL 20% (w/v) tube furnace, and arsenic hollow cathode lamp
KOH. Neutralize with 20% (v/v) HNO3 to a or EDL and arsine generation system.
phenolphthalein endpoint. Add 10 mL conc. 4. Regulators, two-stage, for air, hydrogen and
HNO3 and dilute to 1 L with distilled or argon.
deionized water. 5. Beakers, Phillips, 125-mL, or Griffin, 50-mL,
6. Ashing acid, 3 volumes HNO3, 1 volume with watchglass covers.*
H2SO4, and 1 volume HCIO4. 6. Volumetric flasks, 25- and 100-mL*
7. Hydrogen. 7. Pipets, volumetric, as needed.*
8. Argon. 8. Hotplate, surface temperature 140 °C.
9. Distilled or deionized water.
10. Sodium borohydride, pellets. * Clean all glassware with conc, nitric acid
11. Air, compressed. before use and rinse thoroughly with
distilled or deionized water.
SPECIAL PRECAUTIONS: Arsenic is a recognized carcinogen. Handle appropriately [2]. Perform all
perchloric acid digestions in a perchloric acid fume hood.
SAMPLING:

1000 L Do not exceed ca. 2 mg total dust loading on the filter.
SAMPLE PREPARATION:
3. Open the cassette filter holders and transfer the samples and blanks to clean beakers.
NOTE: Analyze the backup pad separately if qualitative indication of As2O3 vapor is desired.
Use Method 7901 if quantitative collection of As2O3 vapor is desired.
4. Add 5 mL ashing acid and cover with a watchglass.
5. Heat on hotplate (140 °C) until the solution is colorless.
6. Add 1 mL conc. HNO3 and/or 70% HCIO4 drop by drop as needed to complete the ashing.
7. Remove the watchglass.
8. Heat on 140 °C hotplate until dense SO3 fumes appear.
9. Allow the mixture to cool.
10. Transfer the solution quantitatively to a 25-mL volumetric flask.
11. Dilute to volume with distilled or deionized water.
12. Prepare working standards. Add known amounts, covering the range 0.2 to 8 /yg As/100 mL
(0.05 to 2 JJQ As per sample), of 1000 //g/mL As calibration stock solution to 100-mL volumetric
flasks containing 4 mL conc. H2SO4 and dilute to volume with distilled or deionized water.

ARSENIC and compounds, as As: METHOD 7900, Issue 2, dated 15 August 1994 - Page 3 of 3
13. Analyze working standards together with the blanks and samples (steps 18 through 25).
14. Prepare calibration graph (absorbance vs. solution concentration, //g/mL).
15. Analyze a standard for every 10 samples.
16. Check analytical recoveries with at least one spiked media blank per 10 samples.
17. Use method of standard additions occasionally to check for interferences.
ANALYTICAL PROCEDURE:
18. Set spectrophotometer according to manufacturer's recommendations and to conditions on

page 7900-1 .
19. Set up arsine generator per manufacturer's instructions.
20. Pipet 5 mL aliquot of the 25-mL sample into the arsine generation flask.
21. Add 25 mL distilled or deionized water, 3 mL conc. HCI, and mix well.
22. Connect the flask to the generation system.
23. Introduce a single sodium borohydride pellet or sodium borohydride solution to the sample
solution.
24. Allow the gases to flush into the flame of the atomic absorption instrument.
25. Record the absorbance readings.
NOTE: If the absorbance values of the samples are above the linear range of the standards,
dilute the solutions, or use a smaller aliquot, reanalyze, and use the appropriate dilution
factor in calculations.
CALCULATIONS:
26. Using the measured absorbances, calculate the corresponding solution concentrations
of As in the sample, Cs, and average media blank, Cb, from the calibration graph.
concentration, C (mg/m3), of As in the air volume sampled, V (L):
C .
This method was evaluated in July, 1976, over the range 0.02 to 3 mg per sample by laboratory testing
with spiked filters. Precision and accuracy data are given on page 7900-1 [1].
REFERENCES:
[1] NIOSH Manual of Analytical Methods, 2nd. ed., V. 1, P&CAM 139, U.S. Department of Health,
[2] Criteria for a Recommended Standard. ..Occupational Exposure to Inorganic Arsenic, U.S.
METHOD WRITTEN BY:
Mark Millson, NIOSH/DPSE.

ARSENIC, organo- 5022
(1) CH3AsO3H2 MW: (1) 139.96 CAS: (1) 124-58-3 RTECS: (1) PA1 575000
(2) (CH3)2AsO2H (2) 137.99 (2) 75-60-5 (2) CH7525000
(3) H2NC6H4AsO3H (3) 217.07 (3) 98-50-0 (3) CF7875000

OSHA : 0.5 mg/m3 (as As) PROPERTIES: solids; MP (1) 161 °C, (2) 195 °C;
NIOSH: no REL (3) 232 °C
ACGIH: 0.2 mg/m3 (as As)
SYNONYMS: (1) Methylarsonic acid: methanearsonic acid. (2) Dimethylarsinic acid: cacodylic acid; hydroxydimethyl arsine
oxide. (3) g-Aminophenyl arsonic acid: g-arsanilic acid; atoxylic acid.
SAMPLER: FILTER TECHNIQUE: ION CHROMATOGRAPHY/

(1-^Tl PTFE) HYDRIDE ATOMIC ABSORPTION
FLOW RATE: 1 to 3 L/min ANALYTE: anions (1C); AsH3 (AAS)
VOL-MIN: 50 L @ 0.01 mg/m3 EXTRACTION: borate-carbonate buffer, 25 mL

-MAX: 1000 L
ION CHROMATOGRAPHY:
SHIPMENT: routine INJECTION LOOP VOLUME: 0.8 mL
COLUMNS: two, 3 x 150-mm anion
SAMPLE ELUENT: borate-carbonate buffer;
STABILITY: stable 2.5 mL/min; 3450 kPa
(500 psi); ambient
BLANKS: 2 to 10 field blanks per set temperature
AAS:
QUARTZ FURNACE: 800 °C
WAVELENGTH: 193.7 nm (no D2)
ACCURACY
CALIBRATION: organoarsenicals in water
RANGE STUDIED: 0.005 to 0.2 mg/m3 [1 ,2]
RANGE: 0.5 to 2 fjg As per sample
BIAS: not significant
OVERALL PRECISION (SrT): 0.047 @ 0.02 mg/m3 [1]; ESTIMATED LOD: 0.2 //g As per sample [1]
0.14 @ 0.005 mg/m3 [1]
PRECISION (Sr): Table 1
ACCURACY: ± 20% @ 0.02 mg/m3
APPLICABILITY: The working range is 0.005 to 10 mg/m3 (as As) for a 100-L air sample. The method is designed to quantitate
particulate organo-arsenic compounds.
INTERFERENCES: Inorganic arsenic (III) co-elutes with dimethylarsenic acid using Eluent A but the two may be separated with
Eluent B. Other ions at high concentrations in the sample can interfere with the chromatographic separation of the arsenicals.
As2O3 is not efficiently sampled by this sampler; for quantitation of that compound see Method 7901.
OTHER METHODS: This is P&CAM 320 in revised format [2]. Method 7200 measures total As by hydride/AAS. Method 7901
measures As2O3, which can exist as a vapor and aerosol.

ARSENIC, organo-: METHOD 5022, Issue 2, dated 15 August 1994 - Page 2 of 6
1. Deionized water. 1. Sampler: PTFE polyethylene-backed

2. Hydrochloric acid, conc. membrane filter, 1-//m pore size (MilliporeType
3. Eluent A (2.4 mM HCO3/1.9 mM C0,*/1-0 FA or equivalent), 37-mm diameter with
mM B4O72'). Dissolve 0.8067 g NaHCO3 backup pad; in cassette filter holder.
0.8055 g Na2CO3, and 1.5257 g Na2B4O7 2. Personal sampling pump, 1 to 3 L/min, with
•10H2O in 4 L deionized water. flexible connecting tubing.
Eluent B (5 mM B4O7Z"). Dissolve 7.6284 g
4. 3. Ion chromatograph with suppressor and
Na2B4O7»10H2O in 4 L deionized water. detector bypassed. Route column effluent via
5. Potassium persulfate solution,* KÔg, Microbore PTFE tubing (0.3-mm ID x 0.6-mm
saturated in 15% (v/v) HCI. OD, Dionex) directly into arsine generator
6. Sodium borohydride, 1% NaBH4 (w/v) in 0.2% (Figure 1).
KOH (w/v). Add 5 g NaBH4 and 1 g KOH to 4. Syringes, plastic, 1 0-mL, with male luer fittings.
deionized water; dilute to 500 mL. Prepare 5. Arsine generator: proportioning pump with
fresh weekly. flow-rated pump tubes and 1 .5-mm ID x 3-mm
7. Stock standards, 1000 fjg As/mL: OD manifold mixing coils, 5-turn and 20-turn
a. Methylarsonic acid.* Dissolve 0.9341 g (Technicon or equivalent), 1.5-mm ID x
CH3AsO3H2 (Ansul Co., Weslaco, TX), in 3.5-mm OD glass "T" connectors; gas-liquid
deionized water; dilute to 500 mL separator and expansion chamber (Figure 2);
b. Dimethylarsenic acid.* Dissolve 0.9210 g -1 m of 1/4" OD PTFE tubing; three PTFE
(CH3)2AsO2H (Ansul Co.) in deionized 1/4" ID Swagelok fittings; and rotometer (100
water; dilute to 500 mL to 900 mL/min).
c. p_-Aminophenylarsonic acid.* Dissolve 6. Atomic absorption spectrophotometer
1 .4485 g p_-H2NC6H4AsO3H2 in 5 mL 1 N (reciprocal linear UV dispersion -0.65
NaOH. Dilute to 500 mL with deionized nm/mm); As electrodeless discharge lamp and
water. Protect from light. power supply; and atomization cell (16-cm x
d. Arsenic trioxide.* Dissolve 0.6602 g As2O3 13-rmm ID windowless quartz tube with 18-cm
in 5 mL 1 N NaOH. Dilute to 500 mL with x 4-mm ID inlet tube fused in the center),
deionized water. wound with Nichrome wire (14 Q/m, spaced 2
e. Arsenic pentoxide.* Dissolve 0.7669 g to 3 mm between turns and wrapped with heat
As205 in 5 mL 1 N NaOH. Dilute to 500 resistant tape) (Figure 3). Temperature in the
mL with deionized water. cell is measured by a thermocouple (800 °C).
8. Calibration stock solution, 1 //g/mL mixed Mount the cell on top of a single-slot AAS
analyte. Dilute 0.1 mL of each stock standard burner head and align with burner alignment
(REAGENTS, 7.) with Eluent A in a 100-mL controls.
volumetric flask. Prepare fresh daily. Beakers, 50-mL*
9. Argon. Ultrasonic waterbath.
Volumetric flasks, 10-, 100- and 500-mL
10. Pipets, 25-//L and 0.1- to 1-mL
See SPECIAL PRECAUTIONS
* Soak all glassware in mild detergent,
rinse with deionized water, 10% HNO3,
and deionized water.
SPECIAL PRECAUTIONS: Potassium persulfate is a powerful oxidizing agent. Arsine gas is extremely
toxic and can be fatal. The arsenic compounds used in the stock standards are poisonous [3].

SAMPLING:

2. Sample at an accurately known flow rate between 1 and 3 L/min for a total sample volume of 50
to 1000 L
3. Cap the cassettes and pack securely for shipment.
SAMPLE PREPARATION:
4. For each sample, pipet 25 mL Eluent A into a clean 50-mL beaker.

5. Open the cassette, remove the PTFE filter with clean forceps, and transfer it to the beaker.
Place the exposed side of the filter in contact with the solution. Cover beaker.
6. Agitate contents of the beaker for 30 min in an ultrasonic water bath. If the extracts will not be
analyzed immediately, store at ca. 4 °C until measurement.
7. Calibrate daily with at least six working standards over the range 0.2 to 2 //g As per sample
(0.008 to 0.08 //g As/mL).
a. Add known amounts of calibration stock solution to Eluent A in 10-mL volumetric flasks and
dilute to the mark.
b. Analyze together with the samples and blanks (steps 8 through 12).
c. Prepare calibration graph for each arsenic species (peak area or height vs. //g As).
MEASUREMENT:
8. Set the ion chromatograph to the conditions given on page 5022-1 . Allow the columns to
equilibrate with eluent >1 h before connecting effluent to the arsine generator.
NOTE: Eluent A allows the separation of methylarsonic acid (tr = 2 min), p_-aminophenylarsonic
acid (tr = 4 min), and As(V) (tr = 7.5 min); As(lll) and dimethylarsenic acid (tr = 1 min)
are not resolved. If a signal is obtained at the approximate retention time of the latter
two compounds, or if both compounds are known to be present in the sample, perform
a second analysis using Eluent B (lower ionic strength). If either of the two compounds
is known not to be present, Eluent A will effectively determine the remaining
compounds. With Eluent B the other species have very long retention times and will
accumulate on the column, tying up active resin sites. Therefore, flush the column with
Eluent A after each 10 to 15 samples and reequilibrate with Eluent B before further
analysis.
9. Connect the IC effluent to the arsine generator into which the following flow:
Saturated rC,S2O8 solution: 0.8 mL/min

NaBH4 solution: 2.0 mL/min
Ar carrier gas: 300 mL/min
NOTE: The gaseous arsines formed in the arsine generator are first separated from liquid
solution using the gas-liquid separator (Figure 2) and then transferred by argon carrier
gas through PTFE tubing to the heated quartz furnace.
10. Set the AAS according to manufacturer's recommendations and to the conditions given on page
5022-1. Align the quartz cell in the optical path. Heat the quartz cell gradually to 800 °C using
a variable transformer and thermocouple.
11. Using a syringe, inject a sample aliquot (ca. 2 to 3 mL) into the chromatograph, flushing the
injection loop to avoid contamination from the previous injection. Rinse the syringe with
deionized water and dry it between samples, or use disposable syringes.

12. Identify the component peaks. Measure peak height or area.
CALCULATIONS:
13. From the calibration graphs, calculate the amount (/jg) of arsenic for each species in the sample
(W) and in the average media blank (B).
14. Calculate the arsenic concentrations, C, (mg/m3) in the air volume sampled, V (L):
c.
The measurement precision obtained under the conditions recommended in this procedure is presented
in Table 1 [1]. The overall precision of the method was tested using filters loaded in a dynamic aerosol
generation/sampling system with particulates of the three organoarsenical compounds. The
concentration levels tested for each species were 5, 10, and 20 //g As/m3 of air. Depending on the
concentration and species, the relative standard deviation ranged from 14.4% at the lowest level to 4.7%
at the highest level.
The collection efficiency of the method for organoarsenicals in the range of 5 to 20 //g/m3 using a 300-L
sample was found to be >99%. The collection efficiency of the method for inorganic arsenic was not
determined.
The accuracy of the overall method was determined by analyzing additional aerosol samples from each
set using Neutron Activation (NAA) and X-ray Fluorescence (XRF) analyses. Since NAA and XRF
techniques provide only the total elemental arsenic, the total arsenic obtained from the IC-AAS analysis
was used for comparison. The accuracy ranged from 90 to 120% of the values obtained by NAA and
XRF.
REFERENCES:
[1] Colovos, G., N. Hester, G. Ricci, and L Shepard: "Development of a Method for the
Determination of Organoarsenicals in Air," NIOSH Contract #210-77-0134, available through
National Technical Information Service, Springfield, VA 22161 as Order No. PB83-1 80794.
[3] The Merck Index, 11th ed., Merck & Co., Rahway, NJ (1989).
METHOD REVISED BY:
Mary Ellen Cassinelli, NIOSH/DPSE; P&CAM 320 originally developed under NIOSH Contract
210-77-0134.

TABLE 1. SENSITIVITY, DETECTION LIMIT AND WORKING RANGE DATA FOR ANALYSIS OF
PARTICULATE ARSENICALS [1].
Detection Limit (as As) Range1

300 L 300 L Measurement
Sensitivity Sample Volume Solution Sample Volume Solution Precision
Arsenical (nq/mL/1% Abs) p/q/m3) ng/mL (ug/m3) nq/mL (% S.)
Dimethylarsenic
acid 1 .3 0.62 7 1.7 -6 7 20 - 80 11.2 - 1.6
Arsenic (III) 2 .1 0.71 8 1.7 -6. 7 20 -80 11.2 - 1.3
Methylarsonic
acid 2 .1 0.72 9 1.7 -6. 7 20 -80 8.1 - 4.4
g-Aminophenyl-
arsonic acid 6.3 0.64 8 1.7 -6. 7 20 -80 6.0 -3.0
Arsenic (V) 13.,0 0.46 6 1.7 -6. 7 20 -80 10.8 - 1.0
'The upper limit of the range can be increased by using higher concentration standards which
are injected via loops of smaller volume. Although not tested with air samples, the useful
range can be extended from 5 ^9/m3 down to 1.7 /ug/mj based upon the measurement range r
TUIUtl THIN
r- -
PMTNTNIIK nm
HAITI FUHACt I
IN CNHMATOUAPK UATMtt MSMPTM SPCCT.

-tipAism OUMIEI
All ION
ceuiil
MIC10IOK
Ttimc
Ctll
S-TVINS
CAS-U08IO
KMttfN
FIGURE 1. IC/AAS Analytical System.

AISIRE CAS
JL
111*I0 + CAS
oo>
1 •IMOID WASTE
i" 14" 1.0. TIIIIC
5"
j nV
ElfAISIOI CRANIEI
NCt CUIIDIKAL Vl'ir
\^
FIGURE 2. Gas-Liquid Separator and Expansion Chamber.
13 MM ID
VAIIAC '
TIAHSFOWR !
' 1
.s
FIGURE 3. Quartz Furnace Atomization Cell.

ARSENIC TRIOXIDE, as As 7901
As203 MW: 197.84 CAS: 1327-53-3 RTECS: CG3325000

OSHA : 0.01 mg/nrr (As) PROPERTIES: solid; MP 275 °C or 313 °C (sublimes);

NIOSH: C 0.002 mg/m3 (As)/15 min; carcinogen VP 0.0075 Pa (5.6 x 10"5mmHg; 0.45 //g
ACGIH: 0.01 mg/m3; carcinogen As/m3) @ 25 °C
SYNONYMS: arsenous acid anhydride; arsenous sesquioxide; arsenolite; claudetite
SAMPLER: FILTER TECHNIQUE: ATOMIC ABSORPTION, GRAPHITE

(Na2CO3-impregnated, 0.8-//m cellulose FURNACE
ester membrane + backup pad)
ANALYTE: arsenic
O
ASHING: 15 mL HNO3 + 6 mL H202; 150 °C
VOL-MIN: 30 L @ 0.01 mg/nT3
-MAX: 1000 L FINAL
SOLUTION: 10 mL 1% HN03, 0.1% Ni2 +
SHIPMENT: routine
WAVELENGTH: 193.7 nm; D2 or H2 correction
SAMPLE
STABILITY: stable GRAPHITE TUBE: pyrolytic
BLANKS: 2 to 10 field blanks per set GRAPHITE

FURNACE: DRY: 100 °C, 70 sec; CHAR: 1300 °C,
30 sec; ATOMIZE: 2700 °C, 10 sec
ACCURACY INJECTION: 25 fjL
RANGE STUDIED: 0.67 to 32 fjg/m3 [1,2] CALIBRATION: As in 1% HN03, 0.1% Ni2 +

(400-L samples)
BIAS: - 0.55% RANGE: 0.3 to 13 fjg per sample
OVERALL PRECISION (SrT): 0.075 [1,2] ESTIMATED LOD: 0.06 //g per sample
ACCURACY: ± 11.9%
PRECISION (Sr): 0.029 [3,4]
APPLICABILITY: The working range is 0.001 to 0.06 mg/m3 for a 200-L air sample. This method collects particulate arsenic
compounds as well as arsenic trioxide vapor. If only total particulate arsenic is of interest, the use of the treated filter and
analysis of the backup pad is not required. Arsine is not collected by this sampling method.
INTERFERENCES: Background absorption is overcome by the use of a deuterium background corrector. Matrix modification
with Ni solution allows the use of a higher char temperature in the graphite furnace. Other particulate arsenic compounds
will interfere.
OTHER METHODS: This method combines and replaces P&CAM 346 [3], S309 [4], and P&CAM 286 [5]. Method 7300
(ICP-AES) and arsine generation (Method 7900 and the criteria document method [1]) are for particulate arsenic compounds.
Other methods (P&CAM 173 [7], P&CAM 180 [8], and P&CAM 188 [9]) have not been revised because of interferences or poor
sensitivity.

ARSENIC TRIOXIDE, as As: METHOD 7901, Issue 2, dated 15 August 1994 - Page 2 of 4
1. Nitric acid, conc. 1. Sampler: Cellulose ester membrane filter,

2. Nitric acid, 1% (v/v). Dilute 10 mL conc. 0.8-fjm pore size, 37-mm diameter, and
HNO3 to 1 L with distilled or deionized water. cellulose backup pad in cassette filter holder
3. Hydrogen peroxide, 30% (w/w). treated as follows:
4. Ni2+ in 1% HNO3, 1000 fjg/mL Dilute 4.95 a. Remove inlet plug from the loaded
g Ni(NO3)2 to 1 L with 1% HNO3. cassette.
5. Calibration stock solution*, 1000 //g As/mL, b. Add 250 fjL 20:1 Na2CO3:glycerol solution
commercially available, or dissolve 1.320 g with a micropipet directly onto filter (wet
primary standard As2O3 in 25 mL 20% (w/v) entire surface).
KOH. Neutralize with 20% (v/v) HNO3 to a c. Attach to vacuum source and draw 30 to
phenolphthalein endpoint. Dilute to 1 L with 60 L clean air through the filter.
1% HNO3. d. Let dry overnight or dry 8 h @ 120 °C.
6. 1 M Na2CO3:glycerol solution, 20:1. Dissolve Replace the inlet plug.
9.5 g sodium carbonate in 100 mL distilled or e. Use within one week.
deionized water. Add 5 mL pure glycerol. 2. Personal sampling pump, 1 to 3 L/min, with
7. Distilled or deionized water. flexible connecting tubing.
8. Argon. NOTE: The treated filter has a high pressure
drop; a personal sampling pump with
flow rate control is required.
See Special Precautions 3. Atomic absorption spectrophotometer with
graphite furnace atomizer, arsenic
electrodeless discharge lamp, and background
correction.
4. Regulator, two-stage for argon.
5. Beakers, Phillips, 125-mL, or Griffin, 50-mL
with watchglass covers.*
6. Volumetric flasks, 10-mL*
7. Assorted volumetric pipets as needed.*
8. Hotplate, surface temperature to 150 °C.
9. Steambath.
* Clean all glassware with conc, nitric acid

and rinse thoroughly with distilled or
deionized water before use.
SPECIAL PRECAUTIONS: Arsenic is a carcinogen [6]. Handle appropriately. Perform all digestions
in a fume hood.
SAMPLING:

1000 L Do not exceed a filter loading of ca. 2 mg total dust.
SAMPLE PREPARATION:
3. Transfer both the treated filter and backup pad to a clean beaker.
4. Add 15 mL conc. HNO3 and cover with a watchglass.
NOTE: Start reagent blanks at this step.
5. Heat on a 150 °C hotplate until the liquid volume is reduced to about 1 mL

ARSENIC TRIOXIDE, as As: METHOD 7901, Issue 2. dated 15 August 1994 - Page 3 of 4
6. Carefully rinse the material on the bottom of the watchglass, and the sides of the beaker into the
sample solution with distilled water. Add 6 ml_ 30% h^C^.
7. Evaporate just to dryness on the steambath.
8. Cool beakers. Add 10.0 mL 1000 ^g/mL Ni2 + solution, cover, and mix for 30 min in an
ultrasonic bath.
9. Dilute the calibration stock solution 1:100 with 1000 fJQ/mL Ni+ + solution. This standard is
10.0 ^g/mL As. Prepare fresh daily.
10. Prepare six working standards covering the range 0 to 1.25 //g/mL As.
a. Add aliquots of the 10.0 vg/mL As solution to 10-mL volumetric flasks and dilute to volume
with 1000//g/mL Ni2+ solution.
b. Analyze the working standards together with the samplers and blanks (steps 13 and 14).
c. Prepare calibration graph (absorbance vs. solution concentration, //g/mL). Inject a standard
for every other sample to check instrument drift.
11. Check recoveries with at least two spiked media blanks per ten samples.
MEASUREMENT:
13. Set spectrophotometer according to manufacturer's recommendations to conditions on

page 7901-1.
14. Inject standards and samples. Record absorbance (peak height) readings.
dilute the solutions with 1000 //g/mL Ni2 + solution, reanalyze, and use the appropriate
dilution factor in calculations.
CALCULATIONS:
15. Record the actual solution volumes to which the sample, Vs (mL), and media blanks, Vb (mL)
were diluted in step 8.
16. Calculate the solution concentration of arsenic in the sample, Cs (^g/mL), and average media
blank, Cb (jjg/mL), from the calibration graph.
17. Calculate the concentration of arsenic, C (mg/m ), in the air volume sampled, V(L):
. m8/m3.
Method S309 [4] was issued on September 26, 1975, and validated with aerosols generated from As2O3
solutions in dilute NaOH [2]. Method P&CAM 346 was developed in August, 1981, over the range 0.67
to 32.2 ^g/m for a 400-L air sample, corresponding to 0.268 to 12.8 fjg As per sample [1].
Atmospheres were generated by passing air over heated As2O3. Collection efficiencies (CE) for As2O3
under these conditions were determined to be 0.42 and 0.67 for untreated 0.8-mm cellulose ester
membrane filters, and cellulose backup pads, respectively. Under the same conditions, the
Na2CO3-treated filter had CE = 0.93 [5]. This method was used in a lead-acid battery manufacturing
plant in which vapor was found to be significant [10].

ARSENIC TRIOXIDE, as As: METHOD 7901, Issue 2, dated 15 August 1994 - Page 4 of 4
REFERENCES:
[1] Carlin, L M., G. Colovos, D. Garland, M. E. Jamin, M. Klenck, T. J. Long, and C. L Nealy.
Analytical Methods Evaluation and Validation - As, Ni, W, V, Talc, and Wood Dust, Rockwell
International, Final Report on NIOSH Contract No. 210-79-0060; available as Order No. PB
83-155325 from NTIS, Springfield, VA 22161.
[3] Ibid, NIOSH Manual of Analytical Methods, 2nd ed., V. 7, P&CAM 346, U.S. Department of
[4] Ibid, V. 3, S309, U.S. Department of Health, Education, and Welfare, Publ. (NIOSH) 77-1 57-C
(1977).
[5] Ibid, P&CAM 286.
79-1 41 -C (1979).
77-1 57-A (1977).
[9] Ibid, P&CAM 188.
[10] Costello, R. J., P. M. Eller, and R. D. Hull. Measurement of Multiple Inorganic Arsenic Species,
Am. Ind. Hyg. Assoc. J., 44, 21-28 (1983).
METHOD REVISED BY:
M. Millson and P. M. Eller, Ph.D., NIOSH/DPSE; P&CAM 346 originally developed under NIOSH Contract
210-79-0060.

ARSINE 6001
AsH- MW: 77.95 CAS: 7784-42-1 RTECS: CG6475000

OSHA : 0.05 ppm PROPERTIES: gas; d 3.484 g/L @ 20 °C;

NIOSH: C 0.002 mg/m3/15 min; carcinogen BP -62.5 °C; MP -116.3 °C
ACGIH: 0.05 ppm; carcinogen
(1 ppm = 3.19 mg/m3 @ NTP)
SYNONYMS: hydrogen arsenide; arsenic trihydride.
SAMPLER: SOLID SORBENT TUBE TECHNIQUE: ATOMIC ABSORPTION, GRAPHITE

(coconut shell charcoal, 100 mg/50 mg) FURNACE
FLOW RATE: 0.01 to 0.2 L/min ANALYTE: arsenic
VOL-MIN: 0.1 L @ 0.05 ppm DESORPTION: 1 mL 0.01 M HNO3; 30 min in

-MAX: 10 L ultrasonic bath
SHIPMENT: routine MATRIX

MODIFIER: Ni2 + , 1000 //g/mL
SAMPLE
STABILITY: at least 6 days @ 25 °C [1] WAVELENGTH: 193.7 nm; D2 or H2 correction
BLANKS: 2 to 10 field blanks per set GRAPHITE

FURNACE: DRY: 40 sec @ 110 °C; CHAR: 15 sec
@ 1200 °C; ATOMIZE 7 sec @ 2540 °C
INJECTION: 50 fjL
ACCURACY
CALIBRATION: As(lll) in 0.01 M HNO3 with
RANGE STUDIED: 0.09 to 0.4 mg/m3 [1] 100 mg charcoal present
(10-L samples);
0.001 to 0.01 mg/m3 [2] RANGE: 0.01 to 0.3 fjg per sample [2]
BIAS: -6.13% at 0.01 to 0.2 L/min rates [1];
ESTIMATED LOD: 0.004 fjg per sample
-11% @ 0.876 L/min [2]
OVERALL PRECISION (SrT): 0.087 [2] PRECISION (Sr): 0.060 @ 0.01 2 to 0.1 1//g
per sample [2]
ACCURACY: ± 23.2%
APPLICABILITY: The working range is 0.0003 to 0.06 ppm (0.001 to 0.2 mg/m ) for a 10-L air sample. This is an elemental
analysis and is not compound-specific.
INTERFERENCES: Use background correction to control molecular absorption. Other arsenic compounds (gases or aerosols)
may be collected on the sampler and would be erroneously reported as arsine. A cellulose ester filter in front of the charcoal
tube may be used to remove aerosols [3,4]. The effect of relative humidity on the capacity of charcoal for arsine has not been
studied.
OTHER METHODS: This method combines and replaces P&CAM 265 [5] and S229 [6] for arsine.

ARSINE: METHOD 6001, Issue 2, dated 15 August 1994 - Page 2 of 4
1. Water, distilled or deionized. 1. Sampler: glass tube, 7 cm long, 6-mm CD,

2. Nitric acid, conc.* 4-mm ID, flame-sealed ends, containing two
3. Nitric acid, 0.01 M- Dilute 0.4 mL conc. HNO3 sections of activated (600 °C) coconut shell
to 1 L with water. charcoal (front = 100 mg; back = 50 mg)
4. Nitric acid, 0.1 M- Dilute 4 mL conc. HNO3 to separated by a 2-mm urethane foam plug. A
1 L with water. silylated glass wool plug precedes the front
5. Arsenic stock solution, 1000 //g As(lll)/mL* section and a 3-mm urethane foam plug
Commercial standard or dissolve 1.322 g follows the back section. Pressure drop
dried, certified reagent As2O3 in 100 mL 0.1 M across the tube at 1 L/min airflow must be
HNO3; dilute to 1 L with 0.1 M HNO3. less than 3.4 kPa. Tubes are commercially
6. Calibration stock solution, 1.0 JJQ As(lll)/mL* available.
Dilute 0.1 mL arsenic stock solution (1000 //g NOTE: Use a cellulose ester membrane filter
As/mL) to 100 mL with 0.01 M HNO3. in front of the sampler if particulate
Prepare fresh daily. arsenic is present [3,4].
7. Nickel nitrate solution, 1000 //g Ni/mL 2. Personal sampling pump, 0.01 to 0.2 L/min,
Commercial nickel atomic absorption standard with flexible connecting tubing.
or dissolve 3.112 g dried reagent Ni(NO3)2 in 3. Atomic absorption spectrophotometer with
100 mL 0.1 M HNO3; dilute to 1 L with water. graphite furnace, non-pyrolytic tubes,
8. Argon, compressed. background correction and electrodeless
9. Arsine, *99%, or certified mixture in nitrogen. discharge (and power supply) or hollow
cathode lamp for arsenic.
4. Volumetric flasks, 1-Land 100-mL*
5. Micropipets, 5- to 500-juL*
* See Special Precautions 6. Centrifuge tubes, 10- or 15-mL*
7. Ultrasonic bath.
8. Centrifuge.
9. Syringe, gas, 0.1 -mL, readable to 1 //L
*Clean all glassware with conc, nitric acid and

rinse thoroughly with distilled or deionized
water before use.
SPECIAL PRECAUTIONS: Arsenic is a human carcinogen [7]. Perform all concentrated acid handling
in a fume hood. Arsine is extremely poisonous by inhalation. Handle in well-ventilated hood.
SAMPLING:

NOTE: Use a cellulose ester membrane prefilter if particulate arsenic compounds may be
present [3,4].
0.1 to 10 L
4. Cap the sampler with plastic (not rubber) caps and pack securely for shipment.
SAMPLE PREPARATION:
5. Place the front and back sorbent sections of the sampler tube in separate centrifuge tubes.
Discard the glass wool and foam plugs.
6. Add 1.0 mL 0.01 M HNO3 to each tube. Cap each tube.

7. Agitate for 30 min in an ultrasonic bath.

8. Centrifuge each tube.
9. Calibrate daily with at least six working standards over the range 0.004 to 0.3 //g arsenic per
sample.
a. Add known amounts of calibration stock solution and 0.01 M HNO3 for a 1.0-mL final
solution volume to centrifuge tubes containing 100 mg activated charcoal from a media
blank sampler.
b. Analyze standards together with samples and blanks (steps 12 and 13). Analyze a working
standard for every five samples to check for instrument drift.
c. Prepare a calibration graph (absorbance vs. //g arsenic).
in the range 0.004 to 2 //g arsenic per sample. Prepare three tubes at each of five levels plus
three media blanks.
b. Inject a known amount of pure arsine gas (or a certified gas mixture containing arsine)
directly onto front sorbent section with a microliter syringe.
e. Prepare a graph of DE vs. //g arsenic recovered.
11. Analyze three quality control spikes to ensure that the calibration graph is in control.
MEASUREMENT:
12. Set the spectrophotometer and furnace to manufacturer's recommendations and to conditions
given on page 6001-1.
13. Inject a 50-//L aliquot of sample or standard followed by a 50-fjL aliquot of nickel nitrate solution
prior to initiating the analysis program. Measure peak area.
NOTE 1: If sample absorbance is above the linear range of the standards, dilute with 0.01 M
HNO3, reanalyze and apply the appropriate dilution factor in calculations.
NOTE 2: Monitor the reproducibility of peak area for a working standard throughout the
measurements. If erratic results occur, reoptimize instrumental parameters and replace
the graphite tube.
CALCULATIONS:
14. Determine the mass, //g, of arsine found in the sample front (Wf) and back (Wb) sorbent
sections, and in the average media blank front (Bf) and back (Bb) sorbent sections by
multiplying the mass of arsenic found for each of these sections by 1.040 (M.W. of arsine/M.W.
of arsenic).
15. Calculate concentration, C, of arsine in the air volume sampled, V (L):
c - w' * w» B' -

Method S229 [6] was evaluated over the range 0.094 to 0.404 mg/m3 using 10-L air samples collected
on SKC Lot 105 activated coconut charcoal [1]. Breakthrough (onto the backup section) did not occur
after 240 min of sampling at 0.227 L/min from an arsine concentration of 0.405 mg/m3 (0.022 mg
loading). The recovery was found to be 93.7%. Desorption efficiency was 0.90 at 1 //g arsine per
sample and 1.00 at 2 and 4 fjg arsine per sample.
Method P&CAM 265 [5] was evaluated over the range 0.001 to 0.01 mg/m3 using 15-L air samples [2].
These samples were collected on SKC Lot 106 activated coconut charcoal at a sampling flow rate of
0.875 L/min for 15 min. At this flow rate, a collection efficiency of 89.1% was found [3]. The effect of
high humidity on the sampler capacity was not studied. Desorption efficiency was 0.90 in the range
0.015 to 0.2 //g arsine per sample.
REFERENCES:
Welfare, Publ. (NIOSH) 77-185 (1977), also available as Order No. PB 263959 from NTIS,
Springfield, VA 22161 (1975).
[2] Evaluation and Refinement of Personal Sampling Method for Arsine, NIOSH Research Report,
prepared under NIOSH Contract No. 210-76-0142 (NIOSH, unpublished, 1977).
[3] Costello, R. J., P. M. Eller and R. D. Hull. Measurement of Multiple Inorganic Arsenic Species,
Am. Ind. Hyg. Assoc. J.. 44(1). 21-28 (1983).
[4] Methods 7900 (Arsenic) and 7901 (Arsenic Trioxide), this Manual.
Education, and Welfare, Publ. (NIOSH) 77-1 57-C (1977).
METHOD REVISED BY:
R. D. Hull, Ph.D., NIOSH/DBBS.

ASBESTOS (bulk) by PLM 9002
various MW: various CAS: 1332-21-4 RTECS: CI6475000

EPA Standard (Bulk): 1% PROPERTIES: solid, fibrous, crystalline, anisotropic
SYNONYMS [CAS #]: actinolite [77536-66-4], orferroactinolite [15669-07-5]; amosite [12172-73-5]; anthophyllite [77536-67-5];
chrysotile [12001-29-5]; serpentine [18786-24-8]; crocidolite [12001 -28-4]; tremolite [77536-68-6]; amphibole asbestos [1332-21-4],
BULK SAMPLE: 1 to 10 grams TECHNIQUE: MICROSCOPY, STEREO AND

POLARIZED LIGHT, WITH DISPERSION
SHIPMENT: seal securely to prevent escape of STAINING
asbestos
ANALYTE: actinolite asbestos, amosite, anthophyllite
SAMPLE asbestos, chrysotile, crocidolite, tremolite
STABILITY: stable asbestos
BLANKS: none required EQUIPMENT: microscope, polarized light; 100-400X

dispersion staining objective , stereo
microscope: 10-45X
RANGE: 1% to 100% asbestos
ESTIMATED LOD: < 1% asbestos [1]
ACCURACY
RANGE STUDIED: < 1% to 100% asbestos
APPLICABILITY: this method is useful for the qualitative identification of asbestos and the semi-quantitative determination of
asbestos content of bulk samples. The method measures percent asbestos as perceived by the analyst in comparison to
standard area projections, photos, and drawings, or trained experience. The method is not applicable to samples containing
large amounts of fine fibers below the resolution of the light microscope.
INTERFERENCES: Other fibers with optical properties similar to the asbestos minerals may give positive interferences. Optical
properties of asbestos may be obscured by coating on the fibers. Fibers finer than the resolving power of the microscope (ca.
0.3 fjm) will not be detected. Heat and acid treatment may alter the index of refraction of asbestos and change its color.
OTHER METHODS: This method (originally designated as method 7403) is designed for use with NIOSH Methods 7400 (phase
contrast microscopy) and 7402 (electron microscopy/EDS). The method is similar to the EPA bulk asbestos method [1].

ASBESTOS (bulk): METHOD 9002, Issue 2, dated 15 August 1994 - Page 2 of 9
1. Refractive index (Rl) liquids for Dispersion 1 . Sample containers: screw-top plastic vials of
Staining: high-dispersion (HD) series, 1.550, 10- to 50-mL capacity.
1.605, 1.620. 2. Microscope, polarized light, with polarizer,
2. Refractive index liquids: 1.670, 1.680, and analyzer, port for retardation plate, 360°
1.700. graduated rotating stage, substage condenser
3. Asbestos reference samples such as SRM with iris, lamp, lamp iris, and:
#1866, available from the National Institute of a. Objective lenses: 10X, 20X, and 40X or
Standards and Technology.* near equivalent.
4. Distilled Water (optional). b. Ocular lense: 1 0X minimum.
5. Concentrated HCI: ACS reagent grade. c. Eyepiece reticle: crosshair.
d. Dispersion staining objective lens or
equivalent.
e. Compensator plate: ca. 550 nm ± 20 nm,
See SPECIAL PRECAUTIONS. retardation: "first order red" compensator.
3. Microscope slides: 75 mm x 25 mm.
4. Cover slips.
5. Ventilated hood or negative-pressure glove
box.
6. Mortar and pestle: agate or porcelain.
7. Stereomicroscope, ca. 10 to 45X.
8. Light source: incandescent or fluorescent.
9. Tweezers, dissecting needles, spatulas,
probes, and scalpels.
10. Glassine paper or clean glass plate.
11. Low-speed hand drill with coarse burr bit
(optional).
SPECIAL PRECAUTIONS: Asbestos, a human carcinogen, should be handled only in an exhaust hood
(equipped with a HEPA filter) [2]. Precautions should be taken when collecting unknown samples, which
may be asbestos, to preclude exposure to the person collecting the sample and minimize the disruption
to the parent material [3]. Disposal of asbestos-containing materials should follow EPA Guidelines [4].
SAMPLING:
1. Place 1 to 10 g of the material to be analyzed in a sample container.

NOTE: For large samples (i.e., whole ceiling tiles) that are fairly homogenous, a representative
small portion should be submitted for analysis. Sample size should be adjusted to
ensure that it is representative of the parent material.
2. Make sure that sample containers are taped so they will not open in transit.
3. Ship the samples in a rigid container with sufficient packing material to prevent damage or
sample loss.
SAMPLE PREPARATION:
4. Visually examine samples in the container and with a low-magnification stereomicroscope in a

hood. (If necessary, a sample may be carefully removed from the container and placed on
glassine transfer paper or clean glass plate for examination). Break off a portion of the sample
and examine the edges for emergent fibers. Note the homogeneity of the sample. Some hard
tiles can be broken, and the edges examined for emergent fibers. If fibers are found, make an
estimate of the amount and type of fibers present, confirm fiber type (step 14) and quantify (step
15).

5. In a hood, open sample container and with tweezers remove small, representative portions of
the sample.
a. If there are obvious separable layers, sample and analyze each layer separately.
b. If the sample appears to be slightly inhomogeneous, mix it in the sample container with
tweezers or a spatula before taking the portion of analysis. Alternatively, take small
representative portions of each type of material and place on a glass slide.
c. On hard tiles that may have thin, inseparable layers, use a scalpel to cut through all the
layers for a representative sample. Then cut it into smaller pieces after placing Rl liquid on it
before trying to reduce the thickness. Alternatively, use a low-speed hand drill equipped
with a burr bit to remove material from hard tiles. Avoid excessive heating of the sample
which may alter the optical properties of the material.
NOTE: This type of sample often requires ashing or other specialized preparation, and may
require transmission electron microscopy for detection of the short asbestos fibers
which are characteristic of floor tiles.
d. If the sample has large, hard particles, grind it in a mortar. Do not grind so fine that fiber
characteristics are destroyed.
e. If necessary, treat a portion of the sample in a hood with an appropriate solvent to remove
binders, tars, and other interfering materials which may be present in the sample. Make
corrections for the non-asbestos material removed by this process.
NOTE: Other methods of sample preparation such as acid washing and sodium
metaphosphate treatment and ashing may be necessary, especially to detect low
concentrations of asbestos. If needed, use as described in Reference [1].
6. After placing a few drops of Rl liquid on the slide, put a small portion of sample in the liquid.
Tease apart with a needle or smash small clumps with the flat end of a spatula or probe,
producing a uniform thickness or particles so that better estimates of projected area
percentages can be made. Mix the fibers and particles on the slide so that they are as
homogeneous as possible.
NOTE: An even dispersion of sample should cover the entire area under the cover slip, some
practice will be necessary to judge the right amount of material to place on the slide.
Too little sample may not give sufficient information and too much sample cannot be
easily analyzed.
7. Check for contamination each day of operation. Wipe microscope slides and cover slips with
lens paper before using. Check refractive index liquids. Record results in a separate logbook.
8. Verify the refractive indices of the refractive index liquids used once per week of operation.
Record these checks in a separate logbook.
9. Follow the manufacturer's instructions for illumination, condenser alignment and other
microscope adjustments. Perform these adjustments prior to each sample set.
1 0. Determine percent of each identified asbestos species by comparison to standard projections
(Figure 1) [1]. If no fibers are detected in a homogeneous sample, examine at least two
additional preparations before concluding that no asbestos is present.
11. If it appears that the preparation technique might not be able to produce a homogeneous or
representative sample on the slide, prepare a duplicate slide and average the results.
Occasionally, when the duplicate results vary greatly, it will be necessary to prepare additional
replicate slides and average all the replicate results. Prepare duplicate slides of at least 10% of
the samples analyzed. Average the results for reporting.
12. Analyze about 5% blind samples of known asbestos content.
13. Laboratories performing this analytical method should participate in the National Voluntary
Laboratory Accreditation Program [5] or a similar interlaboratory quality control program. Each
analyst should have complete formal training in polarized light microscopy and its application to
crystalline materials. In lieu of formal training, laboratory training in asbestos bulk analysis under
the direction of a trained asbestos bulk analyst may be substituted. Owing to the subjective
nature of the method, frequent practice is essential in order to remain proficient in estimating
projected area percentages.

QUALITATIVE ASSESSMENT:
14. Scan the slide to identify any asbestos minerals using the optical properties of morphology,
refractive indices, color, pleochroism, birefringence, extinction characteristics, sign of elongation,
and dispersion staining characteristics.
NOTE: Identification of asbestos using polarized light microscopy is unlike most other analytical
methods. The quality of the results is dependent on the skill and judgment of the
analyst. This method does not lend itself easily to a step-wise approach. Various
procedures devised by different analysts may yield equivalent results. The following
step-wise procedure repeatedly utilizes the sample preparation procedure previously
outlined.
a. Prepare a slide using 1.550 HD Rl liquid. Adjust the polarizing filter such that the polars are
partially crossed, with ca. 15° offset. Scan the preparation, examining the morphology for
the presence of fibers. If no fibers are found, scan the additional preparations. If no fibers
are found in any of the preparations, report that the sample does not contain asbestos, and
stop the analysis at this point.
b. If fibers are found, adjust the polarizing filter such that the polars are fully crossed. If all of
the fibers are isotropic (disappear at all angles of rotation) then those fibers are not
asbestos. Fibrous glass and mineral wool, which are common components of suspect
samples, are isotropic. If only isotropic fibers are found in the additional preparations, report
no asbestos fibers detected, and stop the analysis.
c. If anisotropic fibers are found, rotate the stage to determine the angle of extinction. Except
for tremolite-actinolite asbestos which has oblique extinction at 10-20°, the other forms of
asbestos exhibit parallel extinction (Table 1). Tremolite may show both parallel and oblique
extinction.
d. Insert the first order red compensator plate in the microscope and determine the sign of
elongation. All forms of asbestos have a positive sign of elongation except for crocidolite. If
the sign of elongation observed is negative, go to step "g."
NOTE: To determine the direction of the sign of elongation on a particular microscope
configuration, examine a known chrysotile sample and note the direction (NE-SW or
NW-SE) of the blue coloration. Chrysotile has a positive sign of elongation.
e. Remove the first-order red compensator and uncross the polarizer. Examine under plane
polarized light for blue and gold-brown Becke colors at the fiber-oil interface (i.e., index of
refraction match). Becke colors are not always evident. Examine fiber morphology for
twisted, wavy bundles of fibers which are characteristic of chrysotile. Twisted, ribbon-like
morphology with cellular internal features may indicate cellulose fibers. It may be necessary
to cross the polars partially in order to see the fibers if the index of refraction is an exact
match at 1.550. If the fibers appear to have higher index of refraction, go to step "h,"
otherwise continue.
f. Identification of chrysotile. Insert the dispersion staining objective. Observation of
dispersion staining colors of blue and blue-magenta confirms chrysotile. Cellulose, which is
a common interfering fiber at the 1.550 index of refraction, will not exhibit these dispersion
staining colors. If chrysotile is found, go to step 15 for quantitative estimation.
g. Identification of crocidolite. Prepare a slide in 1 .700 Rl liquid. Examine under plane-
polarized light (uncrossed polars); check for morphology of crocidolite. Fibers will be
straight, with rigid appearance, and may appear blue or purple-blue. Crocidolite is
pleochroic, i.e., it will appear to change its color (blue or gray) as it is rotated through plane
polarized light. Insert the dispersion staining objective. The central stop dispersion staining
color are red magenta and blue magenta, however, these colors are sometimes difficult to
impossible to see because of the opacity of the dark blue fibers. If observations above
indicate crocidolite, go to step 15 for quantitative estimation.
h. Identification of amosite. Prepare a slide in 1.680 Rl liquid. Observed the fiber morphology
for amosite characteristics: straight fibers and fiber bundles with broom-like or splayed
ends. If the morphology matches amosite, examine the fibers using the dispersion staining
objective. Blue and pale blue colors indicate the cummingtonite form of amosite, and gold
and blue colors indicate the grunerite form of amosite. If amosite is confirmed by this test,

go to step 15 for quantitative estimation, otherwise continue.
i. Identification of anthophyllite-tremolite-actinolite. Prepare a slide in 1.605 HD Rl liquid.

Examine morphology for comparison to anthophyllite-tremolite-actinolite asbestos. The
refractive indices for these forms of asbestos vary naturally within the species. Anthophyllite
can be distinguished from actinolite and tremolite by its nearly parallel extinction. Actinolite
has a light to dark green color under plane-polarized light and exhibits some pleochroism.
For all three, fibers will be straight, single fibers possibly with some larger composite fibers.
Cleavage fragments may also be present. Examine using the central stop dispersion
staining objective. Anthophyllite will exhibit central stop colors of blue and gold/gold-
magenta; tremolite will exhibit pale blue and yellow; and actinolite will exhibit magenta and
golden-yellow colors.
NOTE: In this refractive index range, wollastonite is a common interfering mineral with
similar morphology including the presence of cleavage fragments. It has both
positive and negative sign of elongation, parallel extinction, and central stop
dispersion staining colors of pale yellow and pale yellow to magenta. If further
confirmation of wollastonite versus anthophyllite is needed, go to step "['• If any of
the above forms of asbestos were confirmed above, go to step 15 for quantitative
estimation. If none of the tests above confirmed asbestos fibers, examine the
additional preparations and if the same result occurs, report the absence of
asbestos in this sample.
j. Wash a small portion of the sample in a drop of concentrated hydrochloric acid on a slide.
Place the slide, with cover slip in place, on a warm hot plate until dry. By capillary action,
place 1 .620 Rl liquid under the cover clip and examine the slide. Wollastonite fibers will
have a "cross-hatched" appearance across the length of the fibers and will not show central
stop dispersion colors. Anthophyllite and tremolite will still show their original dispersion
colors.
NOTE: There are alternative analysis procedures to the step-wise approach outlined above
which will yield equivalent results. Some of these alternatives are:
i. Perform the initial scan for the presence of asbestos using crossed polars as
well as the first-order red compensator. This allows for simultaneous viewing of
birefringent and amorphous materials as well as determine their sign of
elongation. Some fibers which are covered with mortar may best be observed
using this configuration.
ii. Some analysts prefer to mount their first preparation in a Rl liquid different than
any asbestos materials and conduct their initial examination under plane-
polarized light.
III. If alternative Rl liquids are used from those specified, dispersion staining colors
observed will also change. Refer to an appropriate reference for the specific
colors associated with asbestos in the Rl liquids actually used.
QUANTITATIVE ASSESSMENT:
15. Estimate the content of the asbestos type present in the sample using the 1.550 Rl preparation.
Express the estimate as an area percent of all material present, taking into account the loading
and distribution of all sample material on the slide. Use Figure 1 as an aid in arriving at your
estimate. If additional unidentified fibers are present in the sample, continue with the qualitative
measurement (step 14).
NOTE: Point-counting techniques to determine percentages of the asbestos minerals are not
generally recommended. The point-counting method only produces accurate
quantitative data when the material on the slide is homogeneous and has a uniform
thickness, which is difficult to obtain [6]. The point-counting technique is, recommended
by the EPA to determine the amount of asbestos in bulk [1]; however, in the more
recent Asbestos Hazard Emergency Response Act (AHERA) regulations, asbestos
quantification may be performed by a point-counting or equivalent estimation
method [7].

16. Make a quantitative estimate of the asbestos content of the sample from the appropriate
combination of the estimates from both the gross and microscopic examinations. If asbestos
fibers are identified, report the material as "asbestos-containing". Asbestos content should be
reported as a range of percent content. The range reported should be indicative of the analyst's
precision in estimating asbestos content. For greater quantities use Figure 1 in arriving at your
estimate.
The method is compiled from standard techniques used in mineralogy [8-13], and from standard
laboratory procedures for bulk asbestos analysis which have been utilized for several years. These
techniques have been successfully applied to the analysis of EPA Bulk Sample Analysis Quality
Assurance Program samples since 1982 [1,5]. However, no formal evaluation of this method, as written,
has been performed.
REFERENCES:
[I] Perkins, R.L. and B.W. Harvey, U.S. Environmental Protection Agency. Test Method for the
Determination of Asbestos in Bulk Building Materials. EPA/600/R-93/116 (June. 1993).
[2] Criteria for a Recommended Standard... Occupational Exposure to Asbestos (Revised), U.S.
Department of Health, Education, and Welfare, Publ. (NIOSH) 77-169 (1976), AS AMENDED IN
NIOSH Statement at OSHA Public Hearing, (June 21, 1984).
[3] Jankovic, J.T. Asbestos Bulk Sampling Procedure, Amer. Ind. Hvg. Assoc. J., B-8 to B-10,
(February, 1985).
[4] U.S. Environmental Protection Agency, "Asbestos Waste Management Guidance" EPA/530-SW-
85-007, (May, 1985).
[5] National Voluntary Laboratory Accreditation Program, National Institute of Standards and
Technology, Bldg 101, Room A-807 Gaithersburg, MD. 20899.
[6] Jankovic, J.T., J.L Clere, W. Sanderson, and L Piacitelli. Estimating Quantities of Asbestos in
Building Materials. National Asbestos Council Journal, (Fall, 1988).
[7] Title 40, Code of Federal Regulations, Part 763. Appendix A to Subpart F. Interim Method of the
Determination of Asbestos in Bulk Insulation Samples, (April 15, 1988).
[8] Bloss, F. Donald, Introduction to the Methods of Optical Crystallography. Holt, Rinehart, &
Winston, (1961).
[9] Kerr, Paul F., Optical Mineralogy. 4th Ed., New York, McGraw-Hill, (1977).
[10] Shelley, David, Optical Mineralogy, 2nd Ed.. New York, Elsevier, (1985).
[II] Phillips, W.R. and D.T. Griffen, Optical Mineralogy. W. H. Freeman and Co., (1981).
[12] McCrone, Walter, The Asbestos Particle Atlas. Ann Arbor Science, Michigan, (1980).
[13] "Selected Silicate Minerals and their Asbestiform Varieties," Bureau of Mines Information Circular
lC 8751, (1977).
METHOD WRITTEN BY:
Patricia A. Klinger, CIHT, and Keith R. Nicholson, CIH, DataChem Laboratories, Inc., Salt Lake City, Utah,
under NIOSH Contract 200-84-2608. and Frank J. Heart, PE, NIOSH/DRDS and John T. Jankovic, CIH.

AMOSITE CHRYSOTILE
IN NON-FIBROUS IN NON-FIBROUS
CARBONATE MINERAL CARBONATE MINERAL
MATRIX PERCENT MATRIX
ASBESTOS
8-10
15-20
20-30
35-4 0 (
Table 1. Optical Properties of Asbestos Fibers
Refractive Index
(Approximate Values)
4. to | to
Mineral Morphology and Color Elongation Elongation Birefringence
Chrysotile Wavy fibers with kinks. 1.54 1.55 0.002-0.014

Splayed ends on larger
bundles. Colorless to
light brown upon being
heated. Nonpleochroie.
Aspect ratio typically
Cummingtonite- Straight fibers and fiber 1.67 1.70 0.02 - 0.03

Grunerite bundles. Bundle ends
(Amosite) appear broom-like or
splayed. Colorless to
brown upon heating.
May be weakly
pleochroie. Aspect ratio
typically >10:1.
Crocidolite Straight fibers and fiber 1.71 1.70 0.014-0.016

(Riebeckite) bundles. Longer fibers Interference colors
show curvature. Splayed may be masked by
ends on bundles. blue color.
Characteristic blue color.
Pleochroie. Aspect ratio
typically >10:1.
Anthophyllite Straight fibers and fiber 1.61 1.63 0.019 - 0.024

bundles. Cleavage
fragments may be
present. Colorless to
light brown.
Nonpleochroic to weakly
pleochroic. Aspect ratio
generally <10:1.
Tremolite- Straight and curved 1.60- 1.62 1.62- 1.64 0.02 - 0.03
Actinolite fibers. Cleavage (tremolite) (tremolite)
fragments common.
Large fiber bundles show
splayed ends. Tremolite 1.62- 1.67 1.64- 1.68
is colorless. Actinolite is (actinolite) (actinolite)
green and weakly to
moderately pleochroie.
Aspect ratio generally

Table 1. Optical Properties of Asbestos Fibers (Continued)
Central Stop Dispersion Staining Colors
Sign of -L* I to
Mineral Extinction Elongation Rl Liquid Vibration Vibration
Chrysotile Parallel to fiber + (length slow) 1.550HD Blue Blue-magenta

length
Cummingtonite- Parallel to fiber + (length slow) 1.670 Red magenta to Yellow

Grunerite length blue
(Amosite) Fibers subjected
to high
temperatures will
not dispersion-
stain.
Cummingtonite 1.680 pale blue blue
Grunerite 1.680 blue gold
Crocidolite Parallel to fiber - (length fast) 1.700 Red magenta Blue-magenta

(Riebeckite) length
1.680 yellow pale yellow
Anthophyllite Parallel to fiber + (length slow) 1.605HD Blue Gold to gold-

length magenta
1.620HD Blue-green Golden-yellow
Tremolite- Oblique - 10 to + (length slow) 1.605HD Pale blue Yellow

Actinolite 20° for (tremolite) (tremolite)
fragments. Some
composite fibers
show | Yellow Pale yellow
extinction. (actinolite) (actinolite)
HD = high-dispersion Rl liquid series.

ASBESTOS, CHRYSOTILE by XRD 9000
Mg3Si205(OH), MW: ca. 283 CAS: 12001-29-5 RTECS: CI6478500

EPA Standard (Bulk): 1% by weight PROPERTIES: solid, fibrous mineral; conversion to

Forsterite at 580 °C; attacked by acids;
loses water above 300 °C
SYNONYMS: Chrysotile
BULK SAMPLE: 1 to 10 grams TECHNIQUE: X-RAY POWDER DIFFRACTION
SHIPMENT: seal securely to prevent escape of asbestos ANALYTE: chrysotile
SAMPLE PREPARATION: grind under liquid N2; wet-sieve through

STABILITY: indefinitely 10-Affn sieve
BLANKS: none required DEPOSIT: 5 mg dust on 0.45-//m Ag membrane filter
XRD: Cu target X-ray tube; Optimize for

intensity; 1 ° slit; Integrated intensity with
background subtraction
CALIBRATION: suspensions of asbestos in 2-propanol
ACCURACY RANGE: 1 to 100% (w/w) asbestos
RANGE STUDIED: 1 to 100% in talc [1] ESTIMATED LOD: 0.2% asbestos in talc and calcite; 0.4% in
heavy X-ray absorbers such as Fe2O3
BIAS: negligible if standards and samples are
matched in particle size [1]
PRECISION (Sr): 0.07 (5 to 100%); 0.10 (@ 3%); 0.125
OVERALL PRECISION (SrT): unknown; depends on (@1%)
matrix and concentration
ACCURACY: ± 14% to ± 25%
APPLICABILITY: Analysis of percent chrysotile asbestos in bulk samples.
INTERFERENCES: Antigorite (massive serpentine), Chlorite, Kaolinite, Bementite, and Brushite interfere. X-ray fluorescence
and absorption is a problem with some elements; fluorescence can be circumvented with a diffracted beam monochromator,
and absorption is corrected for in this method.
OTHER METHODS: This is P&CAM 309 [2] applied to bulk samples only, since the sensitivity is not adequate for personal air
samples. The EPA Test Method for the determination of asbestos in bulk insulation samples is similar to this one [3]. Method
7400 is an optical counting procedure for airborne fibers in personal samples. Methods 7402 (Asbestos by Transmission Electron
Microscopy) and 9002 (Asbestos by Polarized Light Microscopy) are also useful for positive identification of asbestos.

CHRYSOTILE ASBESTOS (BULK): METHOD 9000, Issue 2, dated 15 August 1994 - Page 2 of 6
1. Chrysotile*, available from: Analytical 1. Vials, plastic (for bulk sample).

Reference Minerals, Measurements Research 2. Freezer mill, liquid N2-cooled, (Spex Model
Branch, DPSE, NIOSH, 4676 Columbia 6700 or equivalent), grinding vials (Spex 6701),
Parkway, Cincinnati, OH 45226; or UICC extractor (Spex 6704).
Asbestos Reference Sample Set, UICC MRC 3. Ultrasonic bath.
Pneumoconiosis Unit Uandough Hospital, 4. Sieve, 10-jum, for wet-sieving.
Penarth, Glamorgan, CF6 1XW, UK.2. 5. Filters, polycarbonate, 1.0-//m, 37-mm
2. 2-Propanol.* (Nuclepore or equivalent).
3. Desiccant. 6. Filtration apparatus and side-arm vacuum flask
4. Glue or tape for securing Ag filters to XRD with 25- and 37-mm filter holders.
holders. 7. Oven, drying, 110 °C.
8. Analytical balance, readable to 0.01 mg.
9. Beaker, Griffin, 50-mL, with watchglass cover.
10. Filters, silver membrane, 25-mm diameter,
0.45-//m pore size (Millipore Corp., Poretics
* See SPECIAL PRECAUTIONS. Corp., or equivalent).
11. Desiccator.
12. Bottles, glass, 1-L, with ground glass stoppers.
13. Wash bottle, polyethylene.
14. Magnetic stirrer.
1 5. X-ray powder d iffractometer with coppertarget
x-ray tube and scintillation detector.
1 6. Reference specimen (mica, Arkansas stone or
other stable standard) for data normalization.
17. Volumetric pipettes and flasks.
SPECIAL PRECAUTIONS: Asbestos, a human carcinogen, should be handled in a hood [4].
2-Propanol is flammable.
SAMPLING:
1. Place several grams of the dust to be analyzed in a plastic vial, seal the vial securely and ship in
a padded carton.
SAMPLE PREPARATION:
2. Place ca. 0.5 g of sample dust in a grinding vial and grind in a liquid nitrogen-cooled mill for 2 to
10 min.
3. Wet sieve the ground dust using a 10-//m sieve and 2-propanol. Place the dust on the sieve and
place the sieve directly in an ultrasonic bath or in a wide dish in the bath. Use enough
2-propanol to cover the dust (put water in the bath if a dish is used to contain the 2-propanol).
Apply ultrasonic power to sieve the dust.
NOTE: It may take some time to obtain several mg of dust. Heating of the 2-propanol is likely
and cooling periods may be required.
4. Recover the sieved sample dust from the 2-propanol by filtering the suspension through a
non-fibrous filter (polycarbonate) or by driving off the 2-propanol on a hot plate. Dry the sieved
sample in 1 10 °C oven for 4 h or more.

9 5. Weigh out ca. 5 mg of the sieved material onto a small square of tared weighing paper. Record
the actual weight, W, to the nearest 0.01 mg. Transfer the dust to a 50-mL beaker, washing the
weighing paper with several mL of 2-propanol. Add 10 to 15 mL 2-propanol to the beaker.
6. Cover the beaker with a watchglass. Agitate in an ultrasonic bath at least 3 min until all
agglomerated particles are dispersed. Wash the underside of the watchglass with 2-propanol,
collecting the washings in the beaker.
7. Place a silver filter in the filtration apparatus. Attach the funnel securely over the entire filter
circumference. With no vacuum, pour 2 to 3 mL 2-propanol onto the filter. Pour the sample
suspension from the beaker into the funnel and apply vacuum. During filtration, rinse the beaker
several times and add rinsings to the funnel.
NOTE: Control the filtration rate to keep the liquid level in the funnel near the top during rinsing.
Do not wash the walls or add 2-propanol to the funnel when the liquid level is lower than
4 cm above the filter. Leave the vacuum on after filtration for sufficient time to produce
a dry filter.
8. Remove the filter with forceps and attach it to the sample holder for XRD analysis.
9. Prepare and analyze working standard filters:

a. Prepare two suspensions of chrysotile asbestos in 2-propanol by weighing 10 and 100 mg of
the dry powder to the nearest 0.01 mg. Quantitatively transfer each to a 1-L glass-stoppered
bottle using 1 .00 L 2-propanol.
NOTE: Depending on the particle size of the standard, it may need to be ground and wet
sieved (step 3). Dry the standards in a 1 10 °C oven for 4 h or more. Store in a
desiccator.
b. Suspend the powder in the 2-propanol with an ultrasonic probe or bath for 20 min.
Immediately move the flask to a magnetic stirrer with thermally-insulated top and add a
stirring bar to the suspension. Cool the solution to room temperature before withdrawing
aliquots.
c. Mount a filter on the filtration apparatus. Place several mL 2-propanol on the filter surface.
Turn off the stirrer and shake vigorously by hand. Within a few seconds of setting the bottle
down, remove the lid and withdraw an aliquot from the center of the 10 or 100 mg/L
suspension. Do not adjust the volume in the pipet by expelling part of the suspension. If
more than the desired aliquot is withdrawn, return all of the suspension to the bottle, rinse
and dry the pipet, and take a new aliquot. Transfer the aliquot from the pipet to the filter.
Keep the tip of the pipet near the surface but not submerged in the delivered suspension.
d. Rinse the pipet with several mL 2-propanol, draining the rinse into the funnel. Repeat the
rinse several more times. Prepare working standard filters, in triplicate, by this technique, at
e.g., 0, 20, 30, 50 100, 200 and 500 //g.
e. Apply vacuum and rapidly filter the suspension. Leave vacuum on until filter is dry. Do not
wash down the sides of the funnel after the deposit is in place since this will rearrange the
material on the filter. Transfer the filter to the sample holder.
f. Analyze by XRD (step 12). The XRD intensities (12. d.) are designated lxo and are then
normalized (I2.e.) to obtain lx°. The intensities for standards greater than 200 mg should be
corrected for matrix absorption (12.f. and 13).
g. Prepare a calibration graph by plotting lx°, as a function of //g of each standard.
NOTE: Poor repeatability (greater than 10% above 0.04 mg chrysotile) indicates that new
standards should be made. The data should lie along a straight line. It is preferable
to use a weighted least squares with 1 /a2 weighing, where o2 is the variance of the
data at a given loading,
h. Determine the slope, m, of the calibration curve in counts///g. The intercept on the abscissa
should be within ±5 //g of zero.

NOTE: A large intercept indicates an error in determining the background, i.e., an incorrect
baseline has been calculated or interference by another phase.
10. Select six silver membrane filters as media blanks (for determination of sample self-absorption,
step 13) randomly from the same box of filters to be used for depositing the samples. Mount
each of the media blanks on the filtration apparatus and apply vacuum to draw 5 to 10 mL of
2-propanol through the filter. Remove, let dry and mount on sample holders. Determine the net
normalized count for the silver peak, 1A°8, for each media blank (step 12). Obtain an average
value for the six media blanks.
MEASUREMENT:
11. Obtain a qualitative X-ray diffraction scan (e.g., 10 to 80 degrees 2-theta) of the sample to
determine the presence of chrysotile and interferences. The expected diffraction peaks are as
follows:
Peak (2-Theta Degrees)

Mineral Primary Secondary
Chrysotile 12.08 24.38

Silver 38.12 44.28
12. Mount the filter (sample, standard or blank) in the XRD instrument and:
a. Determine the net intensity, lr, of the reference specimen before each filter is scanned.
Select a convenient normalization scale factor, N, which is approximately equivalent to the
net count for the reference specimen peak, and use this value of N for all analyses.
b. Measure the diffraction peak area of a chrysotile peak that is free of interference. Scan
times should be long, e.g., 15 min.
c. Measure the background on each side of the peak for one-half the time used for peak
scanning. The sum of these two counts is the average background. Determine the position
of the background for each sample.
d. Calculate the net intensity, lx (the difference between the peak integrated count and the total
background count).
e. Calculate and record the normalized intensity, Tx, for the sample peak on each sample and
standard:
N.
NOTE: Normalizing to the reference specimen intensity compensates for long-term drift in X-ray
tube intensity. If intensity measurements are stable, the reference specimen may be run
less frequently; net intensities should be normalized to the most recently measured
reference intensity.
f. Determine the net count, lAg, of an interference-free silver peak on the sample filter following the
same procedure. Use a short scan time for the silver peak (e.g., 5% of scan time for analyte
peaks) throughout the method.
g. Scan each field blank over the same 2-theta range used for the analyte and silver peaks. These
analyses serve only to verify that contamination of the filters has not occurred. The analyte peak
should be absent. The normalized intensity of the silver peak should match that of the media
blanks.

CALCULATIONS:
13. Calculate the percentage of chrysotile in the bulk dust sample:

(Jx-f(T)-b)-100
where: Tx = normalized intensity for sample peak

b = intercept of calibration graph (lx° vs. W)
m = slope of calibration graph (counts///g)
f(T) = - = absorption correction factor (Table 1)
1 - TR
R = sin (6^ )/sin (6J
T = TAg/(average TA°a) = transmittance of sample
TAg = normalized silver peak intensity from sample
average 1A0B = normalized silver peak intensity from media blanks (average of six values)
W = mass of deposited sample in fjg.
NOTE: For a more detailed discussion of the absorption correction procedure, see references
[5] to [8].
This method is based on the work of B.A. Lange in developing P&CAM 309 [1,2]. Samples in the range
of 1 to 100% chrysotile in talc were studied to establish the feasibility of an XRD method for airborne
asbestos. Analytical precision was as follows:
% Chrysotile
in Talc Sr (%)
100 6.9
10 4.7
7 9.8
5 8.2
3 10.1
1 12.5
This work also showed that bias of results after absorption corrections are made is negligible.
REFERENCES:
[1] Lange, B. A. Determination of Microgram Quantities of Asbestos by X-Ray Diffraction: Chrysotile

in Thin Dust Layers of Matrix Material, Anal. Chem., 51:520(1979).
[3] Perkins, R.L and B.W. Harvey. U.S. Environmental Protection Agency Test Method for the
Determination of Asbestos in Bulk Building Materials, EPA/600/R-93/116 (June, 1993).
[4] Criteria for a Recommended Standard. ..Occupational Exposure to Asbestos (Revised), U.S.
[5] Leroux, J. and C. Powers. Direct X-Ray Diffraction Quantitative Analysis of Quartz in Industrial
Dust Films Deposited on Silver Membrane Filters, Occup. Health Rev.. 2.1:26 (1970).
[6] Williams, D. D. Direct Quantitative Diffractometric Analysis, Anal. Chem., 31:1841 (1959).

[7] Abell, M. T., D. D. Dollberg, B. A. Lange, R. W. Hornung and J. C. Haartz. Absorption

Corrections in X-ray Diffraction Dust Analyses: Procedures Employing Silver Filters, Electron
Microscopy and X-ray Applications. V. 2, 115, Ann Arbor Science Publishers, Inc. (1981).
[8] Dollberg, D. D., M. T. Abell, and B. A. Lange. Occupational Health Analytical Chemistry:
Quantitation Using X-Ray Powder Diffraction, ACS Symposium Series, No. 120, 43 (1980).
METHOD REVISED BY:
M. T. Abell, NIOSH/DPSE.
TABLE 1. ABSORPTION CORRECTION FACTOR AS A FUNCTION OF TRANSMITTANCE FOR

SOME CHRYSOTILE-SILVER PEAK COMBINATIONS.
f(D Jffl_
Transmittance Chrysotile 12.08 24.38 Transmittance 12.08 24.38
T Silver 38.12 38.12 T 38.12 38.12
1.00 1.0000 1.0000 0.69 1 .6839 1.3142

0.99 1.0157 1 .0078 0.68 1.7151 1 .3277
0.98 1.0317 1.0157 0.67 1 .7470 1.3414
0.97 1.0480 1.0237 0.66 1.7797 1.3555
0.96 1 .0647 1.0319 0.65 1.8132 1 .3698
0.95 1.0817 1 .0402 0.64 1.8475 1.3845
0.94 1.0991 1 .0486 0.63 1 .8827 1 .3995
0.93 1.1168 1 .0572 0.62 1.9188 1.4148
0.92 1.1350 1 .0659 0.61 1.9558 1.4305
0.91 1.1535 1 .0747 0.60 1.9938 1 .4465
0.90 1.1724 1.0837 0.59 2.0328 1 .4629
0.89 1.1917 1.0928 0.58 2.0728 1 .4797
0.88 1.2114 1.1021 0.57 2.1139 1 .4969
0.87 1.2316 1.1115 0.56 2.1560 1.5145
0.86 1 .2522 1.1212 0.55 2.1993 .5325
0.85 1 .2733 1.1309 0.54 2.2438 .5510
0.84 1 .2948 1.1409 0.53 2.2895 .5700
0.83 1.3168 1.1510 0.52 2.3365 .5895
0.82 1.3394 1.1613 0.51 2.3848 .6095
0.81 1.3624 1.1718 0.50 2.4344 .6300
0.80 1 .3859 1.1825 0.49 2.4855 .6510
0.79 1.4100 1.1933 0.48 2.5380 1 .6727
0.78 1.4346 1 .2044 0.47 2.5921 1.6950
0.77 1 .4598 1.2157 0.46 2.6478 1.7179
0.76 1 .4856 1 .2272 0.45 2.7051 1.7414
0.75 1.5120 1 .2389 0.44 2.7642 1.7657
0.74 1.5390 1.2508 0.43 2.8251 1.7907
0.73 1.5666 1.2630 0.42 2.8879 1.8165
0.72 1.5949 1 .2754 0.41 2.9526 1.8431
0.71 1.6239 1.2881 0.40 3.0195 1 .8705
0.70 1 .6536 1.3010

ASBESTOS and OTHER FIBERS by PCM 7400
Various MW: Various CAS: Various RTECS: Various
METHOD: 7400, Issue 2 EVALUATION: FULL Issue 1: Rev. 3 on 15 May 1989

OSHA : 0.1 asbestos fiber (> 5 fjm long)/cc; PROPERTIES: solid, fibrous, crystalline, anisotropic
1 f/cc/30 min excursion; carcinogen
MSHA: 2 asbestos fibers/cc
NIOSH: 0.1 f/cc (fibers > 5 //m long)/400 L; carcinogen
ACGIH: 0.2 crocidolite; 0.5 amosite; 2 chrysotile and other
asbestos, fibers/cc; carcinogen
SYNONYMS[CAS#]:actinolite[77536-66-4]orferroactinolite [15669-07-5]; amosite [12172-73-5]; anthophyllite [77536-67-5];

chrysotile [12001-29-5]; serpentine [18786-24-8]; crocidolite [12001-28-4]; tremolite [77536-68-6]; amphibole asbestos [1332-
21-4]; refractory ceramic fibers [142844-00-6]; fibrous glass.
SAMPLER: FILTER TECHNIQUE: LIGHT MICROSCOPY, PHASE

(0.45- to 1.2-;/m cellulose ester CONTRAST
membrane, 25-mm; conductive cowl on
cassette) ANALYTE: fibers (manual count)
FLOW RATE*: 0.5 to 16 L/min SAMPLE

PREPARATION: acetone - collapse/triacetin - immersion
VOL-MIN*: 400 L @ 0.1 fiber/cc method [2]
-MAX*: (step 4, sampling)
•Adjust to give 100 to 1300 fiber/mm2 COUNTING
RULES: described in previous version of this
SHIPMENT: routine (pack to reduce shock) method as "A" rules [1,3]
SAMPLE EQUIPMENT: 1. positive phase-contrast microscope

STABILITY: stable 2. Walton-Beckett graticule (100-//m
field of view) Type G-22
BLANKS: 2 to 10 field blanks per set 3. phase-shift test slide (HSE/NPL)
ACCURACY CALIBRATION: HSE/NPL test slide
RANGE STUDIED: 80 to 100 fibers counted RANGE: 100 to 1300 fibers/mm2 filter area
ESTIMATED LOD: 7 fibers/mm2 filter area
OVERALL PRECISION (£„): 0.115 to 0.13 [1]
PRECISION (Sr): 0.10 to 0.12 [1]; see EVALUATION
ACCURACY: see EVALUATION OF METHOD
OF METHOD
APPLICABILITY: The quantitative working range is 0.04 to 0.5 fiber/cc for a 1000-L air sample. The LOD depends on sample
volume and quantity of interfering dust, and is <0.01 fiber/cc for atmospheres free of interferences. The method gives an index
of airborne fibers. It is primarily used for estimating asbestos concentrations, though PCM does not differentiate between
asbestos and other fibers. Use this method in conjunction with electron microscopy (e.g., Method 7402) for assistance in
identification of fibers. Fibers < ca. 0.25 fjm diameter will not be detected by this method [4]. This method may be used for
other materials such as fibrous glass by using alternate counting rules (see Appendix C).
INTERFERENCES: If the method is used to detect a specific type of fiber, any other airborne fiber may interfere since all
particles meeting the counting criteria are counted. Chain-like particles may appear fibrous. High levels of non-fibrous dust
particles may obscure fibers in the field of view and increase the detection limit.
OTHER METHODS: This revision replaces Method 7400, Revision #3 (dated 5/15/89).

ASBESTOS and OTHER FIBERS by PCM: METHOD 7400, Issue 2, dated 15 August 1994 - Page 2 of 15
1. Acetone,* reagent grade. 1. Sampler: field monitor, 25-mm, three-piece

2. Triacetin (glycerol triacetate), reagent grade. cassette with ca. 50-mm electrically conductive
extension cowl and cellulose ester filter, 0.45-
to 1 .2-fjm pore size, and backup pad.
NOTE 1: Analyze representative filters for
fiber background before use to
* See SPECIAL PRECAUTIONS. check for clarity and background.
Discard the filter lot if mean is >5
fibers per 100 graticule fields.
These are defined as laboratory
blanks. Manufacturer-provided
quality assurance checks on filter
blanks are normally adequate as
long as field blanks are analyzed
as described below.
NOTE 2: The electrically conductive
extension cowl reduces
electrostatic effects. Ground the
cowl when possible during
sampling.
NOTE 3: Use 0.8-//m pore size filters for
personal sampling. The 0.45-//m
filters are recommended for
sampling when performing TEM
analysis on the same samples.
However, their higher pressure
drop precludes their use with
personal sampling pumps.
NOTE 4: Other cassettes have been
proposed that exhibit improved
uniformity of fiber deposit on the
filter surface, e.g., bellmouthed
sampler (Envirometrics,
Charleston, SC). These may be
used if shown to give measured
concentrations equivalent to
sampler indicated above for the
application.
2. Personal sampling pump, battery or line-
powered vacuum, of sufficient capacity to
meet flow-rate requirements (see step 4 for
flow rate), with flexible connecting tubing.
3. Wire, multi-stranded, 22-gauge; 1 ", hose clamp
to attach wire to cassette.
4. Tape, shrink- or adhesive-.
5. Slides, glass, frosted-end, pre-cleaned, 25 x
75-mm.
6. Cover slips, 22- x 22-mm, No. 1-1/2, unless
otherwise specified by microscope
manufacturer.
7. Lacquer or nail polish.
8. Knife, #10 surgical steel, curved blade.
9. Tweezers.

EQUIPMENT:
10. Acetone flash vaporization system for clearing

filters on glass slides (see ref. [5] for
specifications or see manufacturer's
instructions for equivalent devices).
11. Micropipets or syringes, 5-//L and 100- to
500-//L
12. Microscope, positive phase (dark) contrast,
with green or blue filter, adjustable field iris, 8
to 10X eyepiece, and 40 to 45X phase
objective (total magnification ca. 400X);
numerical aperture = 0.65 to 0.75.
13. Graticule, Walton-Beckett type with 100-//m
diameter circular field (area = 0.00785 mm2) at
the specimen plane (Type G-22). Available
from Optometrics USA, P.O. Box 699, Ayer,
MA 01432 [phone (508) -772- 1700], and
McCrone Accessories and Components, 850
Pasquinelli Drive, Westmont, IL 60559 [phone
(312) 887-7100].
NOTE: The graticule is custom-made for each
microscope, (see APPENDIX A for
the custom-ordering procedure).
14. HSE/NPL phase contrast test slide, Mark II.
Available from Optometrics USA (address
above).
15. Telescope, ocular phase-ring centering.
16. Stage micrometer (0.01 -mm divisions).
SPECIAL PRECAUTIONS: Acetone is extremely flammable. Take precautions not to ignite it. Heating
of acetone in volumes greater than 1 mL must be done in a ventilated laboratory fume hood using a
flameless, spark-free heat source.
SAMPLING:

2. To reduce contamination and to hold the cassette tightly together, seal the crease between the
cassette base and the cowl with a shrink band or light colored adhesive tape. For personal
sampling, fasten the (uncapped) open-face cassette to the worker's lapel. The open face should
be oriented downward.
NOTE: The cowl should be electrically grounded during area sampling, especially under
conditions of low relative humidity. Use a hose clamp to secure one end of the wire
(Equipment, Item 3) to the monitor's cowl. Connect the other end to an earth ground
(i.e., cold water pipe).
3. Submit at least two field blanks (or 10% of the total samples, whichever is greater) for each set
of samples. Handle field blanks in a manner representative of actual handling of associated
samples in the set. Open field blank cassettes at the same time as other cassettes just prior to
sampling. Store top covers and cassettes in a clean area (e.g., a closed bag or box) with the
top covers from the sampling cassettes during the sampling period.
4. Sample at 0.5 L/min or greater [6]. Adjust sampling flow rate, Q (L/min), and time, t (min), to
produce a fiber density, E, of 100 to 1300 fibers/mm2 (3.85 • 10" to 5 • 10s fibers per 25-mm filter
with effective collection area A<.= 385 mm2) for optimum accuracy. These variables are related

to the action level (one-half the current standard), L (fibers/cc), of the fibrous aerosol being
sampled by:
t = , min.
Q • L • 103
NOTE 1: The purpose of adjusting sampling times is to obtain optimum fiber loading on the
filter. The collection efficiency does not appear to be a function of flow rate in the
range of 0.5 to 16 L/min for asbestos fibers [7]. Relatively large diameter fibers (>3
fjm) may exhibit significant aspiration loss and inlet deposition. A sampling rate of 1
to 4 L/min for 8 h is appropriate in atmospheres containing ca. 0.1 fiber/cc in the
absence of significant amounts of non-asbestos dust. Dusty atmospheres require
smaller sample volumes (<400 L) to obtain countable samples. In such cases take
short, consecutive samples and average the results over the total collection time.
For documenting episodic exposures, use high flow rates (7 to 16 L/min) over
shorter sampling times. In relatively clean atmospheres, where targeted fiber
concentrations are much less than 0.1 fiber/cc, use larger sample volumes (3000 to
10000 L) to achieve quantifiable loadings. Take care, however, not to overload the
filter with background dust. If > 50% of the filter surface is covered with particles,
the filter may be too overloaded to count and will bias the measured fiber
concentration.
NOTE 2: OSHA regulations specify a minimum sampling volume of 48 L for an excursion
measurement, and a maximum sampling rate of 2.5 L/min [3].
5. At the end of sampling, replace top cover and end plugs.
6. Ship samples with conductive cowl attached in a rigid container with packing material to prevent
jostling or damage.
NOTE: Do not use untreated polystyrene foam in shipping container because electrostatic
forces may cause fiber loss from sample filter.
SAMPLE PREPARATION:
NOTE 1: The object is to produce samples with a smooth (non-grainy) background in a

medium with refractive index <1.46. This method collapses the filter for easier
focusing and produces permanent (1-10 years) mounts which are useful for quality
control and interlaboratory comparison. The aluminum "hot block" or similar flash
vaporization techniques may be used outside the laboratory [2]. Other mounting
techniques meeting the above criteria may also be used (e.g., the laboratory fume
hood procedure for generating acetone vapor as described in Method 7400 -
revision of 5/15/85, or the non-permanent field mounting technique used in P&CAM
239 [3,7,8,9]). Unless the effective filtration area is known, determine the area and
record the information referenced against the sample ID number [1,9,10,11].
NOTE 2: Excessive water in the acetone may slow the clearing of the filter, causing material
to be washed off the surface of the filter. Also, filters that have been exposed to
high humidities prior to clearing may have a grainy background.
7. Ensure that the glass slides and cover slips are free of dust and fibers.
8. Adjust the rheostat to heat the "hot block" to ca. 70 °C [2].
NOTE: If the "hot block" is not used in a fume hood, it must rest on a ceramic plate and be
isolated from any surface susceptible to heat damage.
9. Mount a wedge cut from the sample filter on a clean glass slide.
a. Cut wedges of ca. 25% of the filter area with a curved-blade surgical steel knife using a
rocking motion to prevent tearing. Place wedge, dust side up, on slide.
NOTE: Static electricity will usually keep the wedge on the slide.

b. Insert slide with wedge into the receiving slot at base of "hot block". Immediately place tip
of a micropipet containing ca. 250 fjL acetone (use the minimum volume needed to
consistently clear the filter sections) into the inlet port of the PTFE cap on top of the "hot
block" and inject the acetone into the vaporization chamber with a slow, steady pressure on
the plunger button while holding pipet firmly in place. After waiting 3 to 5 sec for the filter to
clear, remove pipet and slide from their ports.
CAUTION: Although the volume of acetone used is small, use safety precautions. Work in
a well-ventilated area (e.g., laboratory fume hood). Take care not to ignite the
acetone. Continuous use of this device in an unventilated space may produce
explosive acetone vapor concentrations.
c. Using the 5-//L micropipet, immediately place 3.0 to 3.5 jjl triacetin on the wedge. Gently
lower a clean cover slip onto the wedge at a slight angle to reduce bubble formation. Avoid
excess pressure and movement of the cover glass.
NOTE: If too many bubbles form or the amount of triacetin is insufficient, the cover slip may
become detached within a few hours. If excessive triacetin remains at the edge of
the filter under the cover slip, fiber migration may occur.
d. Mark the outline of the filter segment with a glass marking pen to aid in microscopic
evaluation.
e. Glue the edges of the cover slip to the slide using lacquer or nail polish [12]. Counting may
proceed immediately after clearing and mounting are completed.
NOTE: If clearing is slow, warm the slide on a hotplate (surface temperature 50 °C) for up
to 15 min to hasten clearing. Heat carefully to prevent gas bubble formation.
10. Microscope adjustments. Follow the manufacturers instructions. At least once daily use the
telescope ocular (or Bertrand lens, for some microscopes) supplied by the manufacturer to
ensure that the phase rings (annular diaphragm and phase-shifting elements) are concentric.
With each microscope, keep a logbook in which to record the dates of microscope cleanings
and major servicing.
a. Each time a sample is examined, do the following:
(1) Adjust the light source for even illumination across the field of view at the condenser iris.
Use Kohler illumination, if available. With some microscopes, the illumination may have
to be set up with bright field optics rather than phase contract optics.
(2) Focus on the particulate material to be examined.
(3) Make sure that the field iris is in focus, centered on the sample, and open only enough
to fully illuminate the field of view.
b. Check the phase-shift detection limit of the microscope periodically for each
analyst/microscope combination:
(1) Center the HSE/NPL phase-contrast test slide under the phase objective.
(2) Bring the blocks of grooved lines into focus in the graticule area.
NOTE: The slide contains seven blocks of grooves (ca. 20 grooves per block) in
descending order of visibility. For asbestos counting the microscope optics
must completely resolve the grooved lines in block 3 although they may appear
somewhat faint, and the grooved lines in blocks 6 and 7 must be invisible when
centered in the graticule area. Blocks 4 and 5 must be at least partially visible
but may vary slightly in visibility between microscopes. A microscope which
fails to meet these requirements has resolution either too low or too high for
fiber counting.
(3) If image quality deteriorates, clean the microscope optics. If the problem persists,
consult the microscope manufacturer.
11. Document the laboratory's precision for each counter for replicate fiber counts.
a. Maintain as part of the laboratory quality assurance program a set of reference slides to be
used on a daily basis [13]. These slides should consist of filter preparations including a
range of loadings and background dust levels from a variety of sources including both field

and reference samples (e.g., PAT, AAR, commercial samples). The Quality Assurance
Officer should maintain custody of the reference slides and should supply each counter with
a minimum of one reference slide per workday. Change the labels on the reference slides
periodically so that the counter does not become familiar with the samples,
b. From blind repeat counts on reference slides, estimate the laboratory intra- and intercounter
precision. Obtain separate values of relative standard deviation (Sr) for each sample matrix
analyzed in each of the following ranges: 5 to 20 fibers in 100 graticule fields, >20 to 50
fibers in 100 graticule fields, and >50 to 100 fibers in 100 graticule fields. Maintain control
charts for each of these data files.
NOTE: Certain sample matrices (e.g., asbestos cement) have been shown to give poor
precision [9]
12. Prepare and count field blanks along with the field samples. Report counts on each field blank.
NOTE 1 : The identity of blank filters should be unknown to the counter until all counts have
been completed.
NOTE 2: If a field blank yields greater than 7 fibers per 100 graticule fields, report possible
contamination of the samples.
13. Perform blind recounts by the same counter on 10% of filters counted (slides relabeled by a
person other than the counter). Use the following test to determine whether a pair of counts by
the same counter on the same filter should be rejected because of possible bias: Discard the
sample if the absolute value of the difference between the square roots of the two counts (in
fiber/mm2) exceeds 2.77 (X)S,, where X = average of the square roots of the two fiber counts
(in fiber/mm2) and Sr= —'- , where Sr is the intracounter relative standard deviation for the
appropriate count range (in fibers) determined in step 11. For more complete discussions see
reference [13].
NOTE 1 : Since fiber counting is the measurement of randomly placed fibers which may be
described by a Poisson distribution, a square root transformation of the fiber count
data will result in approximately normally distributed data [13].
NOTE 2: If a pair of counts is rejected by this test, recount the remaining samples in the set
and test the new counts against the first counts. Discard all rejected paired counts.
It is not necessary to use this statistic on blank counts.
14. The analyst is a critical part of this analytical procedure. Care must be taken to provide a non-
stressful and comfortable environment for fiber counting. An ergonomically designed chair
should be used, with the microscope eyepiece situated at a comfortable height for viewing.
External lighting should be set at a level similar to the illumination level in the microscope to
reduce eye fatigue. In addition, counters should take 10-to-20 minute breaks from the
microscope every one or two hours to limit fatigue [14]. During these breaks, both eye and
upper back/neck exercises should be performed to relieve strain.
15. All laboratories engaged in asbestos counting should participate in a proficiency testing program
such as the AIHA-NIOSH Proficiency Analytical Testing (PAT) Program for asbestos and
routinely exchange field samples with other laboratories to compare performance of counters.
MEASUREMENT:
16. Center the slide on the stage of the calibrated microscope under the objective lens. Focus the
microscope on the plane of the filter.
17. Adjust the microscope (Step 10).
NOTE: Calibration with the HSE/NPL test slide determines the minimum detectable fiber
diameter (ca. 0.25//m) [4].
18. Counting rules: (same as P&CAM 239 rules [1,10,11]: see examples in APPENDIX B).
a. Count any fiber longer than 5 //m which lies entirely within the graticule area.
(1) Count only fibers longer than 5 //m. Measure length of curved fibers along the curve.
(2) Count only fibers with a length-to-width ratio equal to or greater than 3:1.
b. For fibers which cross the boundary of the graticule field:

(1) Count as 1/2 fiber any fiber with only one end lying within the graticule area, provided
that the fiber meets the criteria of rule a above.
(2) Do not count any fiber which crosses the graticule boundary more than once.
(3) Reject and do not count all other fibers.
c. Count bundles of fibers as one fiber unless individual fibers can be identified by observing
both ends of a fiber.
d. Count enough graticule fields to yield 100 fibers. Count a minimum of 20 fields. Stop at 100
graticule fields regardless of count.
19. Start counting from the tip of the filter wedge and progress along a radial line to the outer edge.
Shift up or down on the filter, and continue in the reverse direction. Select graticule fields
randomly by looking away from the eyepiece briefly while advancing the mechanical stage.
Ensure that, as a minimum, each analysis covers one radial line from the filter center to the outer
edge of the filter. When an agglomerate or bubble covers ca. 1 /6 or more of the graticule field,
reject the graticule field and select another. Do not report rejected graticule fields in the total
number counted.
NOTE 1 : When counting a graticule field, continuously scan a range of focal planes by
moving the fine focus knob to detect very fine fibers which have become embedded
in the filter. The small -diameter fibers will be very faint but are an important
contribution to the total count. A minimum counting time of 15 seconds per field is
appropriate for accurate counting.
NOTE 2: This method does not allow for differentiation of fibers based on morphology.
Although some experienced counters are capable of selectively counting only fibers
which appear to be asbestiform, there is presently no accepted method for ensuring
uniformity of judgment between laboratories. It is, therefore, incumbent upon all
laboratories using this method to report total fiber counts. If serious contamination
from non-asbestos fibers occurs in samples, other techniques such as transmission
electron microscopy must be used to identify the asbestos fiber fraction present in
the sample (see NIOSH Method 7402). In some cases (i.e., for fibers with diameters
>1 //m), polarized light microscopy (as in NIOSH Method 7403) may be used to
identify and eliminate interfering non-crystalline fibers [15].
NOTE 3: Do not count at edges where filter was cut. Move in at least 1 mm from the edge.
NOTE 4: Under certain conditions, electrostatic charge may affect the sampling of fibers.
These electrostatic effects are most likely to occur when the relative humidity is low
(below 20%), and when sampling is performed near the source of aerosol. The
result is that deposition of fibers on the filter is reduced, especially near the edge of
the filter. If such a pattern is noted during fiber counting, choose fields as close to
the center of the filter as possible [5].
NOTE 5: Counts are to be recorded on a data sheet that provides, as a minimum, spaces on
which to record the counts for each field, filter identification number, analyst's name,
date, total fibers counted, total fields counted, average count, fiber density, and
commentary. Average count is calculated by dividing the total fiber count by the
number of fields observed. Fiber density (fibers/mm2) is defined as the average
count (fibers/field) divided by the field (graticule) area (mm2/field).
CALCULATIONS AND REPORTING OF RESULTS
20. Calculate and report fiber density on the filter, E (fibers/mm2), by dividing the average fiber
count per graticule field, F/nf, minus the mean field blank count per graticule field, B/nb, by the
graticule field area, A, (approx. 0.00785 mm2):
E = , fibers/mm2.

NOTE: Fiber counts above 1300 fibers/mm2 and fiber counts from samples with >50% of filter
area covered with particulate should be reported as "uncountable" or "probably biased."
Other fiber counts outside the 100-1300 fiber/mm2 range should be reported as having
"greater than optimal variability" and as being "probably biased."
21. Calculate and report the concentration, C (fibers/cc), of fibers in the air volume sampled, V (L),
using the effective collection area of the filter, Ac (approx. 385 mm2 for a 25-mm filter):
- ( E )( Ac )
V • 103
NOTE: Periodically check and adjust the value of Ac, if necessary.

22. Report intralaboratory and interlaboratory relative standard deviations (from Step 1 1 ) with each
set of results.
NOTE: Precision depends on the total number of fibers counted [1,16]. Relative standard
deviation is documented in references [1,15-17] for fiber counts up to 100 fibers in 100
graticule fields. Comparability of interlaboratory results is discussed below. As a first
approximation, use 213% above and 49% below the count as the upper and lower
confidence limits for fiber counts greater than 20 (Fig. 1).
A. This method is a revision of P&CAM 239 [10]. A summary of the revisions is as follows:
1 . Sampling:
The change from a 37-mm to a 25-mm filter improves sensitivity for similar air volumes. The
change in flow rates allows for 2-m3 full-shift samples to be taken, providing that the filter is not
overloaded with non-fibrous particulates. The collection efficiency of the sampler is not a
function of flow rate in the range 0.5 to 16 L/min [10].
2. Sample Preparation Technique:
The acetone vapor-triacetin preparation technique is a faster, more permanent mounting
technique than the dimethyl phthalate/diethyl oxalate method of P&CAM 239 [2,4,10]. The
aluminum "hot block" technique minimizes the amount of acetone needed to prepare each
sample.
3. Measurement:
a. The Walton-Beckett graticule standardizes the area observed [14,18,19].
b. The HSE/NPL test slide standardizes microscope optics for sensitivity to fiber diameter
[4,14].
c. Because of past inaccuracies associated with low fiber counts, the minimum recommended
loading has been increased to 100 fibers/mm2 filter area (a total of 78.5 fibers counted in
100 fields, each with field area = .00785 mm2.) Lower levels generally result in an
overestimate of the fiber count when compared to results in the recommended analytical
range [20]. The recommended loadings should yield intracounter Sr in the range of 0.10 to
0.17 [21,22,23].
B. Interlaboratory comparability:
An international collaborative study involved 16 laboratories using prepared slides from the asbestos
cement, milling, mining, textile, and friction material industries [9]. The relative standard deviations
(Sr) varied with sample type and laboratory. The ranges were:

Intralaboratorv Sr Interlaboratory Sr Overall Sr
AIA (NIOSH A Rules)* 0.12 to 0.40 0.27 to 0.85 0.46

Modified CRS (NIOSH B Rules)** 0.1 1 to 0.29 0.20 to 0.35 0.25
* Under AIA rules, only fibers having a diameter less than 3 //m are counted and fibers attached to
particles larger than 3 //m are not counted. NIOSH A Rules are otherwise similar to the AIA rules.
** See Appendix C.
A NIOSH study conducted using field samples of asbestos gave intralaboratory Sr in the range 0.17 to
0.25 and an interlaboratory Sr of 0.45 [21]. This agrees well with other recent studies [9,14,16].
At this time, there is no independent means for assessing the overall accuracy of this method. One
measure of reliability is to estimate how well the count for a single sample agrees with the mean count
from a large number of laboratories. The following discussion indicates how this estimation can be
carried out based on measurements of the interlaboratory variability, as well as showing how the results
of this method relate to the theoretically attainable counting precision and to measured intra- and
interlaboratory Sr. (NOTE: The following discussion does not include bias estimates and should not be
taken to indicated that lightly loaded samples are as accurate as properly loaded ones).
Theoretically, the process of counting randomly (Poisson) distributed fibers on a filter surface will give an
S, that depends on the number, N, of fibers counted:
S = 1/( N 1/2 (D
Thus Sr is 0.1 for 100 fibers and 0.32 for 10 fibers counted. The actual Sr found in a number of studies is
greater than these theoretical numbers [17,19,20,21].
An additional component of variability comes primarily from subjective interlaboratory differences. In a

study of ten counters in a continuing sample exchange program, Ogden [15] found this subjective
component of intralaboratory Sr to be approximately 0.2 and estimated the overall Sr by the term:
[ N + ( 0.2 • N )2 I1/2 (2)
N
Ogden found that the 90% confidence interval of the individual intralaboratory counts in relation to the
means were +2 Sr and - 1.5 Sr. In this program, one sample out of ten was a quality control sample.
For laboratories not engaged in an intensive quality assurance program, the subjective component of
variability can be higher.
In a study of field sample results in 46 laboratories, the Asbestos Information Association also found that
the variability had both a constant component and one that depended on the fiber count [14]. These
results gave a subjective interlaboratory component of Sr (on the same basis as Ogden's) for field
samples of ca. 0.45. A similar value was obtained for 12 laboratories analyzing a set of 24 field samples
[21]. This value falls slightly above the range of Sr (0.25 to 0.42 for 1984-85) found for 80 reference
laboratories in the NIOSH PAT program for laboratory-generated samples [17].
A number of factors influence Sr for a given laboratory, such as that laboratory's actual counting
performance and the type of samples being analyzed. In the absence of other information, such as from
an interlaboratory quality assurance program using field samples, the value for the subjective component
of variability is chosen as 0.45. It is hoped that the laboratories will carry out the recommended
interlaboratory quality assurance programs to improve their performance and thus reduce the Sr.

The above relative standard deviations apply when the population mean has been determined. It is
more useful, however, for laboratories to estimate the 90% confidence interval on the mean count from a
single sample fiber count (Figure 1). These curves assume similar shapes of the count distribution for
interlaboratory and intralaboratory results [16].
For example, if a sample yields a count of 24 fibers, Figure 1 indicates that the mean interlaboratory
count will fall within the range of 227% above and 52% below that value 90% of the time. We can apply
these percentages directly to the air concentrations as well. If, for instance, this sample (24 fibers
counted) represented a 500-L volume, then the measured concentration is 0.02 fibers/mL (assuming 100
fields counted, 25-mm filter, 0.00785 mm2 counting field area). If this same sample were counted by a
group of laboratories, there is a 90% probability that the mean would fall between 0.01 and 0.08
fiber/mL These limits should be reported in any comparison of results between laboratories.
Note that the Sr of 0.45 used to derive Figure 1 is used as an estimate for a random group of
laboratories. If several laboratories belonging to a quality assurance group can show that their
interlaboratory Sr is smaller, then it is more correct to use that smaller Sr. However, the estimated Sr of
0.45 is to be used in the absence of such information. Note also that it has been found that Sr can be
higher for certain types of samples, such as asbestos cement [9].
Quite often the estimated airborne concentration from an asbestos analysis is used to compare to a
regulatory standard. For instance, if one is trying to show compliance with an 0.5 fiber/mL standard
using a single sample on which 100 fibers have been counted, then Figure 1 indicates that the 0.5
fiber/mL standard must be 213% higher than the measured air concentration. This indicates that if one
measures a fiber concentration of 0.16 fiber/mL (100 fibers counted), then the mean fiber count by a
group of laboratories (of which the compliance laboratory might be one) has a 95% chance of being less
than 0.5 fibers/mL; i.e., 0.16 + 2.13 x 0.16 = 0.5.
It can be seen from Figure 1 that the Poisson component of the variability is not very important unless
the number of fibers counted is small. Therefore, a further approximation is to simply use +213% and
-49% as the upper and lower confidence values of the mean for a 100-fiber count.
90% CONFIDENCE INTERVAL ON MEAN COUNT

500 (SUBJECTIVE COMPONENT (0.45) *•
POISSON COMPONENT)
400
£1
u O
> <J 300 05% PROBABUTY MEAN COUNT'
6 BELOWTHJS LEVEL
200
100
10 20 30 40 SO 60 J70 •0 JOO
.,00 L .Wfc PROBABUTY MEAN COUNT
B ABOVE THB LEVEL ""
NUMBER OF FWEM COUNTED IN A HNOLE SAMPLE
Figure 1. Interlaboratory Precision of Fiber Counts

The curves in Figures 1 are defined by the following equations:
UCL = 2 X + 2.25 + [(2.25 + 2 X)2 - 4 ( 1 - 2.25 Sr2) X2]1/a

(3)
2(1- 2.25 Sr2)
UCL = 2 X + 4 - [(4 + 2 X )2 - 4 ( 1 - 4 Sr2 ) X2 ]1B (4)
2(1 - 4 S* )
where Sr = subjective Intel-laboratory relative standard deviation, which is close to the total
Intel-laboratory Sr when approximately 100 fibers are counted.
X = total fibers counted on sample
LCL = lower 95% confidence limit.
UCL = upper 95% confidence limit.
Note that the range between these two limits represents 90% of the total range.
REFERENCES:
[1] Leidel, N. A., S. G. Bayer, R. D. Zumwalde, and K. A. Busch. USPHS/NIOSH Membrane Filter
Method for Evaluating Airborne Asbestos Fibers, U.S. Department of Health, Education, and
[2] Baron, P. A. and G. C. Pickford. "An Asbestos Sample Filter Clearing Procedure," Appl. Ind.
Hva. 1:169-171, 199 (1986).
[3] Occupational Safety and Health Administration, U.S. Department of Labor, Occupational
Exposure to Asbestos, Tremolite, Anthophyllite, and Actinolite Asbestos; Final Rules, 29 CFR Part
1910.1001 Amended June 20, 1986.
[4] Rooker, S. J., N. P. Vaughn, and J. M. LeGuen. "On the Visibility of Fibers by Phase Contrast
Microscopy," Amer. Ind. Hyg. Assoc. J_., 43, 505-515 (1982).
[5] Baron, P. and G. Deye, "Electrostatic Effects in Asbestos Sampling," Parts I and II Amer. Ind.
Hva. Assoc. J.. 51. 51-69 (1990).
[6] Johnston, A. M., A. D. Jones, and J. H. Vincent. 'The Influence of External Aerodynamic Factors
on the Measurement of the Airborne Concentration of Asbestos Fibers by the Membrane Filter
Method," Ann. OCCUD. Hyg., 25, 309-316 (1982).
[7] Beckett, ST., 'The Effects of Sampling Practice on the Measured Concentration of Airborne
Asbestos," Ann. Occup. Hyg., 21, 259-272 (1980).
[8] Jankovic, J. T., W. Jones, and J. CIere. "Field Techniques for CIearing Cellulose Ester Filters
Used in Asbestos Sampling," Appl. kid. Hva.. 1, 145-147 (1986).
[9] Crawford, N. P., H. L Thorpe, and W. Alexander. "A Comparison of the Effects of Different
Counting Rules and Aspect Ratios on the Level and Reproducibility of Asbestos Fiber Counts,"
Part I: Effects on Level (Report No. TM/82/23), Part II: Effects on Reproducibility (Report No.
TM/82/24), Institute of Occupational Medicine, Edinburgh, Scotland (December, 1982).
[10] NIOSH Manual of Analytical Methods, 2nd ed., Vol. 1., P&CAM 239, U.S. Department of Health,
[11] Revised Recommended Asbestos Standard, U.S. Department of Health, Education, and Welfare,
Publ. (NIOSH) 77-169 (1976); as amended in NIOSH statement at OSHA Public Hearing, June
21, 1984.
[12] Asbestos International Association, AIA Health and Safety Recommended Technical Method #1
(RTMI). "Airborne Asbestos Fiber Concentrations at Workplaces by Light Microscopy"
(Membrane Filter Method), London (1979).
[13] Abell, M., S. Shulman and P. Baron. The Quality of Fiber Count Data, Appl. Ind. Hva.. 4, 273-
285 (1989).

[14] "A Study of the Empirical Precision of Airborne Asbestos Concentration Measurements in the
Workplace by the Membrane Filter Method," Asbestos Information Association, Air Monitoring
Committee Report, Arlington, VA (June, 1983).
[15] McCrone, W., L McCrone and J. Delly, "Polarized Light Microscopy," Ann Arbor Science (1978).
[16] Ogden, T. L 'The Reproducibility of Fiber Counts," Health and Safety Executive Research Paper
18 (1982).
[17] Schlecht, P. C. and S. A. Schulman. "Performance of Asbestos Fiber Counting Laboratories in
the NIOSH Proficiency Analytical Testing (PAT) Program," Am. Ind. Hyg. Assoc. J., 47, 259-266
(1986).
[18] Chatfield, E. J. Measurement of Asbestos Fiber Concentrations in Workplace Atmospheres,
Royal Commission on Matters of Health and Safety Arising from the Use of Asbestos in Ontario,
Study No. 9, 180 Dundas Street West, 22nd Floor, Toronto, Ontario, CANADA M5G 128.
[19] Walton, W. H. 'The Nature, Hazards, and Assessment of Occupational Exposure to Airborne
Asbestos Dust: A Review," Ann. Occup. Hyg., 25, 115-247 (1982).
[20] Cherrie, J., A.D. Jones, and A.M. Johnston. 'The Influence of Fiber Density on the Assessment of
Fiber Concentration Using the membrane filter Method." Am. Ind. Hyg. Assoc. J., 47(8). 465-74
(1986).
[21] Baron, P. A. and S. Shulman. "Evaluation of the Magiscan Image Analyzer for Asbestos Fiber
Counting." Am. Ind. Hvg. Assoc. J., (in press).
[22] Taylor, D. G., P. A. Baron, S. A. Shulman and J. W. Carter. "Identification and Counting of
Asbestos Fibers," Am. Ind. Hvg. Assoc. J. 45(2). 84-88 (1984).
[23] "Potential Health Hazards of Video Display Terminals," NIOSH Research Report, June 1981.
[24] "Reference Methods for Measuring Airborne Man-Made Mineral Fibers (MMMF)," WHO/EURO
Technical Committee for Monitoring an Evaluating Airborne MMMF, World Health Organization,
Copenhagen (1985).
[25] Criteria for a Recommended Standard. ..Occupational Exposure to Fibrous Glass, U.S.
METHOD WRITTEN BY:
Paul A. Baron, Ph.D., NIOSH/DPSE.
APPENDIX A: CALIBRATION OF THE WALTON-BECKETT GRATICULE:
Before ordering the Walton-Beckett graticule, the following calibration must be done to obtain a counting
area (D) 100 //m in diameter at the image plane. The diameter, dc (mm), of the circular counting area
and the disc diameter must be specified when ordering the graticule.
1. Insert any available graticule into the eyepiece and focus so that the graticule lines are sharp and
clear.
2. Set the appropriate interpupillary distance and, if applicable, reset the binocular head adjustment
so that the magnification remains constant.
3. Install the 40 to 45X phase objective.
4. Place a stage micrometer on the microscope object stage and focus the microscope on the
graduated lines.
5. Measure the magnified grid length of the graticule, L,, (//m), using the stage micrometer.
6. Remove the graticule from the microscope and measure its actual grid length, La (mm). This can
best be accomplished by using a stage fitted with verniers.
7. Calculate the circle diameter, dc (mm), for the Walton-Beckett graticule:

(5)
Example: If L^ = 112 //m, L, = 4.5 mm and D = 100 //m, then dc = 4.02 mm.
8. Check the field diameter, D (acceptable range 100 fjm ± 2 f/m) with a stage micrometer upon
receipt of the graticule from the manufacturer. Determine field area (acceptable range 0.00754
mm2 to 0.00817 mm2).
APPENDIX B: COMPARISON OF COUNTING RULES:
Figure 2 shows a Walton-Beckett graticule as seen through the microscope. The rules will be discussed
as they apply to the labeled objects in the figure.
Figure 2. Walton-Beckett graticule with fibers.

These rules are sometimes referred to as the "A" rules.
FIBER COUNT
Object Count DISCUSSION
1 1 fiber Optically observable asbestos fibers are actually bundles of fine fibrils. If the
fibrils seem to be from the same bundle the object is counted as a single
fiber. Note, however, that all objects meeting length and aspect ratio criteria
are counted whether or not they appear to be asbestos.
2 fiber If fibers meeting the length and aspect ratio criteria (length >5 fjm and
length-to-width ratio >3 to 1) overlap, but do not seem to be part of the
same bundle, they are counted as separate fibers.
1 fiber Although the object has a relatively large diameter (>3 //m), it is counted as
fiber under the rules. There is no upper limit on the fiber diameter in the
counting rules. Note that fiber width is measured at the widest compact
section of the object.
1 fiber Although long fine fibrils may extend from the body of a fiber, these fibrils
are considered part of the fiber if they seem to have originally been part of
the bundle.
Do not If the object is <5 //m long, it is not counted.

count
1 fiber A fiber partially obscured by a particle is counted as one fiber. If the fiber
ends emanating from a particle do not seem to be from the same fiber and
each end meets the length and aspect ratio criteria, they are counted as
separate fibers.
1/2 fiber A fiber which crosses into the graticule area one time is counted as 1 /2
fiber.
Do not Ignore fibers that cross the graticulate boundary more than once,
count count
Do not Ignore fibers that lie outside the graticule boundary.

count

APPENDIX C. ALTERNATE COUNTING RULES FOR NON-ASBESTOS FIBERS
Other counting rules may be more appropriate for measurement of specific non-asbestos fiber types,
such as fibrous glass. These include the "B" rules given below (from NIOSH Method 7400, Revision #2,
dated 8/15/87), the World Health Organization reference method for man-made mineral fiber [24], and
the NIOSH fibrous glass criteria document method [25]. The upper diameter limit in these methods
prevents measurements of non-thoracic fibers. It is important to note that the aspect ratio limits
included in these methods vary. NIOSH recommends the use of the 3:1 aspect ratio in counting fibers.
It is emphasized that hybridization of different sets of counting rules is not permitted. Report specifically
which set of counting rules are used with the analytical results.
"B" COUNTING RULES:
1. Count only ends of fibers. Each fiber must be longer than 5 //m and less than 3 //m diameter.
2. Count only ends of fibers with a length-to-width ratio equal to or greater than 5:1.
3. Count each fiber end which falls within the graticule area as one end, provided that the fiber meets
rules 1 and 2 above. Add split ends to the count as appropriate if the split fiber segment also meets
the criteria of rules 1 and 2 above.
4. Count visibly free ends which meet rules 1 and 2 above when the fiber appears to be attached to
another particle, regardless of the size of the other particle. Count the end of a fiber obscured by
another particle if the particle covering the fiber end is less than 3 fjm in diameter.
5. Count free ends of fibers emanating from large clumps and bundles up to a maximum of 10 ends (5
fibers), provided that each segment meets rules 1 and 2 above.
6. Count enough graticule fields to yield 200 ends. Count a minimum of 20 graticule fields. Stop at
100 graticule fields, regardless of count.
7. Divide total end count by 2 to yield fiber count.
APPENDIX D. EQUIVALENT LIMITS OF DETECTION AND QUANTITATION
fiber density on filter* fiber concentration in air, f/cc

fibers 400-Lair 1000-Lair
per 100 fields fibers/mm2 sample sample
200 255 0.25 0.10

100 127 0.125 0.05
LOO- ...80 102 0.10 0.04
50 64 0.0625 0.025
25 32 0.03 0.0125
20 25 0.025 0.010
10 12.7 0.0125 0.005
8 10.2 0.010 0.004
LCD 5.5 ,,.....7 0.00675 0.0027
* Assumes 385 mm2 effective filter collection area, and field area = 0.00785 mm2, for relatively "clean"
(little particulate aside from fibers) filters.

ASBESTOS by TEM 7402
FORMULA: Various MW: Various CAS: Various RTECS: Various
METHOD: 7402 EVALUATION: PARTIAL Issue 1: 15 May 1989

OSHA : 0.1 asbestos fibers (>5//m long)/cc; PROPERTIES: solid, fibrous, crystalline,
1 f/cc/30 min excursion; carcinogen anistropic
MSHA: 2 asbestos fibers/cc
NIOSH: 0.1 f/cc (fibers > 5//m long)/400 L; carcinogen
ACGIH: 0.2 crocidolite; 0.5 amosite; 2 chrysotile
and other asbestos, fibers/cc; carcinogen
SYNONYMS [CAS#]: actinolite [77536-66-4] or ferroactinolite [15669-07-5]; amosite [12172-73-5]; anthophyllite [77536-67-5];
chrysotile [12001-29-5]; serpentine [18786-24-8]; crocidolite [12001-28-4]; tremolite [77536-68-6]; amphibole asbestos [1332-21-4].
SAMPLER: FILTER TECHNIQUE: MICROSCOPY, TRANSMISSION

(0.45- to 1.2-//m cellulose ester membrane, ELECTRON (TEM)
25-mm diameter; conductive cassette)
ANALYTE: asbestos fibers
SAMPLE
VOL-MIN*: 400 L @ 0.1 fiber/cc PREPARATION: modified Jaffe wick
-MAX*: (step 4, sampling)
*Adjust for 100 to 1300 fibers/mm2 EQUIPMENT: transmission electron microscope; energy
dispersive X-ray system (EDX) analyzer
SHIPMENT: routine (pack to reduce shock)
CALIBRATION: qualitative electron diffraction; calibration
SAMPLE of TEM magnification and EDX system
STABILITY: stable
RANGE: 100 to 1300 fibers/mm2 filter area [1]
ESTIMATED LOD: 1 confirmed asbestos fiber above 95% of
expected mean blank value
ACCURACY
PRECISION (Sr): 0.28 when 65% of fibers are asbestos;
RANGE STUDIED: 80 to 100 fibers counted 0.20 when adjusted fiber count is applied
to PCM count [2].
OVERALL PRECISION (S^): see EVALUATION OF METHOD
APPLICABILITY: The quantitative working range is 0.04 to 0.5 fiber/cc for a 1000-L air sample. The LOD depends on sample
volume and quantity of interfering dust, and is <0.01 fiber/cc for atmospheres free of interferences. This method is used to
determine asbestos fibers in the optically visible range and is intended to complement the results obtained by phase contrast
microscopy (Method 7400).
INTERFERENCES: Other amphibole particles that have aspect ratios greater than 3:1 and elemental compositions similar to
the asbestos minerals may interfere in the TEM analysis. Some non-amphibole minerals may give electron diffraction patterns
similar to amphiboles. High concentrations of background dust interfere with fiber identification. Some non-asbestos amphibole
minerals may give electron diffraction patterns similar to asbestos amphiboles.
OTHER METHODS: This method is designed for use with Method 7400 (phase contrast microscopy).

ASBESTOS by TEM: METHOD 7402, Issue 2, dated 15 August 1994 - Page 2 of 7
REAGENTS:
1. Acetone. (See SPECIAL PRECAUTIONS.)
EQUIPMENT:
1 . Sampler: field monitor, 25-mm, three-piece cassette with ca. 50-mm electrically-conductive extension
cowl, cellulose ester membrane filter, 0.45- to 1.2-//m pore size, and backup pad.
NOTE 1 : Analyze representative filters for fiber background before use. Discard the filter lot if
mean count is >5 fibers/100 fields. These are defined as laboratory blanks.
NOTE 2: Use an electrically-conductive extension cowl to reduce electrostatic effects on fiber
sampling and during sample shipment. Ground the cowl when possible during
sampling.
NOTE 3: 0.8-//m pore size filters are recommended for personal sampling. 0.45-^m filters are
recommended for sampling when performing TEM analysis on the samples because the
particles deposit closer to the filter surface. However, the higher pressure drop through
these filters normally preclude their use with personal sampling pumps.
2. Personal sampling pump, 0.5 to 16 L/min, with flexible connecting tubing.
3. Microscope, transmission electron, operated at ca. 100 kV, with electron diffraction and
energy-dispersive X-ray capabilities, and having a fluorescent screen with inscribed or overlaid
calibrated scale (Step 15).
NOTE: The scale is most efficient if it consists of a series of lines inscribed on the screen or partial
circles every 2 cm distant from the center.
4. Diffraction grating replica with known number of lines/mm.
5. Slides, glass, pre-cleaned, 25- x 75-mm.
6. Knife, surgical steel, curved-blade.
7. Tweezers.
8. Grids, 200-mesh TEM copper, (optional: carbon-coated).
9. Petri dishes, 15-mm depth. The top and bottom of the petri dish must fit snugly together. To assure
a tight fit, grind the top and bottom pieces together with an abrasive such as carborundum to
produce a ground-glass contact surface.
10. Foam, clean polyurethane, spongy, 12-mm thick.
11. Filters, Whatman No. 1 qualitative paper or equivalent, or lens paper.
12. Vacuum evaporator.
13. Cork borer, (about 8-mm).
14. Pen, waterproof, marking.
15. Reinforcement, page, gummed.
16. Asbestos standard bulk materials for reference; e.g. SRM #1866, available from the National Institute
of Standards and Technology.
17. Carbon rods, sharpened to 1 mm x 8 mm.
18. Microscope, light, phase contrast (PCM), with Walton-Beckett graticule (see method 7400).
19. Grounding wire, 22-gauge, multi-strand.
20. Tape, shrink- or adhesive-.
SPECIAL PRECAUTIONS: Acetone is extremely flammable (flash point = 0 °F). Take precautions not
to ignite it. Heating of acetone must be done in a fume hood using a flameless, spark-free heat source.
Asbestos is a confirmed human carcinogen. Handle only in a well-ventilated fume hood.

SAMPLING:

2. For personal sampling, fasten sampler to worker's lapel near worker's mouth. Remove the top
cover from cowl extension ("open-face") and orient sampler face down. Wrap joint between
extender and monitor body with tape to help hold the cassette together and provide a marking
surface to identify the cassette. Where possible, especially at low %RH, attach sampler to
electrical ground to reduce electrostatic effects during sampling.
3. Submit at least two field blanks (or 10% of the total samples, whichever is greater) for each set
of samples. Remove top covers from the field blank cassettes and store top covers and
cassettes in a clean area (e.g., closed bag or box) during sampling. Replace top covers when
sampling is completed.
4. Sample at 0.5 to 16 L/min [3]. Adjust sampling rate, Q (L/min), and time, t (min), to produce
fiber density, E, of 100 to 1300 fibers/mm2 [3.85 • 104 to 5 • 105 fibers per 25-mm filter with
effective collection area (Ac= 385 mm2)] for optimum accuracy. Do not exceed ca. 0.5 mg total
dust loading on the filter. These variables are related to the action level (one-half the current
standard), L (fibers/cc), of the fibrous aerosol being sampled by:
t = , min.
Q • L • 103
NOTE: The purpose of adjusting sampling times is to obtain optimum fiber loading on the filter.
A sampling rate of 1 to 4 L/min for 8 h (700 to 2800 L) is appropriate in atmospheres
containing ca. 0.1 fiber/cc in the absence of significant amounts of non-asbestos dust.
Dusty atmospheres require smaller sample volumes (<400 L) to obtain countable
samples. In such cases take short, consecutive samples and average the results over
the total collection time. For documenting episodic exposures, use high rates ( 7 to 16
L/min) over shorter sampling times. In relatively clean atmospheres, where targeted
fiber concentrations are much less than 0.1 fiber/cc, use larger sample volumes (3000 to
10000 L) to achieve quantifiable loadings. Take care, however, not to overload the filter
with background dust [3].
5. At the end of sampling, replace top cover and small end caps.
6. Ship samples upright with conductive cowl attached in a rigid container with packing material to
prevent jostling or damage.
NOTE: Do not use untreated polystyrene foam in the shipping container because electrostatic
forces may cause fiber loss from sample filter.
SAMPLE PREPARATION:
7. Remove circular sections from any of three quadrants of each sample and blank filter using a
cork borer [4]. The use of three grid preparations reduces the effect of local variations in dust
deposit on the filter.
8. Affix the circular filter sections to a clean glass slide with a gummed page reinforcement. Label
the slide with a waterproof marking pen.
NOTE: Up to eight filter sections may be attached to the same slide.
9. Place the slide in a petri dish which contains several paper filters soaked with 2 to 3 mL
acetone. Cover the dish. Wait 2 to 4 min for the sample filter(s) to fuse and clear.
NOTE: The "hot block" clearing technique [5] of Method 7400 or the DMF clearing technique [6]
may be used instead of steps 8 and 9.
10. Transfer the slide to a rotating stage inside the bell jar of a vacuum evaporator. Evaporate a 1-
by 5-mm section of a graphite rod onto the cleared filter(s). Remove the slide to a clean, dry,
covered petri dish [4].
11. Prepare a second petri dish as a Jaffe wick washer with the wicking substrate prepared from
filter or lens paper placed on top of a 12-mm thick disk of clean, spongy polyurethane foam [7].

Cut a V-notch on the edge of the foam and filter paper. Use the V-notch as a reservoir for
adding solvent.
NOTE: The wicking substrate should be thin enough to fit into the petri dish without touching
the lid.
12. Place the TEM grid on the filter or lens paper. Label the grids by marking with a pencil on the
filter paper or by putting registration marks on the petri dish halves and marking with a
waterproof marker on the dish lid. In a fume hood, fill the dish with acetone until the wicking
substrate is saturated.
NOTE: The level of acetone should be just high enough to saturate the filter paper without
creating puddles.
13. Remove about a quarter section of the carbon-coated filter from the glass slide using a surgical
knife and tweezers. Carefully place the excised filter, carbon side down, on the
appropriately-labeled grid in the acetone-saturated petri dish. When all filter sections have been
transferred, slowly add more solvent to the wedge-shaped trough to raise the acetone level as
high as possible without disturbing the sample preparations. Cover the petri dish. Elevate one
side of the petri dish by placing a slide under it (allowing drops of condensed acetone to form
near the edge rather than in the center where they would drip onto the grid preparation).
14. Determine the TEM magnification on the fluorescent screen:

a. Define a field of view on the fluorescent screen either by markings or physical boundaries.
NOTE: The field of view must be measurable or previously inscribed with a scale or
concentric circles (all scales should be metric) [7].
b. Insert a diffraction grating replica into the specimen holder and place into the microscope.
Orient the replica so that the grating lines fall perpendicular to the scale on the TEM
fluorescent screen. Ensure that goniometer stage tilt is zero.
c. Adjust microscope magnification to 10.000X. Measure the distance (mm) between the same
relative positions (e.g., between left edges) of two widely-separated lines on the grating
replica. Count the number of spaces between the lines.
NOTE: On most microscopes the magnification is substantially constant only within the
central 8- to 10-cm diameter region of the fluorescent screen.
d. Calculate the true magnification (M) on the fluorescent screen:
m = X G
Y
where: X = total distance (mm) between the two grating lines;

G = calibration constant of the grating replica (lines/mm);
Y = number of grating replica spaces counted
e. After calibration, note the apparent sizes of 0.25 and 5.0 //m on the fluorescent screen.
(These dimensions are the boundary limits for counting asbestos fibers by phase contrast
microscopy.)
15. Measure 20 grid openings at random on a 200-mesh copper grid by placing a grid on a glass
slide and examining it under the PCM. Use the Walton-Beckett graticule to measure the grid
opening dimensions. Calculate an average graticule field dimension from the data and use this
number to calculate the graticule field area for an average grid opening.
NOTE: A grid opening is considered as one graticule field.
16. Obtain reference selected area electron diffraction (SAED) or microdiffraction patterns from
standard asbestos materials prepared for TEM analysis.
NOTE: This is a visual reference technique. No quantitative SAED analysis is required [7].
Microdiffraction may produce clearer patterns on very small fibers or fibers partially
obscured by other material,
a. Set the specimen holder at zero tilt.

b. Center a fiber, focus, and center the smallest field-limiting aperture on the fiber. Obtain a
diffraction pattern. Photograph each distinctive pattern and keep the photo for comparison
to unknowns.
NOTE: Not all fibers will present diffraction patterns. The objective lens current may need
adjustment to give optimum pattern visibility. There are many more amphiboles
which give diffraction patterns similar to the analytes named on p. 7402-1. Some,
but not all, of these can be eliminated by chemical separations. Also, some
non-amphiboles (e.g., pyroxenes, some talc fibers) may interfere.
1 7. Acquire energy-dispersive X-ray (EDX) spectra on approximately 5 fibers having diameters
between 0.25 and 0.5 //m of each asbestos variety obtained from standard reference materials
[7]-
NOTE: The sample may require tilting to obtain adequate signal. Use same tilt angle for all
spectra.
a. Prepare TEM grids of all asbestos varieties.
b. Use acquisition times (at least 100 sec) sufficient to show a silicon peak at least 75% of the
monitor screen height at a vertical scale of >500 counts per channel.
c. Estimate the elemental peak heights visually as follows:
(1) Normalize all peaks to silicon (assigned an arbitrary value of 10).
(2) Visually interpret all other peaks present and assign values relative to the silicon peak.
(3) Determine an elemental profile for the fiber using the elements Na, Mg, Si, Ca, and Fe.
Example: 0-4-1 0-3- <1 [7].
NOTE: In fibers other than asbestos, determination of Al, K, Ti, S, P, and F may also be
required for fiber characterization.
(4) Determine a typical range of profiles for each asbestos variety and record the profiles for
comparison to unknowns.
MEASUREMENT:
18. Perform a diffraction pattern inspection on all sample fibers counted under the TEM, using the
procedures given in step 17. Assign the diffraction pattern to one of the following structures:
a. chrysotile;
b. amphibole;
c. ambiguous;
d. none.
NOTE: There are some crystalline substances which exhibit diffraction patterns similar to those
of asbestos fibers. Many of these, (brucite, halloysite, etc.) can be eliminated from
consideration by chemistry. There are, however, several minerals (e.g., pyroxenes,
massive amphiboles, and talc fibers) which are chemically similar to asbestos and can
be considered interferences. The presence of these substances may warrant the use of
more powerful diffraction pattern analysis before positive identification can be made. If
interferences are suspected, morphology can play an important role in making positive
identification.
19. Obtain EDX spectra in either the TEM or STEM modes from fibers on field samples using the
procedure of step 18. Using the diffraction pattern and EDX spectrum, classify the fiber:
a. For a chrysotile structure, obtain EDX spectra on the first five fibers and one out of ten
thereafter. Label the range profiles from 0-5-10-0-0 to 0-10-10-0-0 as "chrysotile."
b. For an amphibole structure, obtain EDX spectra on the first 10 fibers and one out of ten
thereafter. Label profiles ca. 0-2-10-0-7 as "possible amosite"; profiles ca. 1-1-10-0-6 as
"possible crocidolite"; profiles ca. 0-4-10-3-<1 as "possible tremolite"; and profiles ca.
0-3-10-0-1 as "possible anthophyllite."
NOTE: The range of profiles for the amphiboles will vary up to ± 1 unit for each of the
elements present according to the relative detector efficiency of the spectrometer.
c. For an ambiguous structure, obtain EDX spectra on all fibers. Label profiles similar to the
chrysotile profile as "possible chrysotile." Label profiles similar to the various amphiboles as
"possible amphiboles." Label all others as "unknown" or "non-asbestos."

20. Counting and Sizing:

a. Insert the sample grid into the specimen grid holder and scan the grid at zero tilt at low
magnification (ca. 300 to 5COX). Ensure that the carbon film is intact and unbroken over ca.
75% of the grid openings.
b. In order to determine how the grids should be sampled, estimate the number of fibers per
grid opening during a low-magnification scan (500 to 1000X). This will allow the analyst to
cover most of the area of the grids during the fiber count and analysis. Use the following
rules when picking grid openings to count [7,8]:
(1) Light loading (<5 fibers per grid opening): count total of 40 grid openings.
(2) Moderate loading (5 to 25 fibers per grid opening): count minimum of 40 grid openings
or 100 fibers.
(3) Heavy loading (>25 fibers per opening): count a minimum of 100 fibers and at least 6
grid openings.
Note that these grid openings should be selected approximately equally among the three
grid preparations and as randomly as possible from each grid.
c. Count only grid openings that have the carbon film intact. At 500 to 1000X magnification,
begin counting at one end of the grid and systematically traverse the grid by rows, reversing
direction at row ends. Select the number of fields per traverse based on the loading
indicated in the initial scan. Count at least 2 field blanks per sample set to document
possible contamination of the samples. Count fibers using the following rules:
(1) Count all particles with diameter greater than 0.25 //m that meet the definition of a fiber
(aspect ratio >3:1, longer than 5 fjm). Use the guideline of counting all fibers that
would have been counted under phase contrast light microscopy (Method 7400). Use
higher magnification (10000X) to determine fiber dimensions and countability under the
acceptance criteria. Analyze a minimum of 10% of the fibers, and at least 3 asbestos
fibers, by EDX and SAED to confirm the presence of asbestos. Fibers of similar
morphology under high magnification can be identified as asbestos without SAED.
Particles which are of questionable morphology should be analyzed by SAED and EDX
to aid in identification.
(2) Count fibers which are partially obscured by the grid as half fibers.
NOTE: If a fiber is partially obscured by the grid bar at the edge of the field of view,
count it as a half fiber only if more than 2.5 //m of fiber is visible.
(3) Size each fiber as it is counted and record the diameter and length:
(a) Move the fiber to the center of the screen. Read the length of the fiber directly from
the scale on the screen.
NOTE 1 : Data can be recorded directly off the screen in //m and later converted
to fjm by computer.
NOTE 2: For fibers which extend beyond the field of view, the fiber must be
moved and superimposed upon the scale until its entire length has been
measured.
(b) When a fiber has been sized, return to the lower magnification and continue the
traverse of the grid area to the next fiber.
d. Record the following fiber counts:
(1) fs, fb = number of asbestos fibers in the grid openings analyzed on the sample filter and
corresponding field blank, respectively.
(2) Fs, Fb = number of fibers, regardless of identification, in the grid openings analyzed on
the sample filter and corresponding field blank, respectively.

CALCULATIONS:
21. Calculate and report the fraction of optically visible asbestos fibers on the filter,
(fs - fb)/(Fs - Fb). Apply this fraction to fiber counts obtained by PCM on the same filter or on other
filters for which the TEM sample is representative. The final result is an asbestos fiber count. The
type of asbestos present should also be reported.
22. As an integral part of the report, give the model and manufacturer of the TEM as well as the model
and manufacturer of the EDX system.
The TEM method, using the direct count of asbestos fibers, has been shown to have a precision of 0.275
(sr) in an evaluation of mixed amosite and wollastonite fibers. The estimate of the asbestos fraction,
however, had a precision of 0.11 (sr). When this fraction was applied to the PCM count, the overall
precision of the combined analysis was 0.20 [2].
REFERENCES:
[1] Walton, W. H. "The Nature, Hazards, and Assessment of Occupational Exposure to Airborne
Asbestos Dust: A Review," Ann. Occup. Hyg., 25, 115-247 (1982).
[2] Taylor, D. G., P. A. Baron, S. A. Shulman and J. W. Carter. "Identification and Counting of
Asbestos Fibers," Am. Ind. Hyq. Assoc. J. 45(2), 84-88 (1984).
[3] Johnston, A. M., A. D. Jones, and J. H. Vincent. "The Influence of External Aerodynamic Factors
on the Measurement of the Airborne Concentration of Asbestos Fibers by the Membrane Filter
Method," Ann. Occup. Hyg., 25, 309-316 (1982).
[4] Zumwalde, R. D. and J. M. Dement. Review and Evaluation of Analytical Methods for
Environmental Studies of Fibrous Particulate Exposures, NIOSH Technical Information Bulletin
#77-204 (1977).
[5] Baron, P. A. and G. C. Pickford. "An Asbestos Sample Filter CIearing Procedure," Appl. Ind.
Hyg., 1:169-171,199 (1986).
[6] LeGuen, J. M. and S. Galvin "CIearing and Mounting Techniques for the Evaluation of Asbestos
Fibers by the Membrane Filter Method" Ann. Occup. Hyq. 24, 273-280 (1981).
[7] Yamate, G., S. A. Agarwal, and R. D. Gibbons. "Methodology for the Measurement of Airborne
Asbestos by Electron Microscopy," EPA Contract No. 68-02-3266 (in press).
[8] Steel, E. B. and J. A. Small. "Accuracy of Transmission Electron Microcopy for the Analysis of
Asbestos in Ambient Environments," Anal. Chem., 57, 209-213 (1985).
METHOD REVISED BY:
Paul A. Baron, Ph.D.; NIOSH/DPSE.

ASPARTAME 5031
C14H18N2°5 MW: 294.34 CAS: 22839-47-0 RTECS: WM3407000

OSHA : no standard PROPERTIES: solid; MP 248-250 °C

NIOSH: no standard
ACGIH: no standard
SYNONYMS: L-aspartyl-L-phenylalanine methyl ester; 3-amino-N-(alpha-carboxyphenethyl)-succinamic acid N-methyl ester
SAMPLER: FILTER TECHNIQUE: HPLC, UV DETECTION

(1-//m, 37-mm PTFE)
ANALYTE: Aspartame
EXTRACTION: 2 mL of eluent B.
VOL-MIN: [email protected] mg/m3
-MAX: 1200 L INJECTION: 25 fjL
SHIPMENT: routine COLUMN: C18, 10-ATn particle size
SAMPLE DETECTOR: UV, 220 nm

STABILITY: stable at least 30 days at 20 °C [1]
MOBILE PHASE: 60% eluent A/40% eluent B,
FIELD BLANKS: 2 to 10 field blanks per set isocratic
MEDIA BLANKS: at least 3 per sample set CALIBRATION: standard solutions of Aspartame in
eluent B
ACCURACY RANGE: 7 to 800 ATCJ per sample [1]
RANGE STUDIED: not studied ESTIMATED LOD: 2 fjg per sample [1]
BIAS: not determined PRECISION (Sr): 0.026 @ 4.4 to 435 //g per sample [1 ]
APPLICABILITY: The working range is 0.07 to 8 mg/m for a 100-L air sample. The method has been used to analyze
personal and area air samples during a health hazard evaluation at a commercial food packaging plant. [1]
INTERFERENCES: Food additives such as flavoring (artificial flavors), stabilizers (ascorbic acid) and food colors (FD&C yellow)
collected along with Aspartame sampling, did not affect the analysis. [1]
OTHER METHODS: An HPLC method for the analysis of Aspartame in bulk has been reported. [2]

ASPARTAME: METHOD 5031, Issue 2, dated 15 August 1994 - Page 2 of 4
1. Aspartame,™ 96% pure. 1. Sampler: 1-//m, 37-mm PTFE filter (Millipore

2. Water, deionized. FALP or equivalent) with a cellulose backup
3. Acetonitrile, distilled in glass. pad in a 37-mm polystyrene 2-piece cassette.
4. Methanol, distilled in glass. 2. Personal sampling pump capable of 1 to 3
5. 1-Heptanesulfonic acid sodium salt. L/min, with flexible connecting tubing.
6. Monobasic potassium phosphate. 3. High-performance liquid chromatograph
7. Phosphoric acid, reagent grade. (HPLC) with UV detector, 220-nm, integrator
8. EluentA: Add 2.062 g 1-heptanesulfonic acid and C18 column (page 5031-1).
sodium salt and 0.45 g monobasic potassium 4. Syringe filters, 13-mm: 0.45 ^m, PTFE.
phosphate to 1 .0 L deionized water and adjust 5. Syringe, 10-mL, disposable.
pH to 2.5 with dilute phosphoric acid.* 6. Vials, glass, scintillation, 20-mL with
9. Eluent B: Add 2.062 g 1-heptanesulfonic acid PTFE-lined caps.
sodium salt to 1.0 L of 3:2 (v/v) acetonitrile- 7. Syringes, microliter, readable to 0.1 //L
water, and adjust pH to 3.0 with dilute 8. Pipets, various sizes.
phosphoric acid. 9. Tweezers.
10. Calibration stock solution: 5 mg/mL Add 10. Ultrasonic water bath.
0.05 g Aspartame and dilute with 10 mL eluent 11. pH meter.
B.
* See SPECIAL PRECAUTIONS
SPECIAL PRECAUTIONS: Phosphoric acid is extremely corrosive. Work with care in a hood using
protective gloves.
SAMPLING:

2. Remove the front and rear plugs immediately before sampling. Attach sampler to personal
3. Sample at an accurately controlled flow rate between 1 and 3 L/min for a sample volume of 70
to 1200 L
4. At the completion of sampling, replace both plugs and pack the sampler securely for shipment.
Include appropriate number of blanks in the shipment.
SAMPLE PREPARATION:
5. Remove the PTFE filter with tweezers and transfer to a 20-mL scintillation vial. Discard the back
up pad. Add 2.0 mL eluent B.
6. Agitate the samples for 1 hour in an ultrasonic water bath.
7. Filter the sample solution using a disposable syringe fitted with a 0.45-//m PTFE filter into a clean
vial.
8. Calibrate daily with at least six working standards.

a. Add known amounts of calibration stock solutions to eluent B, using serial dilutions as
needed to obtain concentrations in the range of 1 to 400 //g /mL
b. Analyze with samples and blanks (steps 11 through 13).

ASPARTAME: METHOD 5031. Issue 2, dated 15 August 1994 - Page 3 of 4
c. Prepare a calibration graph (peak area vs. mass of Aspartame, //g per sample).
9. Determine the recovery at least once for each lot of filters used for sampling in the range of
interest. Prepare six filters at each of three levels plus three media blanks.
a. Add known amounts of Aspartame in methanol to the filters.
b. Cover filters. Allow to stand overnight for solvent evaporation.
c. Prepare samples (step 5 through 7), and analyze (step 11 through 13) together with
standards.
d. Determine recovery (R). Construct a graph of R vs. //g Aspartame recovered.
graph and recovery graph are in control.
MEASUREMENT:
11. Set the liquid chromatograph to manufacturer's recommendations and parameters given on
page 5031-1.
12. Inject sample aliquot manually or with autosampler.
13. Measure peak areas.
CALCULATIONS:
14. Determine the mass, //g (corrected for recovery) of Aspartame found on the sample filter (W)
and the average blank filter (B).
15. Calculate concentration, C, of Aspartame in the air volume sampled, V (L):
C . .. mg/m°.
A calibration curve constructed from nine standards over the range 0.5 to 463 fjg/mL Aspartame in
solution was linear and indicated a limit of detection (LOD) of 2 //g per filter and a limit of quantitation
(LOQ) of 7 //g per filter. Test samples were prepared by spiking filters with known amounts of
Aspartame from a solution in methanol at levels between 4.4 //g per filter and 434 //g per filter. At each
level, three filters were subjected to each of the following studies (Table 1):
a. To evaluate extraction efficiency, the filters were analyzed immediately.
b. To assess storage stability, spiked filters were stored for 1 month prior to analysis.
c. To investigate the stability of the material on the filter during sampling, spiked filters were
attached to a sampling pump and 1000 L of laboratory air was drawn through them at 2.5 L/min
before analysis.
TABLE 1: Average Percent Recovery (n = 3) of Aspartame
Spiked Amount Extraction Sampling Storage

(A/g) Efficiency Stability Stability @ 30 days
(n-3) (%RSD) (%RSD) (%RSD)
4.4 100 (2.3) 100 (1.3)

43.5 103 (4.8) 98 (3.1) 102 (2.7)
217 101 (1.8) 100 (2.4)
435 101 (1.3) 101 (1.3)

ASPARTAME: METHOD 5031, Issue 2, dated 15 August 1994 - Page 4 of 4
REFERENCES:
[1] Albrecht, W., G. Burr, and C. Neumeister. Sampling and Analytical Method for Workplace
Monitoring of Aspartame in Air., App. Ind. Hva, 4:9 (1989).
[2] Verzella, G., F. Bagnasco, and A. Mangia. Ion-Pair High-Performance Liquid Chromatographic
Analysis of Aspartame and Related Products., J. Chromatogr., 349. 83 (1985).
METHOD WRITTEN BY:
Charles Neumeister, NIOSH/DPSE.

AZELAIC ACID 5019
HOOC(CH2)7COOH MW: 188.25 CAS: 123-99-9 RTECS: CM 1980000

OSHA : no PEL PROPERTIES: solid; d 1.225 g/mL @ 25 °C;

NIOSH: no REL MP 106.5 °C; BP >360 °C (decomposes)
ACGIH: no TLV
SYNONYMS: nonanedioic acid; 1,7-heptanedicarboxylic acid; lepargylic acid
SAMPLER: FILTER TECHNIQUE: GAS CHROMATOGRAPHY, FID

(5-fjm PVC membrane)
ANALYTE: bis(trimethylsilyl)ester of azelaic acid
EXTRACTION: 5 mL ethanol; stand 20 min @ 70 °C;
VOL-MIN: 200 L @ 5 mg/m3 evaporate to dryness, derivatize and
-MAX: 1000 L redissolve in pyridine
SHIPMENT: routine DERIVATIZATION: BSTFA/TMCS in pyridine;

20 min @ 70 °C
SAMPLE
STABILITY: not determined INJECTION VOLUME: 1 fjL
BLANKS: 2 to 10 field blanks per set TEMPERATURE-INJECTION: 250 °C;

-DETECTOR: 250 °C;
-COLUMN: 190 to 250 °C; 6 °C/min
or 200 "C isothermal
ACCURACY CARRIER GAS: He, 39 mL/min
RANGE STUDIED: not studied COLUMN: 3 m x 2-mm ID; 6% methyl silicone

on 60/80 mesh Chromosorb WAW
BIAS: not determined DMCS
OVERALL PRECISION (SrT): not determined CALIBRATION: analyte in pyridine
ACCURACY: not determined RANGE: 1 to 10 mg per sample
APPLICABILITY: The working range is 2 to 20 mg/m for a 500-L air sample. The measurement range can be lowered if
adequate recoveries are found. The method may be applicable to other straight-chain aliphatic dicarboxylic acids.
INTERFERENCES: Moisture decomposes both the trimethylsilyl reagents and their corresponding derivatives.
OTHER METHODS: This is P&CAM 256 [2] in a revised format.

AZELAIC ACID: METHOD 5019, Issue 2, dated 15 August 1994 - Page 2 of 3
1. NÔ-bis(trimethylsilyl)trifluoro-acetamide 1. Sampler: PVC membrane filter, 5-//m pore

(BSTFA) containing 1% trimethylchlorosilane size, 37-mm diameter; in cassette filter holder.
(TMCS) obtainable from chromatography 2. Personal sampling pump, 1 to 3 L/min, with
products suppliers. flexible connecting tubing.
NOTE: Store in desiccator. 3. Gas chromatograph, flame ionization detector,
2. Pyridine, spectroquality grade.* integrator and column (page 5019-1).
3. Ethanol, spectroquality grade. 4. Vacuum oven or hotplate.
4. Azelaic acid, highest purity available. 5. Analytical balance, 0.01 mg.
5. Helium, purified. 6. Waterbath, 70 °C.
6. Hydrogen, purified. 7. Vials, glass, 20-mL, PTFE-lined screw caps.
7. Air, "zero grade." 8. Pipets, 1- and 5-mL
9. Syringes, 10-//L
* See Special Precautions 10. Tweezers, microspatula, weighing paper and
an applicator stick.
SPECIAL PRECAUTIONS: Pyridine may cause central nervous system depression and irritation of the
skin and respiratory tract [3]. Work must be performed in a fume hood.
SAMPLING:

2. Sample at an accurately known flow rate between 1 and 3 L/min for a sample size of 200 to
1000 L
3. Cap the samplers with plastic plugs and pack securely for shipment.
SAMPLE PREPARATION:
4. Remove filter from cassette holder with tweezers and insert in a glass vial. Push it gently to the
bottom of the vial.
5. Pipet 5.0 mL ethanol into the vial. Cap the vial.
6. Place the vial in a 70 °C waterbath for 20 min. Shake the vial every 5 min.
NOTE: Use of an ultrasonic bath is not recommended because it breaks up the PVC filter.
7. Lift the filter with tweezers so it is above the ethanol level in the vial. Rinse the filter with ten
1-mL aliquots of ethanol. Discard the filter.
8. Place the vial in a vacuum oven or on a hotplate at 45 to 50 °C. Evaporate to dryness.
9. Derivatize.
a. Add 1 mL pyridine to the vial to dissolve the residue.
b. Add 1 mL BSTFA mixture to the vial. Shake the vial for 1 min.
NOTE: Avoid working in a humid atmosphere because water decomposes the trimethylsilyl
reagent and derivative.
c. Cap the vial. Place the vial in a waterbath at 70 °C for 20 min. Shake the contents of the
vial every 5 min.
10. Calibrate daily with at least six working standards over the range 0.001 to 10 mg azelaic acid per
sample.
a. Add weighed amounts of azelaic acid to marked vials containing 5 mL ethanol.
b. Evaporate and derivatize (steps 8 and 9).

AZELAIC ACID: METHOD 5019, Issue 2, dated 15 August 1994 - Page 3 of 3

d. Prepare calibration graph (peak area vs. mg azelaic acid).
NOTE: If azelaic acid is not 100% pure, correct the mass of azelaic acid standards before
preparation of calibration graph.
11. Determine the recovery of azelaic acid from PVC filters at least once for each lot of filters used.
a. Weigh various amounts of azelaic acid to cover the range of interest onto PVC filters in
marked vials.
b. Treat as in steps 5 through 9 and 12 and 13.
MEASUREMENT:
on page 5019-1. Inject a 1-//L sample.
13. Measure peak area after each injection. Calculate the mean area.
NOTE: Remove daily the white flakes which accumulate on the FID.
CALCULATIONS:
14. Determine the mass, mg, of azelaic acid (W) per filter and the average media blank (B) from the
calibration graph.
15. Calculate the concentration, C, of azelaic acid in the air volume sampled, V (L):
f mg/m3_
The measurement precision, Sr, of this method was determined to be 0.02 using standards in the range
1 to 10 mg per sample. The average recovery of azelaic acid from spiked PVC filters in the range 2 to
10 mg per filter was 94.9 ± 4.3% [1].
REFERENCES:
[1] Palassis, J. The Sampling and Determination of Azelaic Acid in Air, Am. Ind. Hyg. Assoc. J., 39,
731-736 (1978).
[3] NIOSH/OSHA Occupational Health Guidelines for Chemical Hazards, USDHHS Publ. (NIOSH)
81-123 (1981).
METHOD REVISED BY:
John Palassis, NIOSH/DTMD.

BARIUM, soluble compounds 7056
Ba MW: 137.34 CAS: 7440-39-3 RTECS: CQ8370000

OSHA : 0.5 mg/nr PROPERTIES: solubility @ 100 °C:

NIOSH: 0.5 mg/m;; BaCO3: 0.006 g/100 g H20;
ACGIH: 0.5 mg/m3 BaCI2: 59 g/100 g H20;
Ba(NO3)2: 34 g/100 g H2O;
BaO: " 91 g/100 g H2O
SYNONYMS: vary depending upon compound

(0.8-A(m cellulose ester membrane)
ANALYTE: barium ion (Ba2 + )
EXTRACTION: hot water leach, 10 mL, 10 min,
VOL-MIN: 50 L @ 0.5 mg/m3 twice; conc. HCI, 3 drops; evaporate
-MAX: 2000 L to dryness
SHIPMENT: routine FINAL SOLUTION: 5% HCI/1.1 mg/mL Na + , 5 mL
SAMPLE STABILITY: stable FLAME: nitrous oxide-acatylene reducing
FIELD BLANKS: 2 to 10 field blanks per set WAVELENGTH: 553.6 nm
CALIBRATION: standard solutions of Ba2 + in

5% HCI/1.1 mg/mL Na +

ACCURACY
(168-L samples) PRECISION (5r): 0.025® 43 to 180//g per sample [1]
BIAS: - 0.55%
ACCURACY: ± 10.81%
APPLICABILITY: The working range is 0.13 to 10 mg/m3 for a 200-L air sample. This method determines Ba2+ in
water-soluble barium compounds. Insoluble barium compounds (e.g., BaSO^ require an ashing procedure.
INTERFERENCES: lonization of barium in the flame is controlled by addition of sodium chloride to samples and standards.
Calcium, at >0.1%, gives a positive interference unless background correction is used.

BARIUM, soluble compounds: METHOD 7056, Issue 2, dated 15 August 1994 - Page 2 of 3
1. Water, distilled or deionized. 1. Sampler: cellulose ester membrane filter,

2. Nitric acid (HNO3), conc.* 0.8-//m pore size, 37-mm diameter, in cassette
3. Hydrochloric acid (HCI), conc.* filter holder.
4. Sodium chloride (NaCI). 2. Personal sampling pump, 1 to 4 L/min, with
5. 5% HCI (v/v)/1.1 mg/mL Na+: Dilute 5 mL flexible connecting tubing.
conc. HCI and 0.28 g NaCI to 100 mL with 3. Atomic absorption spectrophotometer with
deionized water. nitrous oxide-acetylene burner head and
6. Calibration stock solution, 1000 fjg Ba/mL barium hollow cathode lamp.
Commercially available or dissolve 1.437 g NOTE: Background correction (e.g., D2 or H2
BaCO3 in minimum volume of (1+1) HCI and lamp) needed for samples with >0.1%
dilute to 1 L with 1% (v/v) HCI. (w/v) Ca2+.
7. Nitrous oxide, 98%. 4. Regulators, two-stage, for nitrous oxide and
8. Acetylene, 99.6%. acetylene.
5. Beakers, Phillips, 125-mL, or Griffin, 50-mL,
7. Pipets, 4- to 400-//L, and 5-mL
See SPECIAL PRECAUTIONS 8. Hotplate, surface temperature 140 °C.
9. Forceps or tweezers, plastic-tipped.
10. Centrifuge, and centrifuge tubes, 50-mL
* Clean with conc. HNO3 and rinse

before use.
SPECIAL PRECAUTIONS: Nitric and hydrochloric acids are corrosive liquids. Wear protective clothing
and work in a fume head.
SAMPLING:

L Do not exceed a filter loading of ca. 2 mg total dust.
SAMPLE PREPARATION:
3. Open cassette filter holders and transfer samples and blanks to clean beakers.
4. Add 10 mL boiling distilled water. Let stand 10 min with occasional swirling. Decant extract to a
centrifuge tube.
5. Wash filter and beaker twice with ca. 2 mL hot distilled water and add to centrifuge tube.
6. Repeat extraction and washing (steps 4 and 5), adding the solutions to the centrifuge tube.
7. Remove filter with forceps and rinse with stream of hot distilled water into centrifuge tube.
8. Rinse original beaker three times with ca. 2 mL hot distilled water and add to centrifuge tube.
Centrifuge and decant the solution to a second beaker.
9. Add three drops conc. HCI to sample and evaporate until ca. 0.5 mL liquid remains.
10. Cool each beaker. Pipet 5.0 mL 5% HCI/1.1 mg/mL Na+ solution into each beaker. Swirl to
dissolve residue.

BARIUM, soluble compounds: METHOD 7056, Issue 2, dated 15 August 1994 - Page 3 of 3
11. Add known amounts of calibration stock solution to 10-mL volumetric flasks and dilute to volume
with 5% HCI/1.1 mg/mL Na+ solution to produce Ba2* concentrations in the range 0.4 to 40
//g/mL (0.002 to 0.2 mg per sample). Prepare fresh daily.
12. Analyze working standards with the blanks and samples (steps 17 and 18).
13. Prepare calibration graph (absorbance vs. solution concentration, //g/mL).
14. Aspirate a standard for every ten samples to check instrument drift.
15. Check recoveries with at least one spiked media blank per ten samples.
MEASUREMENT:

page 7056-1 .
NOTE: If absorbance values for samples are above the linear range of the standards, dilute with
5% HCI/1.1 mg/mL Na+ solution, reanalyze, and apply the appropriate dilution factor in
calculations.
CALCULATIONS:
19. Using the measured absorbances, calculate the corresponding concentrations (^g/mL) of
barium in the sample, Cs, and average media blank, Cb, from the calibration graph.
concentration of barium, C (mg/m3), in the volume of air sampled, V (L):
c- mg/m*.
Method S198 was validated using atomized aqueous solutions of barium chloride to generate
atmospheres at approximately 0.3 to 1.1 mg/m3 [1]. Samples taken at 1.4 L/min showed 100%
collection efficiency. Recovery of barium chloride standards spiked on filters was 102% with Sr = 1.4%
in the range 0.043 to 0.18 mg barium per sample.
REFERENCES:
Welfare, Publ. (NIOSH) 77-185 (1977), available as Stock No. PB 274-248 from NTIS, Springfield,
VA 22161.
Education, and Welfare, Publ. (NIOSH) 77-157-C (1977).
METHOD REVISED BY:

BENZENE by portable GC 3700
C6H6 MW: 78.11 CAS: 71-43-2 RTECS: CY1 400000

OSHA : 1 ppm; STEL 5 ppm PROPERTIES: liquid; d 0.879 g/mL @ 20 °C;

NIOSH: 0.1 ppm; C 1ppm/15 min (suspect carcinogen) BP80.1 °C; MP5.5 °C;
ACGIH: 10 ppm; (suspect carcinogen) VP 12.7 kPa (95.2 mm Hg;
(1 ppm = 3.19 mg/m3 @ NTP) 1 2.5% v/v) @ 25 ° C; explosive range
1.3 to 7.1% v/v
SYNONYMS: benzol; cyclohexatriene
SAMPLER: AIR BAG (Tedlar) TECHNIQUE: GAS CHROMATOGRAPHY (PORTABLE),

PHOTOIONIZATION DETECTOR
FLOW RATE: 0.02 (or lower) to 5 L/min (or
higher); fill bag to £80% of ANALYTE: benzene
capacity; spot samples possible
(step 2. a.) COLUMN: CPSil 5CB Macrobore capillary column
operated isothermally at 30 °C (other
SAMPLE STABILITY: bags should be analyzed as soon columns and detectors shown in field
after collection as possible (<4 h). study to be acceptable).
FIELD BLANKS: clean air, either in bag or from a CALIBRATION: bag standards or calibrated gas mixtures
non-work area.
RANGE: lower limit 0.02 to 1 ppm (see
Interferences section below); upper limit
500 ppm.
ESTIMATED LOD: 0.01 ppm for a 1-mL injection.
ACCURACY PRECISION (Sr): 0.127
RANGE STUDIED: 0.03 to 100 ppm [1]

BIAS: not significant
OVERALL PRECISION (SrT): 0.136
ACCURACY: >± 27%
APPLICABILITY: The working range is 0.02 to 500 ppm (0.06 to 1600 mg/m3) (see EVALUATION OF METHOD).
INTERFERENCES: Any compounds having the same or nearly the same retention time as benzene on the column in use are
potential interferences. Such compounds cause positive interferences, however, and the actual benzene concentration will be
less than or equal to the total of the benzene plus these compounds. The presence of a large number of compounds with
retention time similar to benzene will cause a high background resulting in decreased sensitivity, possibly to the point where
the LOQ approaches 1 ppm. Butane, styrene, toluene and xylenes have been shown not to affect this method [1]. Acceptable
estimates of benzene concentration in diesel and gasoline vapors have been made with this method [2].
OTHER METHODS: Methods 1500 (Hydrocarbons, BP 36 - 126 °C) and 1501 (Hydrocarbons, aromatic) use activated charcoal
sampler tubes.

BENZENE by portable GC: METHOD 3700, Issue 2, dated 15 August 1994 - Page 2 of 4
Benzene* in air, working standards prepared 1. Portable gas chromatograph (GC), with
in the field by filling Tedlar bags with photoionization detector, preferably with gas
commercially prepared and certified standards sampling loop and (if appropriate) strip chart
(preferred) or prepared in the field by injecting recorder.
known amounts of pure benzene into Tedlar 2. Personal sampling pump, 0.02 to 5 L/min or
bags containing a metered volume of pure air other rate suitable for filling sample bag, with
or nitrogen. flexible connecting tubing.
2. Cylinder of air, nitrogen or helium for use as NOTE: Pumps lubricated with petroleum
carrier gas and field blanks.* products should not be used.
3. Sample bags, Tedlar, 1- to 20-L or other
appropriate sizes.
* See SPECIAL PRECAUTIONS. 4. Syringes, gas-tight, of various sizes
appropriate to the GC.
NOTE: To reduce the possibility of
contamination, use separate,
previously unused syringes for
working standards and samples. Test
syringes for contamination
occasionally by filling them with clean
air and analyzing the contents.
5. Label tape and marking pen for labeling bags.
SPECIAL PRECAUTIONS: Benzene is a suspect carcinogen [3,4]. Shipment of compressed gases

must comply with 49 CFR 171-177 regulations regarding shipment of hazardous materials.
SAMPLING:
1. Start GC instrument and recorder and allow to warm up according to manufacturer's

instructions.
NOTE: A straight baseline should be attained at the highest sensitivity likely to be used.
2. Select one of the following sampling modes:
a. Spot sample. Draw air sample into the gas sampling loop of the GC with the on-board
sampling pump, if supplied. Alternatively, inject an aliquot of air to be sampled into the GC
with a gas-tight syringe.
NOTE: A large contributor to random error in the method is imprecision of replicate
injections. To improve precision:
(1) use a gas sampling loop for injections, if available;
(2) make at least three replicate determinations per sample;
(3) use an injection volume large enough to be precisely readable, and consistent with that
used in calibration.
b. Integrated air sample for TWA determination.
(1) Evacuate a clean sample bag using the inlet port of a personal sampling pump.
NOTE: To reduce memory effects and contamination, use only previously unused sample
bags. Alternatively, purge used bags at least two times with clean air, then fill with
clean air and analyze for benzene as in step (4) below.
(2) Attach the sample bag to the outlet port of a personal sampling pump with a minimum
length of flexible tubing. To the inlet port of the pump attach a length of Teflon tubing
sufficient to reach the desired site. Alternatively, a rubber squeeze bulb can be used in
place of a personal sampling pump when sample size is small. In either case, tubing
and pump/bulb should be flushed with sample air prior to, and clean air subsequent to,
sample collection.

BENZENE by portable GC: METHOD 3700, Issue 2, dated 15 August 1994 - Page 3 of 4
NOTE: Tygon tubing has been shown to adsorb some materials in complex hydrocarbon
mixtures and to off-gas during later sample collection causing an increase in
hydrocarbon concentration in those subsequent samples.
(3) Pump the air sample into the bag at a rate calculated to fill <80% of the sample bag
capacity over the sampling period.
NOTE: The flow rate must be constant throughout the sampling period.
(4) Within 4 h after completion of sampling, introduce an aliquot of the sample into the GC
(as in step 2.a).
3. Obtain the benzene peak height or area of the injected sample.
4. Perform the following in the laboratory before field work begins:

a. Establish a laboratory calibration graph with at least three replicate determinations of at least
six working standards. Plot peak height or area vs. mass or concentration of benzene.
b. Determine detector drift, averaged over the time period(s) expected to be used in the field.
c. Determine the ability of the GC column to separate the benzene peak from other substances
known or predicted to be present in the field samples.
5. Establish a daily field calibration graph (peak height vs. mass or concentration of benzene) with
triplicate determinations of working standards under the same conditions as for samples (step
2.a). Alternate analyses of samples and working standards, if possible.
CALCULATIONS:
6. Calculate mass, W (ng), of benzene in sample by comparison of sample peak height with daily
calibration graph (step 5). Determine concentration, C, of benzene in the injected sample, V (mL):
C = — , mg/m3.
NOTE: Some GCs will perform this calculation electronically.
This method was evaluated over the range 0.03 to 100 ppm benzene using a Photovac 10S portable GC.
Certified standard gas mixtures of benzene in air were obtained from Scott Specialty Gases Inc., and
these were used to establish the calibration graph. Once this graph was established, bias was assessed
by analyzing a bag sample containing an unknown concentration and comparing the concentration
obtained with that obtained from analysis of replicate charcoal tube sample taken from the same bag.
Additionally, a field evaluation was subsequently conducted in which results obtained using this method
were compared with results obtained using conventional laboratory GC analysis and with results
obtained using laboratory GC/MS analysis. Instruments used in the field evaluation include the
Photovac 10S, the Sentex Scentoscreen and the MSI-301B by Microsensor Systems, Inc.
Previous issues of this method discussed the use of portable GC with ambient temperature packed
columns. That technique was considered to be limited in its ability to separate the analyte from any
interferences present. Evaluation of this method, which uses a capillary column, indicates that benzene
can be separated from butane, styrene, toluene and xylenes, and that a response corresponding to
benzene can be identified in such complex mixtures as gasoline and diesel vapors [1].

BENZENE by portable GC: METHOD 3700, Issue 2. dated 15 August 1994 - Page 4 of 4
REFERENCES:
[1] Burroughs, G.E. and W.J. Woodfin. "On-Site Screening for Benzene in Complex Environments." A
report to the U.S. Coast Guard, Research and Development Center, Groton, CT, in partial fulfillment
of MIPR No. Z51100-2-E00528, August, 1993.
[2] Burroughs, G.E. and W.J. Woodfin, "On-Site Screening for Benzene in Complex Environments - A
Report to the U.S. Coast Guard Research and Development Center," NIOSH/DPSE (unpublished,
August, 1993).
[3] NIOSH/OSHA Occupational Health Guidelines for Chemical Hazards, US DHHS (NIOSH) Publ. 81-
123 (1981).
[4] Criteria for a Recommended Standard. ..Occupational Exposure to Benzene, U.S. Department of
Health, Education, and Welfare, Publ. (NIOSH) 74-137 (1974); as revised in August, 1976, and by E.
J. Baier, NIOSH Testimony to U.S. Department of Labor, July, 1977.
METHOD WRITTEN BY:
G.E. Burroughs and J.C. Posner, Ph.D., NIOSH/DPSE.

BENZIDINE 5509
(C6H4NH2)2 MW: 184.23 CAS: 92-87-5 RTECS: DC9625000

OSHA : carcinogen (29 CFR 1910.1010) PROPERTIES: solid; MP 127 C; BP 400 °C

NIOSH: carcinogen (29 CFR 1910.1010)
ACGIH: carcinogen (skin)
SYNONYMS: [1,1'-biphenyl]-4,4'-diamine; g-diaminodiphenyl.

(13-mm glass fiber)
ANALYTE: benzidine or 3,3'-dichlorobenzidine
FLOW RATE: 0.2 L/min
DESORPTION: 0.5 mL 0.17% (v/v) triethylamine In
VOL-MIN: 20L@10//g/m3 methanol; stand 60 min
-MAX: 100 L
INJECTION
SHIPMENT: ship benzidine samples in dry ice VOLUME: 10 M-
SAMPLE MOBILE PHASE: 60% methanol/40% water;

STABILITY: 11 days @ -15 °C [1]
FLOW RATE: 1.5 mL/min; ambient temperature
COLUMN: //Bondapak C,8, 10-jum particles, 30 cm x
4-mm
DETECTOR: UV, 254 nm

ACCURACY
CALIBRATION: solutions of analyte(s) in eluent
RANGE STUDIED: 21 to63//g/m3 [1]
RANGE: 0.2 to 7//g per sample
BIAS: - 3.0%
ESTIMATED LOD: 0.05 fJQ per sample [1]
ACCURACY: ± 13.7% PRECISION (§r): £0.07 [1]
APPLICABILITY: The working range for benzidine or 3,3'-dichlorobenzidine is 4 to 200 fjg/m3 for a 50-L air sample.
Benzidinium sulfate and 3,3'-dichlorobenzidine dihydrochloride will be collected and converted to benzidine and
3,3'-dichlorobenzidine, respectively, during sample preparation.
INTERFERENCES: Aniline interferes in the determination of benzidine but may be resolved [2].
4,4'-Methylenebis(2-chloroaniline) interferes in the determination of 3,3'-dichlorobenzidine [1]. A number of compounds were
shown not to interfere [1,2] (see NOTE 2, step 12).
OTHER METHODS: This combines and replaces P&CAM 243 and P&CAM 246 [3].

(1) BENZIDINE and (2) 3,3'-DICHLOROBENZIDINE: METHOD 5509, Issue 2, dated 15 August 1994 - Page 2 of 4
1. Methanol, HPLC grade. 1. Sampler: 13-mm, Type AE, glass fiber filter
2. Acetonitrile, HPLC grade. (Gelman, or equivalent) in a 13-mm filter
3. Triethylamine. holder (Swinney, Gelman, or equivalent).
4. Water, distilled, deionized. 2. Personal sampling pump, 0.2 L/min, with
5. Benzidine.* flexible connecting tubing.
6. 3,3'-Dichlorobenzidine.* 3. High-performance liquid chromatograph, UV
7. Eluent: 0. 1 7% (v/v) triethylamine in methanol. detector, integrator and column (page 5509-1 ).
Dilute 170 fjL triethylamine to 100 mL with 4. Test tubes, 1 -mL, with polyethylene stoppers,
methanol. 5. Syringes, glass, 10- and 25-//L, readable to
8. Calibration stock solution, 0.5 //g///L Dissolve 0.1 //L
50 mg analyte in 100 mL eluent. 6. Pipets, delivery, 0.5- and 5-mL, graduated in
9. Recovery (R) stock solution, 0.5 fJQ/fjL 0.1 mL.
Dissolve 50 mg analyte in 100 mL methanol. 7. Flasks, volumetric, 10- and 100-mL
8. Centrifuge.
* See SPECIAL PRECAUTIONS. 9. Test tube shaker, vortex type.
SPECIAL PRECAUTIONS: Benzidine is a recognized human carcinogen and can be absorbed through
the skin [4,5,6]. 3,3'-Dichlorobenzidine is a carcinogen [4,6]. Take appropriate precautions to avoid
personal and area contamination.
SAMPLING:

2. Sample at 0.2 L/min for a total sample size of 20 to 100 L
3. Cap the sampler.
4. Ship and store samples at - 15 °C if benzidine may be present.
NOTE: Samples may be stored at room temperature if only 3,3'-dichlorobenzidine is present.
SAMPLE PREPARATION:
5. Place glass fiber filter in a test tube.

6. Add 0.5 mL eluent to each test tube. Seal each test tube and shake them on a test tube shaker.
7. Allow samples to stand for 1 h with intermittent shaking.
8. Centrifuge each sample for 10 min.
9. Calibrate daily with at least six working standards over the range 0.05 to 7 fjg analyte per
sample.
a. Deliver aliquots of calibration stock solution with microliter syringe to eluent in 10-mL
b. Analyze together with the samples and blanks (steps 12 through 14).
c. Prepare calibration graph (peak area vs. //g analyte).
10. Determine recovery (R) at least once per year for each lot of filters. Prepare four filters at each
of five levels, plus three media blank filters.
a. Place sample filters into separate test tubes.
b. Inject an aliquot of R stock solution, or a dilution thereof in methanol, directly onto the filter.
c. Cap the test tubes. Allow to stand overnight.
d. Prepare (steps 5 through 8) and analyze (steps 12 through 14) with working standards.

e. Prepare a graph of R for each filter vs. JJQ analyte recovered.

and R graphs are in control.
MEASUREMENT:
12. Set the liquid chromatograph to conditions given on page 5509-1 for analyte of interest.
NOTE 1 : If aniline is present, use a Waters Radial Pak A (C1B) column, or equivalent, and
follow the procedures found in reference [2].
NOTE 2: The following compounds were found not to interfere with the determination of either
compound: o-, p.- and m-chloroaniline; 4,4'-methylenedianiline and B-naphthylamine.
2-Chloro-4-methylaniline; 3,3'-dichlorobenzidine; 4,4'-methylenebis(2-chloroaniline);
hydrazobenzene; and 1,2- and 1,4-naphthoquinone do not interfere in the
determination of benzidine. Benzidine, aniline, N-methylaniline, 2-toluidine and
3,3'-dimethylbenzidine will not interfere in the determination of 3,3'-dichlorobenzidine
[1].
13. Inject an aliquot (see page 5509-1 for appropriate size).
CALCULATIONS:
15. Read the mass, fjg (corrected for R), of analyte found on the sample filter (W) and on the media
blank filter (B) from the calibration graph.
C = W^B, mg/m'.
This method was evaluated over the range 21 to 63 //g/m3 for benzidine and the range 20 to 130
for 3,3'-dichlorobenzidine. The generated atmospheres for both compounds were at 30 °C and 80%
relative humidity. The sampling rate was 0.8 L/min. The pooled overall precision (S\T) was 0.07 for 29
benzidine samples and 0.07 for 28 3,3'-dichlorobenzidine samples. The sampling methods were
evaluated for effects of temperature (25, 30, and 35 °C) and relative humidity (20 and 80%). No
detectable quantities of either benzidine or 3,3'-dichlorobenzidine were found on backup silica gel tubes
[1]. At 180 °C, vapors of these carried by a stream of dry nitrogen at 0.3 L/min did not break through
the backup silica gel in 3 h [1].
The average recovery of benzidine from filters was determined to be 97% over the range 0.2 to 2.0 //g
when stored at -15 °C for 11 days. Recoveries dropped to 89% and 75% after 15 days and 21 days,
respectively. Recoveries of benzidine and benzidinium sulfate from filters and silica gel indicated that the
compounds were unstable in these matrices at ambient temperature. Recoveries over the range of 0.5
to 5 fjg 3,3'-dichlorobenzidine and its dihydrochloride were 96% after 21 days from both filters silica gel
and stored at -15 °C and at ambient temperature [1].
REFERENCES:
[1] Morales, R., S. M. Rappaport, R. W. Weeks, Jr., E. E. Campbell, and H. J. Ettinger.

Development of Sampling and Analytical Methods for Carcinogens, January 1 - September
30, 1976, Los Alamos Scientific Laboratory, Los Alamos, NM (1977) available as No. LA-7058-PR,
from NTIS, Springfield, VA 22161.

[2] Kennedy, E. R. and M. J. Seymour. ACS Symposium Series, No. 149, Chemical Hazards in the
Workplace - Measurement and Control, 21-35, American Chemical Society, Washington, DC
(1981).
[3] NIOSH Manual of Analytical Methods, 2nd ed., Vol. 1, P&CAM 243 and P&CAM 246, U.S.
Department of Health, Education, and Welfare, Publ. (NIOSH) 77-1 57-B (1977).
[4] Carcinogenicity and Metabolism of Azo Dyes, Especially Those Derived from Benzidine, NIOSH
Technical Report, U.S. Department of Health and Human Services, Publ. (NIOSH) 80-119 (1980).
[5] NIOSH/NCI, Current Intelligence Bulletin 24, Benzidine-Derived Dyes, U.S. Department of Health,
and Human Services, Publ. (NIOSH) 81-123, available as GPO Stock #17-033-00337-8 from
METHOD REVISED BY: M. J. Seymour, NIOSH/DPSE.

BENZIDINE in urine 8306
MW: 184.24 CAS: 92-87-5 RTECS: DC9625000

BIOLOGICAL INDICATOR OF: exposures to benzidine and benzidine-based azo dyes.
SYNONYMS: [1,1'-biphenyl]-4,4'-diamine
BIOLOGICAL SAMPLING MEASUREMENT
SPECIMEN: urine, 2 to 3 h after exposure TECHNIQUE: GAS CHROMATOGRAPHY, ECD
VOLUME: 100 mL in polyethylene bottle ANALYTE: N,N'-diheptafluorobutyryl benzidine
PRESERVATIVE: 2 drops 12 N HCI after collection INJECTION

VOLUME: 3 fjL, Grab type-splitless
SHIPMENT: frozen and shipped in dry ice
COLUMN: 15 m x 0.25-mm I.D. capillary;
SAMPLE WCOT-SE-54
STABILITY: unknown
CARRIER GAS: 5 % methane in argon, 1 mL/min
CONTROLS: at least 3 urine specimens from non-
exposed individuals per study; 1 per 10 TEMPERATURE-INJECTOR: 260°C
samples -DETECTOR: 350 °C
-COLUMN: 120°Cfor2min;
40°/min to 280°;
hold 6 min
CALIBRATION: solutions of benzidine in benzene

with internal standard
QUALITY CONTROL: spiked urine corrected for

creatine content
RANGE: 10 to 1000//g/L
RECOVERY: 92%
ESTIMATED LOD:
PRECISION (§r): 0.11
ACCURACY: ± 29%
APPLICABILITY: This procedure is useful for monitoring exposures to benzidine or benzidine-based azo dyes which are
absorbed via the skin, lung, or gastrointestinal tract, and whose metabolites are benzidine or acetylbenzidine. This procedure
quantitates benzidine, N-acetylbenzidine, N,N'-diacetylbenzidine, as conjugates of benzidine. Maximum urinary levels occur 2
to 3 h after exposure [1].
INTERFERENCES: None known.
OTHER METHODS: This method is based on references [2] and [3].

BENZIDINE in urine: METHOD 8306, Issue 2, dated 15 August 1994 - Page 2 of 4
1. Hydrochloric acid, conc. (sp. gr. 1.18). 1. Bottles, polyethylene, 125-mL

2. Sodium hydroxide, 10 N. Dissolve 400 g 2. Gas chromatograph with 28Ni63 electron
NaOH in 1:1 methanohwater capture detector, temperature programming,
(v/v) to make 1 L solution. capillary column option, Grob-type injection
CAUTION: EXOTHERMIC REACTION. system, and electronic integrator.
3. Sodium hydroxide, 5 N.. Dilute 3. Shaker and rotator.
10 f^J with 1:1 methanohwater 4. Evaporator and vortex mixer.
4. Acetone, hexane, methanol, and 5. Centrifuge (refrigerated optional).
benzene*, pesticide grade. 6. Waterbath with a temperature range 30 to
5. Hexane:benzene, 3:2 (v/v). 100°C.
6. Sodium sulfate (anhydrous) extracted in 7. Soxhlet extractor.
Soxhlet extractor for 24 h with benzene. 8. Culture tubes, 25 x 200-mm, 20 x 125-mm,
7. Trimethylamine stock solution. and 16 x 150-mm, with PTFE-lined screw
a. Dissolve 2 g (CH3)3NHCI in 5 ml_ 5 N caps.**
NaOH. 9. Pipettes, 1-, 5- and 10-mL and Pasteur
CAUTION: EXOTHERMIC REACTION (disposable).**
b. Extract four times with 5-mL portions of 10. Graduated centrifuge tubes, 15-mL,
benzene. glass-stoppered.**
c. Percolate each 5 mL extract through a 2- 11. Volumetric flasks.**
cm anhydrous sodium sulfate column.
d. Keep in the dark and refrigerated when ** Wash with detergent, clean with chromic
not in use. Reagent stability unknown. acid, rinse with distilled water, acetone,
8. Trimethylamine working solution. and benzene.
Dilute trimethylamine stock solution 1:20 with
benzene. Reagent stability unknown.
9. Benzidine stock solution, 100 fjg/mL.*
Dissolve 10 mg benzidine, accurately weighed,
in benzene to make 100 mL solution.
Refrigerate. Discard if a color develops.
10. Methylenedianiline stock solution, 100//g/mL
Dissolve 10 mg methylenedianiline,, accurately
weighed, in benzene to make 100 mL solution.
Refrigerate. Discard if color develops.
11. Derivatized methylenedianiline stock solution,
1 ^g/mL
a. Add 0.1 mL methylenedianiline stock
solution to 1.5 mL benzene and 0.5 mL
trimethylamine working solution.
b. Derivatize and wash (steps 12 and 13).
c. Percolate the solution through 2 cm
anhydrous sodium sulfate.
d. Dilute to 10.0 mL with benzene. Stable at
least one month.
12. Florisil, PR grade, 60/100 mesh; activated at
650 °C.
a. Extract 24 h in a Soxhlet extractor with
benzene.
b. Heat to 130°Cfor24h.
c. Cool and add 10 g distilled water/1 OOg
Florisil. Shake overnight.

13. Buffer. Dissolve 136 g KH2PO4 in 900 mL H20.

Adjust to pH 6 with 10 N NaOH. Dilute to 1 L
with H20 and extract once with 100 mL
benzene.
14. Paraffin oil.
15. Heptafluorobutyric anhydride.
16. Nitrogen gas, compressed, purified.
SPECIAL PRECAUTIONS: Samples of urine collected from humans pose a real health risk to laboratory
workers who collect and handle these samples. These risks are primarily due to personal contact with
infective biological samples and can have serious health consequences, such as infectious hepatitis, and
other diseases. There is also some risk from the chemical content of these samples, but this is much
less. Those who handle urine specimens should wear protective gloves, and avoid aerosolization of the
samples. Mouth pipetting, of course, must be avoided. Benzidine and benzene are documented human
carcinogens and must be handled in compliance with 29 CFR 1910.1005 and 1910.1028.
SAMPLING:
1. Collect a spot urine sample in a polyethylene bottle. Add 2 drops 12 N HCI as a preservative.
2. Freeze the samples and ship in an insulated container with dry ice.
3. Keep the samples frozen until analysis.
SAMPLE PREPARATION:
4. Perform a creatinine determination on an aliquot of the sample (e.g., [4]).

5. Pipet 10 mL of the urine specimen into a 50-mL culture tube containing 10 mL 10 N NaOH.
6. Seal the tube and incubate 2 h at 80 °C.
7. Cool to room temperature, add 20 mL benzene, seal, and shake 1 h.
8. Remove the benzene layer and percolate it through a 2-cm column of anhydrous sodium sulfate.
Collect the eluate in a 25 x 200-mm culture tube.
9. Repeat step 8 twice. Combine the extracts.
10. Add three or four drops of paraffin oil to the extracts and concentrate the extracts to near
dryness under a gentle stream of nitrogen.
11. Add 1.5 mL benzene and 0.5 mL trimethylamine working solution.
12. Add 50 fjL heptafluorobutyric anhydride. Seal and place in a 50 °C waterbath for 20 min. Cool
to room temperature.
13. Wash the derivatized extract.
a. Add 2 mL pH 6 buffer solution. Seal and shake 2 min.
b. Centrifuge 2 min. Discard the bottom (aqueous) layer.
c. Repeat the washing with two additional 2-mL portions of pH 6 buffer.
14. Place a small glass wool plug in a chromatographic column and add 1.6 g Florisil. Top with
2 cm anhydrous sodium sulfate. Wash the column with 50 mL hexane.
15. Add the buffer-washed, derivatized extract to the Florisil column. Rinse the culture tube twice
with ca. 2 mL benzene and add the rinsings to the Florisil column.
16. When the top of the extract is in the sodium sulfate layer, add 10 mL 3:2 (v/v) hexane:benzene.
Discard the eluate.
17. Elute the N,N'-diheptafluorobutyryl benzidine with 15 mL benzene.
18. Add 0.5 mL derivatized methylenedianiline stock solution to the eluate. Concentrate to 10 mL
under a gentle stream of nitrogen.

19. Prepare six working standards containing between 0 and 10 //g benzidine.
a. Add aliquots of benzidine stock solution to 1.5 mL benzene and 0.5 mL trimethylamine
working solution.
b. Perform steps 12 and 13.
c. Percolate the benzene layer through 2 cm anhydrous sodium sulfate.
d. Add 0.5 mL derivatized methylenedianiline stock solution.
e. Dilute to 10.0 mL with benzene.
f. Analyze the working standards together with samples and blanks (step 21 and 22).
g. Prepare calibration graph (concentration of standards vs. ratio of peak areas of benzidine to
methylenedianiline).
20. Analyze a spiked urine for every 10 samples (minimum three per study).
MEASUREMENT:
21. Set the chromatograph according to manufacturer's recommendations and conditions given on
page 8306-1 .
22. Inject 3 fjL derivatized sample extract (step 18). Measure peak areas of both methylenedianiline
and benzidine. Calculate the ratio of peak areas (benzidine to methylenedianiline). The tr of
methylenedianiline is 7.6 min while the tr of benzidine is 8.0 min under these conditions.
CALCULATIONS:
23. Determine benzidine urine concentrations (/ug/mL) by comparing the ratio of benzidine
methylenedianiline peak areas for the samples to those obtained for standards on the calibration
graph. Report the results as //g benzidine/g creatinine.
GUIDES FOR INTERPRETATION:
Benzidine is an OSHA-regulated human carcinogen. Although no specific standard has been set, the
fact that benzidine is a human carcinogen means it or its metabolites should not be detected in urine or
any other physiological fluid. However, a level of 0.010 //g/mL has been suggested as an indicator of
excessive exposure [1].
REFERENCES:
[1] Baselt, R. C. Biological Monitoring Methods for Industrial Chemicals, 43, Biomedical Publications,
Davis, CA (1980).
[2] Nony, C. R., and M. C. Bowman. Trace Analysis of Potentially Carcinogenic Metabolites of an
Azo Dye and Pigment in Hamster and Human Urine as Determined by Two Chromatographic
Procedures, J. Chromatographic Sci.. 18, 64 (February, 1980).
[3] Benzidine-Based Dyes, 46, U.S. Department of Health and Human Services, Publ. (NIOSH)
80-109 (1980).
[4] Tietz, N. W. Fundamentals of CIinical Chemistry, 2nd ed., 994-997, W. B. Saunders Co.,
Philadelphia, PA (1976).
METHOD REVISED BY:
Anthony W. Smallwood, Karl E. DeBord, and Alex W. Teass, Ph.D., NIOSH/DBBS.

BENZOYL PEROXIDE 5009
(C6H5CO)2O2 MW: 242.22 CAS: 94-36-0 RTECS: DM8575000

OSHA : 5 mg/m3 PROPERTIES: solid; MP 103 °C;d 1.334g/mL@25 °C

NIOSH: 5 mg/m3 VP not significant; autoignition
ACGIH: 5 mg/m3 temperature 80 °C
SYNONYMS: dibenzoyl peroxide, benzoyl superoxide

(0.8-A/m cellulose ester membrane)
ANALYTE: benzoyl peroxide
EXTRACTION: ethyl ether, 10 mL
SHIPMENT: refrigerated PRESSURE-COLUMN: 9000 kPa (1300 psi)
SAMPLE STABILITY: 9% loss from filter after MOBILE PHASE: 70/30 methanol/water; 1.6 mL/min
1 week © 25 °C
DETECTOR: UV photometer @ 254 nm
COLUMN: 250 mm x 3 mm-ID stainless steel;
Spherisorb ODS (spherical silica
particles with 5% bonded coating of
octadecyl groups) or equivalent
ACCURACY
CALIBRATION: benzoyl peroxide in ethyl ether
(90-L samples) RANGE: 0.2 to 1.7 mg per sample [1]
BIAS: - 0.52%
ACCURACY: ± 11.82%
APPLICABILITY: The working range is 2 to 19 mg/m3 for a 90-L air sample.
OTHER METHODS: This is Method S253 [3] in a revised format. A non-specific gravimetric method and a non-specific
colorimetric method appear in the criteria document [4].

BENZOYL PEROXIDE: METHOD 5009, Issue 2, dated 15 August 1994 - Page 2 of 3
1. Benzoyl peroxide, 99% pure.* 1. Sampler: cellulose ester membrane filter,

2. Ethyl ether, purified, without stabilizer.* 0.8-//m pore size, 37-mm diameter, with
3. Methanol, distilled in glass. backup pad in cassette filter holder.
4. Water, deionized and distilled. 2. Personal sampling pump, 1 to 3 L/min, with
5. Calibration stock solution, 10 mg/mL flexible connecting tubing.
Dissolve 250 mg benzoyl peroxide in ethyl 3. Refrigerated, bagged ("Blue Ice," or
ether and dilute to 25 mL. Stable at least one equivalent).
week at 4 °C. 4. Vials, 20-mL, PTFE-lined caps.
5. High performance liquid chromatograph,
254-nm UV detector, sample injection valve
* See SPECIAL PRECAUTIONS. with a 20-fjL external sample loop, syringe
filter, integrator and column (page 5009-1).
6. Tweezers.
7. Microliter syringes, 10- and 100-//L
8. Volumetric flasks, 10- and 25-mL, assorted
sizes.
9. Pipet, 10-mL, with pipet bulb.
SPECIAL PRECAUTIONS: Benzoyl peroxide is a flammable solid and may explode when heated; it
will attack some plastics, rubber, and coatings [4]. Ethyl ether is highly flammable and forms explosive
peroxides on exposure to air.
SAMPLING:

400 L Do not exceed 2 mg particulate loading on the filter.
3. Ship samples in an insulated container with bagged refrigerant.
SAMPLE PREPARATION:
4. Immediately upon receipt at laboratory, refrigerate the samples.

5. As soon as possible after receipt, transfer each filter to a clean vial with tweezers.
6. Pipet 10 mL ethyl ether into each vial; screw on cap. Swirl to mix.
7. Calibrate daily with at least six working standards covering the range 0.01 to 1.7 mg per sample.
a. Add calibration stock solution with a microliter syringe to ethyl ether in a 10-mL volumetric
flask and dilute to the mark.
b. Analyze together with samples, blanks and control samples (steps 10 through 12).
c. Prepare calibration graph of peak area vs. mass (mg) of benzoyl peroxide per sample.
8. Determine recovery of benzoyl peroxide from filters at least once for each lot of samplers in the
calibration range (step 7). Prepare three filters at each of five levels plus media blanks.
a. Add aliquot of calibration stock solution with a microliter syringe directly onto a media blank
filter in a vial.
b. Prepare and analyze together with working standards (steps 5, 6 and 10 through 12).
c. Prepare a graph of recovery vs. mg benzoyl peroxide recovered.

BENZOYL PEROXIDE: METHOD 5009, Issue 2, dated 15 August 1994 - Page 3 of 3
MEASUREMENT:
10. Set high performance liquid chromatograph according to manufacturer's recommendations and
to conditions given on page 5009-1.
11. Flush sample loop thoroughly with sample (0.1 mL) and inject sample.
CALCULATIONS:
13. Read mass, mg (corrected for recovery), of benzoyl peroxide found on sample filters, W (mg),
and on average blank filters, B (mg), from calibration graph.
14. Calculate concentration, C (mg/m3), of benzoyl peroxide in the air volume sampled, V (L):
C . --, mg/m3
Method S253 was issued on January 21, 1977 [3], and validated over the range 3.1 to 19.1 mg/m3
at 26 °C and 764 mm Hg, using 90-L samples [1,5]. The collection efficiency of the filter was
determined to be 1 .00, since no benzoyl peroxide was detected on a backup filter mounted directly
behind the front filter. Storage stability studies on the filters held in the filter cassettes indicated a 9.3%
decrease in the amount of benzoyl peroxide recovered after one week. Benzoyl peroxide was stable in
ethyl ether at room temperature for at least one week. Overall precision, SrT, was 0.060. Recovery was
0.97 in the range 0.225 to 0.900 mg per sample for 18 spiked samples.
REFERENCES:
[1] NIOSH Backup Data Report, S253, for Benzoyl Peroxide, prepared under NIOSH Contract
No. 210-76-0123, available as "Ten NIOSH Analytical Methods, Set 2," Order No. PB 271-464, from
[2] UBTL Memorandum, UBTL Analytical Laboratory Report for Benzoyl Peroxide, Sequence #2182-J
(unpublished, February 29, 1980).
[4] Criteria for a Recommended Standard. ..Occupational Exposure to Benzoyl Peroxide, U.S.
Workplace Toxic Substances, U.S. Department of Health and Human Services, Publ. (NIOSH) 80-133
(1980).
METHOD REVISED BY:
R. Alan Lunsford, Ph.D., NIOSH/DPSE; S253 originally validated under NIOSH Contract 210-76-0123.

BENZYL CHLORIDE
See HYDROCARBONS, HALOGENATED (Method 1003) for procedure

BERYLLIUM and compounds, as Be 7102
Be MW: 9.01 CAS: 7440-41-7 RTECS: DS 1750000

OSHA : 2 //g/m3; C 5 //g/m3; P 25 ^/m3/30 min PROPERTIES: hard, light metal; valence +2;
NIOSH: not to exceed 0.5 fjg/rrt1 (suspect carcinogen) MP 1284 to 1300 °C
ACGIH: 2 //g/m3 (suspect carcinogen)
SYNONYMS: Vary as to compound.
SAMPLER: FILTER TECHNIQUE: ATOMIC ABSORPTION, GRAPHITE

(0.8 //m cellulose ester membrane) FURNACE
FLOW RATE: 1 to 4 L/min ANALYTE: beryllium
VOL-MIN: 25 L @ 2 fjg/m3 ASHING REAGENTS: HNO3, 10 mL; H2SO4, 1 mL

-MAX: 1000 L
CONDITIONS: 150 °Cuntil brown fumes disappear;
SHIPMENT: routine 400 °C to dense fumes of H2SO4
SAMPLE FINAL SOLUTION: 2% Na2SO4/3% H2SO4; 10 mL

STABILITY: stable
GRAPHITE FURNACE : 110 °C dry 20 sec;
BLANKS: 2 to 10 field blanks per set 900 °C char 10 sec;
2800 °C atomize 18 sec
WAVELENGTH: 234.9 nm
ACCURACY BACKGROUND CORRECTION: D2 or H2 continuum
RANGE STUDIED 2.7 to 11.8//g/m3 [1] INJECTION VOLUME: 10//L

(40-L samples)
CALIBRATION: Be2" in 2% Na2SO4/3% H2SO4
BIAS: - 0.39%
OVERALL PRECISION (SrT): 0.064 [1] RANGE: 0.05 to 1 /jg per sample [2]
ESTIMATED LOD: 0.005 //g per sample [2]
ACCURACY: ± 12.42%
APPLICABILITY: The working range is 0.5 to 10 mg/m3 for a 90-L air sample. The method is applicable to ceiling
measurements using a 25-L air sample.
INTERFERENCES: Calcium interference is masked by 3% (v/v) sulfuric acid. Sodium, potassium, and aluminum enhance
beryllium absorbance; this effect is overcome by addition of 2% (w/v) sodium sulfate to both standards and samples. Perchloric,
phosphoric, and hydrofluoric acids produce interfering non-atomic peaks. These must be removed by digesting to dryness.
OTHER METHODS: This revises Method P&CAM 288 [2], which replaced Method S339 [3]. Flame atomic absorption and
plasma emission (ICP-AES) are not sensitive enough for beryllium at these concentrations.

BERYLLIUM and compounds, as Be: METHOD 7102, Issue 2, dated 15 August 1994 - Page 2 of 3
1. Nitric acid, conc., reagent grade or better. 1. Sampler: mixed cellulose ester membrane
2. Sulfuric acid, conc., reagent grade or better. filter, 0.8-//m pore size, 37-mm diameter in
3. Sodium sulfate, reagent grade. two-piece cassette filter holder.
4. Sodium sulfate, 2% (w/v)/3% sulfuric acid 2. Personal sampling pump, 1 to 4 L/min, with
(v/v). Add 10 g sodium sulfate and 15 mL flexible connecting tubing.
H2SO4 to deionized water. Dilute to 500 mL 3. Atomic absorption spectrophotometer with
5. Calibration stock solution, 1000 //g Be/mL,* graphite furnace and background corrector.
commercially available, or dissolve 1 .000 g Be 4. Beryllium hollow cathode lamp.
metal in a minimum volume of 1:1 HCI, dilute 5. Pressure regulator, two-stage, for Argon.
to 1 L with 1 % (v/v) HCI 6. Beakers, Phillips, 125-mL*
6. Argon, prepurified. 7. Watchglasses.*
7. Water, distilled or deionized. 8. Volumetric flasks, 10-mL*
9. Pipets, 10-mL volumetric, with pipet bulb.*
10. Automatic pipettor with tips, 10-/A. and
* See SPECIAL PRECAUTIONS. assorted sizes for standards.
11. Hotplate, 150 to 400 °C.
12. Waterbath, 60 to 70 °C.
13. Bottles, polyethylene, 25-mL
CIean all glassware with conc, nitric acid

and rinse thoroughly before use.
SPECIAL PRECAUTIONS: Beryllium is very toxic and a suspected human carcinogen [4]. Perform all
acid digestions in a fume hood.
SAMPLING:
1. Calibrate each personal sampling pump with a representative filter in line.

L. Do not exceed 2 mg total dust loading on the filter.
SAMPLE PREPARATION:
3. Open cassettes and transfer filters to clean Phillips beakers.

4. Add 10 mL conc. HNO3 and 1 mL conc. H2SO4. Cover with watchglass.
5. Heat in fume hood on hotplate (150 °C) until brown fumes of HNO3 disappear, then at 400 °C
until dense fumes of H2S04 appear.
NOTE: Verify that the compounds in the samples are soluble with this ashing procedure, e.g.,
ore or mining samples will require HF in the digestion. If additional ashing acids are
used (e.g., HF, HCIO4, or H3PO4), evaporate to complete dryness at this point.
6. Cool and rinse watchglass and sides of beaker with distilled water and evaporate just to dryness.
Remove beaker immediately and air-cool.
7. Pipet 10.0 mL 2% Na2SO4/3% H2SO4 solution into beaker and cover.
NOTE: Start sulfate reagent blanks at this step.
8. Heat in 60 to 70 °C waterbath for 10 min. Allow to stand overnight before analysis to ensure
complete dissolution of BeSO4

BERYLLIUM and compounds, as Be: METHOD 7102, Issue 2, dated 15 August 1994 - Page 3 of 3
9. Calibrate daily with at least six working standards over the range 0.005 to 1 /yg Be per sample.
a. Use serial dilutions of known amounts of calibration stock solution in 2% Na2SO4/ 3% H2SO4
to prepare working standards. Store in polyethylene bottles. Stable at least four weeks.
NOTE: Analyze working standards alternately with the samples to compensate for the increasing
Be signal as the graphite tube ages.
10. Analyze three quality control blind spikes and three analyst spikes.
MEASUREMENT:
11. Set spectrophotometer and graphite furnace according to manufacturer's recommendations and
to conditions on page 7102-1.
12. Inject 10-//L aliquots of samples into graphite tube. Record absorbance (peak height mode).
CALCULATIONS:
13. Read absorbance of samples, A; average media blanks, Ab; average sulfate reagent blanks, Ar;
and working standards, As.
14. Using the working standard, Cs 0ug/mL), analyzed adjacent to the sample of interest, calculate
concentration, C (//g/m3), of Be in the air volume sampled, V (L):
(A - Ab) -Cs-104
C = °
(A, - Ar)V
This method was evaluated using NTIS Standard Reference Material No. 2675 for Be over the range of
0.1 to 0.4 fjg Be/filter (equivalent to one-half to two times the OSHA PEL). Beryllium recovery was
98.2% with a measurement precision, Sp of 0.008 [2]. This method is an improvement of S339 [3],
which was validated over the range of 2.68 to 1 1 .84 mg/m3 using a 40-L sample. Mean recovery was
106.9% with overall precision of 0.064 [1].
REFERENCES:
[1] Documentation of the NIOSH Validation Tests, S339, U.S. Department of Health, Education and
Education and Welfare, Publ. (NIOSH) 79-141 (1979).
[3] Ibid., V. 3, S339, U.S. Department of Health, Education, and Welfare, Publ. (NIOSH) 77-1 57-C (1977).
[4] Criteria for a Recommended Standard. ..Occupational Exposure to Beryllium, U.S. Department of
Health, Education and Welfare, Publ. (NIOSH) 72-10268 (1972); and as revised in August, 1977 in
NIOSH testimony at OSHA hearing.
METHOD REVISED BY:
Mary Ellen Cassinelli, NIOSH/DPSE; S339 validated under NIOSH Contract CDC-99-74-45.

BORON CARBIDE 7506
B4C MW: 55.26 CAS: 12069-32-8 RTECS: None

OSHA : no standard PROPERTIES: solid; d 2.51 g/mL; MP 2350 °C

NIOSH: no standard
ACGIH: no standard
SYNONYMS: None
SAMPLER: CYCLONE + FILTER TECHNIQUE: X-RAY POWDER DIFFRACTION

(10-mm cyclone, Higgins-Dewell (HD) +
5-fjm PVC membrane) ANALYTE: boron carbide
FLOW RATE: HD cyclone: 2.2 L/min ASH: RF plasma asher

nylon cyclone: 1.7 L/min
SUSPEND: in 2-propanol
-MAX: 1000 L REDEPOSIT: 0.45-//m Ag membrane filter
SHIPMENT: routine XRD: Cu target X-ray tube

Optimize for intensity; 1 ° receiving slit
SAMPLE STABILITY: stable Graphite monochromator; scintillation
detector
FIELD BLANKS: 2 to 10 field blanks per set Slow step scan, 0.02°/10 sec
Integrated intensity with background
BULK SAMPLE: required; area respirable or settled dust subtraction
CALIBRATION: standard suspensions of B4C in

2-propanol
ACCURACY
OVERALL PRECISION (SrT): not determined PRECISION (§r): 0.04 [1]
APPLICABILITY: The working range is 0.2 to 4 mg/m for a 500-L air sample. The method is specific for determining respirable
boron carbide among other mine dusts.
INTERFERENCES: Titanium dioxide, silver, titanium diboride, niobium oxide, silver chloride interfere; also see APPENDIX A.
OTHER METHODS: This revises P&CAM 324 [1].

BORON CARBIDE: METHOD 7506, Issue 2, dated 15 August 1994 - Page 2 of 7
1. Boron carbide, ACS grade, <10-//m particle 1. Sampler:

size. a. Filter: 37-mm diameter, 5.0-//m pore size,
a. Wet-sieve ultrasonically with a 1 0-//m sieve polyvinyl chloride filter supported with
to approximate respirable dust. Evaporate backup pad in a two-piece, 37-mm
the alcohol. Dry the sieved material in an cassette filter holder (preferrably,
oven at 1 10 °C for 1 h, cool, and store in conductive) held together by tape or
a desiccator. cellulose shrink band.
2. 2-Propanol. NOTE: Test PVC filter for THF digestion
3. Desiccant. (see Step 4).
b. Cyclone: 10-mm nylon, Higgins-Dewell
(HD), or equivalent.
c. Sampling head holder: Holder must keep
the cassette, cyclone and coupler together
rigidly so that air enters only at the
cyclone inlet.
2. Bulk sampler: PVC membrane filter, 37-mm,
5-fjm pore size in two-piece filter cassette.
Sample closed face at 4 L/min.
3. Sampling pumps: HD cyclone, 2.2 L/min;
nylon cyclone, 1.7 L/min; and bulk sampler, 3
L/min.
4. Silver membrane filters, 25-mm diameter,
0.45-//m pore size. Filters commercially
available (e.g., Poretics Corp., Millipore Corp.)
5. X-ray powder diffractometer equipped with
copper target X-ray tube, graphite
monochromator and scintillation detector.
6. Reference specimen (mica, Arkansas stone or
other stable standard) for data normalization.
7. Filtration apparatus and side-arm vacuum flask
with 25- and 37-mm filter holders.
8. Sieve, 10-//m pore size, for wet sieving.
9. Analytical balance (0.01 mg).
10. Magnetic stirrer with thermally-insulated top.
1 1 . Ultrasonic bath or probe.
12. Pipets, 2- to20-mL
13. Flask, volumetric, 1-L
14. Desiccator.
15. Bottles, 1-L, with ground glass stoppers.
16. Drying oven.
17. Polyethylene wash bottle.
18. Beakers, borosilicate, 50-mL, and matching
watchglasses.
19. Glue or tape for securing Ag filters to XRD
sample holder.
SPECIAL PRECAUTIONS: None.

SAMPLING:

2. Sample at 1.7 ± 5% L/min with a nylon cyclone or 2.2 ± 5% with a HD cyclone for a total
sample size of 100 to 1000 L Do not exceed 2 mg dust loading on the filter.
NOTE 1 : Do not allow the sampler assembly to be inverted at any time. Turning the cyclone
to anything more than a horizontal orientation may deposit oversized material from
the cyclone body onto the filter.
NOTE 2: For determination of total boron carbide, sample on the PVC filter, without cyclone,
at 1 to 4 L/min.
3. Take a bulk dust sample (e.g., 1 m3 at 4 L/min).
SAMPLE PREPARATION:
4. Prepare the high-volume respirable dust or settled dust sample for qualitative analysis. Transfer
to a filter and XRD sample holder by: (1) ashing and redepositing as described below for
personal samples, (2) removing part of the dust from a thickly-coated sample and redepositing
it, or (3) mounting all or part of the collection filter on the holder. The settled dust may be
ground and/or wet sieved to best match the airborne dust exposure. Wet-sieving is done with a
I0-//m sieve, 2-propanol, and an ultrasonic bath, followed by evaporation of excess alcohol,
drying in an oven for 2 h, and overnight storage in a dessicator. Deposit the end product on a
filter or pack in a conventional XRD powder holder and follow step 10.
NOTE: For quantitative determination of percent boron carbide, weigh out, in triplicate,
2 mg of the respirable or sieved dust, transfer to a 50-mL beaker, add 10 mL
2-propanol, and continue with steps 6 and 7.
5. Place the filters in 50-mL beakers in the low temperature asher. Ash according to
manufacturer's instructions. After ashing, carefully add 15 mL 2-propanol to each beaker.
6. Cover the beaker with a watchglass. Agitate in an ultrasonic bath for at least 3 min (until
agglomerated particles are broken up). Wash the underside of the watchglass with 2-propanol,
collecting the washings in the beaker.
7. Place a silver filter in the filtration apparatus. Attach the funnel securely over the entire filter
circumference. With no vacuum, pour 2 to 3 mL 2-propanol onto the filter. Pour the sample
suspension from the beaker into the funnel and apply vacuum. During filtration, rinse the beaker
several times and add rinsings to the funnel. Control filtration rate to keep the liquid level in the
funnel near the top during rinsing. Do not wash the walls or add 2-propanol to the funnel when
the liquid level is lower than 4 cm above the filter. Leave vacuum on after filtration to produce a
dry filter. Remove the filter with forceps and mount it in the XRD sample holder.
8. Select six silver membrane filters randomly from the same box of filters used for depositing the
samples. These will be used as media blanks to correct for sample self-absorption. Mount each
media blank on the filtration apparatus and apply vacuum to draw 5 to 10 mL 2-propanol
through the filter. Remove and let dry. Determine the net normalized intensity for the silver
peak, ]°g , for each media blank (step 11). Average the values for the six media blanks.
9. Prepare and analyze working standard filters.
a. Weigh 10- and 100-mg portions of boron carbide to the nearest 0.01 mg. Quantitatively
transfer each to a 1 -L glass-stoppered bottle using 1 .00 L 2-propanol.
b. Suspend the powder in 2-propanol using an ultrasonic probe or bath for 20 min.
Immediately move the flask to a magnetic stirrer and add a stirring bar. Cool to room
temperature before use.
c. Mount a silver filter on the filtration apparatus. Place 2 to 4 mL 2-propanol on the filter.
Turn off the stirrer and shake the suspension vigorously by hand. Immediately withdraw an
aliquot from the center of the suspension. Do not adjust volume in the pipet by expelling

part of the suspension. If more than the desired aliquot is withdrawn, return all of the
suspension to the bottle, rinse and dry the pipet, and take a new aliquot. Transfer the
aliquot from the pipet to the filter, keeping the tip of the pipet just above the surface of the
delivered suspension.
d. Rinse the pipet with several portions of 2-propanol, draining the rinses into the funnel.
e. Apply vacuum and rapidly filter the suspension. Leave vacuum on until filter is dry. Do not
wash down the sides of the funnel after the deposit is in place since this will rearrange the
material on the filter. Prepare working standard filters in triplicate by this technique at, e.g.,
50, 100, 200, 500, 1000, and 2000 //g boron carbide.
f. Analyze by XRD (step 11). Use the same diffraction peaks and instrumental conditions as
for samples. Designate the net and normalized XRD intensities for the working standard
filters as ix° (step 11.d) and Tx" (step 11. e), respectively. Correct Tx" for matrix absorption
for standards containing >200 //g B4C (steps 11.f and 12).
g. Prepare calibration graph ( Tx° vs. //g B4C ) using 1 /a 2 weighted least squares.
h. Determine the slope, m (counts//yg), of the calibration graph. The intercept, b, of the line
with the Tx° axis should be zero ±5 //g.
MEASUREMENT:
10. Obtain a qualitative X-ray diffraction scan (e.g., 10 to 80° 2-8) of the settled dust bulk or
high-volume respirable sample to determine the presence of boron carbide and any matrix
interference (see APPENDIX). The expected diffraction peaks are:
Peak (Degrees 2-0)

Primary Secondary
Boron carbide 37.80° 34.91°

Silver 38.12° 44.28°
11. Mount the filter (sample, standard or blank) in the X-ray diffractometer and:
a. Determine the net intensity, lr, of the reference specimen before each filter is scanned.
Select a convenient normalization scale factor, N (approximately equal to the net count for
the reference specimen peak). Use this value of N for all analyses.
NOTE: Normalizing to the reference specimen intensity compensates for long-term drift in
X-ray tube intensity. If intensity measurements are stable, the reference specimen
may be run less frequently and the net intensities should be normalized to the most
recently measured reference specimen intensity.
b. Measure the area of the most intense, interference-free diffraction peak of B4C. Scan times
must be long, e.g., 15 min.
c. Determine the position of the background for each sample. Measure the background on
each side of the peak for one-half the time used for peak scanning. Add the counts from
each side to obtain total background.
d. Calculate net intensity, lx (peak count minus total background count).
e. Calculate the normalized intensity, lx = lx • N/lr.
f. Determine the net normalized intensity, TAg , of an interference-free silver peak on the
sample filter following the same procedure. Use a short scan time for the silver peak (e.g.,
5% of scan time for analyte peaks) throughout the method.
g. Scan each field blank over the same 2-9 range used for B4C and silver peaks. These
analyses serve only to verify that contamination of the filters has not occurred. The analyte
peak should be absent. The normalized intensity of the silver peak should match that of the
media blanks.

BORON CARBIDE: METHOD 7506. issue 2, dated 15 August 1994 - Page 5 of 7
CALCULATIONS:
12. Calculate the concentration of boron carbide, C (mg/m3), in the air volume sampled, V (L):
c . klSLL*
m • V
, ms/m>.
where: Tx = normalized intensity for sample peak

b = intercept of calibration curve ( ~\° vs. W)
m = initial slope of calibration curve, counts //g
f(T) = "R ln J = absorption correction factor (Table 1 )
R = sin (0Ag)/sin (0X)

T = TAg/(average !A°g ) = transmittance of sample
TAg = normalized silver peak intensity from sample
average TA°g = normalized silver peak intensity from media blanks (average of
six values)
NOTE: For a more detailed discussion of the absorption correction procedure, see references
[2] and [3].
The method was developed using the secondary B4C peak because the primary B4C peak interfered
with the primary peak of AgCI, which is usually found on silver filters [1]. B4C that was previously
ground, sieved through a 10-//m sieve and dried, was used to prepare 30 working standards on 25-mm
silver filters in the range 20 to 2000 //g per filter (10 levels, three at each level). The detection limit was
50 fjg per filter. The limit of quantitation was 100 //g per filter. The calibration graph had a linear
correlation coefficient of 0.9999 and a pooled relative standard deviation of 0.04 (n = 24). Recovery was
0.92 with sr = 0.02 from five FWS-B (MSA Co.) filters spiked at the 600 //g level; the filters were ashed in
a low temperature asher and were treated as described in SAMPLE PREPARATION.
REFERENCES:
[1] NIOSH Manual of Analytical Methods, 2nd ed., Vol. 6, P&CAM 324, U.S. Department of Health and
[2] Leroux, J. and C. Powers. Direct X-Ray Diffraction Quantitative Analysis of Quartz in Industrial Dust
Films Deposited on Silver Membrane Filters, Occup. Health Rev.. 21, 26 (1970).
[3] Williams, D. D. Direct Quantitative Diffractometric Analysis, Anal. Chem.. 31, 1841 (1959).
METHOD WRITTEN BY:
J. Palassis, NIOSH/DTMD.

APPENDIX:
INTERFERENCES
When using copper Ka X-radiation, titanium dioxide (anatase) and the primary peak of silver interfere
with the primary boron carbide peak; therefore, no measurements can be done with either the primary
boron carbide or the silver peak. The secondary boron carbide peak is chosen as the analytical peak if
no other interferences are present.
The secondary titanium diboride peak interferes to a small extent with the secondary boron carbide
peak. The primary titanium diboride peak interferes with the secondary silver peak.
Niobium oxide interferes with the tertiary boron carbide peak.
Silver chloride, found as an impurity in the silver filter, may interfere with some low-intensity boron
carbide peaks.
When peak overlaps are not severe, a smaller receiving slit or chromium X-radiation may be used;
however, a new calibration graph will be necessary.
The presence of some elements in the sample (iron, in particular) can result in appreciable X-ray
fluorescence, leading to high background intensity. This can be minimized by a diffracted beam
monochromator.
The interfering effects of X-ray absorption by the sample result in attenuation of the diffracted beam and
correction must be made (step 12 and Table 1).

Table 1 . Matrix absorption correction factors, boron carbide/silver peak, degrees 26.
Boron Carbide 34.91 23.54 22.11 34.91 23.54 21.11

Silver 44.28 44.28 44.28 44.28 44.28 44.28
T f(T) f(T) f(T) T fm f(T) f(T)
1. 00 1 .000 1.000 1.000 0.74 1.2011 1 .3038 1 .3249

0.99 1 .0063 1 .0093 1 .0099 0.73 1.2107 1 .3187 1.3409
0. 98 1 .0127 1.0188 1 .0200 0.72 1 .2205 1 .3340 1 .3573
0,97 1 .0193 1 .0284 1 .0302 0.71 1 .2305 1 .3495 1 .3740
0.96 1 .0259 1 .0382 1 .0407 0.70 1 .2407 1 .3654 1.3911
0.95 1 .0326 1.0481 1.0513 0.69 1.2512 1 .3816 1 .4086
0,,94 1 .0394 1 .0582 1 .0620 0.68 1.2618 1.3982 1 .4264
0.93 1 .0463 1 .0685 1 .0730 0.67 1 .2726 1 .4152 1 .4447
0.,92 1 .0533 1 .0790 1 .0842 0.66 1 .2836 1 .4325 1 .4633
0.,91 1 .0604 1 .0897 1 .0955 0.65 1 .2949 1 .4502 1 .4824
0.90 1 .0676 1.1005 1.1071 0.64 1 .3064 1 .4683 1 .5019
0. 89 1 .0750 1.1115 1.1189 0.63 1.3182 1 .4868 1 .5218
0,,88 1 .0825 1.1227 1.1309 0.62 1.3302 1 .5058 1 .5423
0.,87 1 .0900 1.1342 1.1431 0.61 1.3425 1 .5252 1 .5632
0..86 1 .0977 1.1458 1.1555 0.60 1 .3550 1 .5450 1 .5846
0. 85 1 .1056 1.1576 1.1682 0.59 1 .3678 1 .5654 1 .6066
0..84 1 .1135 1.1697 1.1811 0.58 1 .3809 1 .5862 1 .6290
0, 83 1 .1216 1.1820 1.1943 0.57 1 .3944 1 .6076 1 .6521
0 82 1 .1298 1.1945 1.2077 0.56 1.4081 1 .6295 1 .6757
0. 81 1 .1382 1 .2073 1.2213 0.55 1.4221 1 .6519 1 .7000
0.80 1 .1467 1.2203 1.2353 0.54 1.4365 1 .6750 1 .7249
0.,79 1 .1554 1 .2335 1.2495 0.53 1.4513 1 .6986 1 .7504
0..78 1 .1642 1 .2470 1.2640 0.52 1 .4664 1 .7229 1 .7766
0..77 1 .1732 1 .2608 1.2787 0.51 1.4819 1 .7478 1 .8036
0,.76 1 .1823 1 .2749 1 .2938 0.50 1.4979 1 .7734 1 .8312
0,,75 1 .1916 1 .2892 1.3092
T = sample transmittance (step 12).

f(T) = sample correction factor (step 12).

BROMINE 6011
See CHLORINE, Method 6011, for procedure
Br, MW: 159.82 CAS: 7726-95-6 RTECS: EF9 100000
METHOD: 6011 .Issue 2 EVALUATION: FULL Issue 1: 15 May 1989

OSHA : 0.1 ppm PROPERTIES: liquid; d 3.1 19 g/mL @ 20 °C;

NIOSH: 0.1 ppm; STEL 0.3 ppm BP 58.78 °C; VP 23.3 kPa (175 mm Hg)
ACGIH: 0.1 ppm; STEL 0.3 ppm @ 20 °C vapor density (air= 1) 5.5
(1 ppm = 6.53 mg/m3)
SYNONYMS: None.
SAMPLER: PREFILTER + FILTER TECHNIQUE: ION CHROMATOGRAPHY,

(PTFE, 0.5-//m + silver membrane, CONDUCTIVITY
25-mm, 0.45-^m)
ANALYTE: bromide ion (Br)
EXTRACTION: 3 mL 6 mM NajSgOg, 10 min
VOL-MIN: 8 L (5)0.1 ppm
SHIPMENT: routine, protect from light COLUMN: Dionex HPIC-AG4A guard, HPIC-AS4A
separator, MFC-1 precolumn, AMMS
SAMPLE anion suppressor
STABILITY: 2:30 days at 25 °C [1]
DETECTOR SETTING: 10 fjS full scale
ELUENT: 0.25 mM NaHCO.j/4 mM
NajCOg/OJa mM p-cyanophenol,
2 mL/min
ACCURACY
CALIBRATION: standard solutions of Br in
RANGE STUDIED: 0.07 to 1 .42 mg/m3 deionized water
(72-L samples)
RANGE: 5 to 150 //g Br per sample [1]
BIAS: - 1.2%
OVERALL PRECISION (SrT): 0.069 [1] ESTIMATED LOD: 1.6 //g Br per sample [1]
ACCURACY: ± 13.6%
PRECISION (§r): 0.045 @ 5 to 100^g per sample [1]
APPLICABILITY: The working ranges for Br2 and CI2 are 0.008 to 0.4 ppm (0.06 to 2.6 mg/m3) and 0.007 to 0.5 ppm (0.02 to
1.5 mg/m3) respectively for a 90-L air sample. The method has sufficient sensitivity for STEL samples.
INTERFERENCES: Hydrogen sulfide gives a negative interference. HCI gives a positive interference upon a maximum of 15
fjg per sample. HBr gives a positive interference as it is sampled continuously [1].
OTHER METHODS: P&CAM 209 (colorimetric) [2], OSHA Methods ID-101 [3] and 10-108 [4] are alternative methods.

BROMOFORM

(1) BROMOXYNIL and (2) BROMOXYNIL OCTANOATE 5010
(1) C7H3Br2NO MW: (1) 276.93 CAS: (1) 1689-84-5 RTECS: (1) DI3150000
(2) Cl5H17Br2NO2 (2) 403.13 (2) 1689-99-2 (2) DI3325000

OSHA : no PEL PROPERTIES: (1) liquid; BP 194 to 195 °C;

NIOSH: no REL (2) solid; MP 45 to 47 °C
ACGIH: noTLV
SYNONYMS: (1): 2,6-dibromo-4-cyanophenol; 3,5-dibromo-4-hydroxybenzonitrile;

(2): 2,6-dibromo-4-cyanophenyl octanoate.

ANALYTE: Bromoxynil; Bromoxynil octanoate
EXTRACTION: 3 mL acetonitrile; 60 min
VOL-MIN: 2 [email protected] mg/m3
-MAX: 400 L MOBILE PHASE: acetonitrile/water gradient; 1 mL/min
SHIPMENT: refrigerated; protect from light COLUMN: //-Bondapack C18, 25 cm x 4.6 mm-ID
reverse phase or equivalent
SAMPLE
STABILITY: at least 25 days @ 4 °C in the dark [1] DETECTOR: UV detector @ 254 nm
BLANKS: 2 to 10 field blanks per set CALIBRATION: solutions of analytes in acetonitrile
ESTIMATED LOD: (1) 0.6 and (2) 0.3 fjg per sample [1]
ACCURACY
PRECISION (Sr): (1) 0.011 @ IS fjg per sample [1]
RANGE STUDIED: not studied (2) 0.042 @ 35 //g per sample [1]
APPLICABILITY: The working range is 0.02 to 0.3 mg/m3 for a 100-L air sample. This method permits the simultaneous
determination of both analytes.
INTERFERENCES: None known. Both analytes photodecompose.
OTHER METHODS: A gas chromatographic method has been described [2].

BROMOXYNIL and BROMOXYNIL OCTANOATE: METHOD 5010, Issue 2, dated 15 August 1994 - Page 2 of 3
1. Bromoxynil. 1. Sampler: PTFE-coated glass fiber (Pallflex

2. Bromoxynil octanoate. T60A20) or 2-//m PTFE membrane (GHIA),
3. Acetonitrile, HPLC grade. 37-mm diameter. (Filters commercially
4. Water, distilled, deionized. available).
5. Calibration stock solution, 1 mg/mL Dissolve NOTE: Use opaque or light-protected
0.100 g each of Bromoxynil and Bromoxynil cassette filter holder.
octanoate in acetonitrile; dilute to 100 mL in a 2. Personal sampling pump, 1 to 3 L/min, with
volumetric flask. Prepare daily, in duplicate. flexible connecting tubing.
3. Jars, ointment, 60-mL, squat form, with PTFE-
lined screw caps.
5. Pipet, 3-mL
6. Vials (for autosampler).
7. Liquid chromatograph with gradient capability,
UV detector (254 nm) and column, (see page
5010-1).
8. Syringes, 5-mL
9. Syringe filters, PTFE; or Swinnex adaptor with
luer fitting containing 0.5-//m PTFE filter,
13-mm.
SPECIAL PRECAUTIONS: None.
SAMPLING:

400 L Do not exceed 2 mg total dust loading on filter.
3. After sampling, cap the filter holders, ship at 4 °C and protect from light.
SAMPLE PREPARATION:
4. Transfer the filter to a jar. Add 3.0 mL acetonitrile and desorb with occasional swirling for at
least 1 h.
5. Filter an aliquot through a PTFE syringe filter or a 0.5-//m PTFE filter using a syringe with a
Swinnex adaptor to remove particulate. Transfer the aliquot to a sample vial and seal.
6. Calibrate daily with at least six working standards over the range 0.6 to 30 //g of both analytes
per sample.
a. Add known amounts of calibration stock solution to acetonitrile in 10-mL volumetric flasks
and dilute to the mark.
c. Prepare calibration graph (peak area vs. //g analyte).
NOTE: Before processing any samples, demonstrate, through the analysis of a solvent
blank, that all glassware and reagents are interference-free. Each time a new set of
samples is analyzed or there is a change in reagents, process a solvent blank as a
safeguard against chronic laboratory contamination.

BROMOXYNIL and BROMOXYNIL OCTANOATE: METHOD 5010, Issue 2, dated 15 August 1994 - Page 3 of 3
MEASUREMENT:
7. Set the liquid chromatograph to the conditions on page 5010-1 using the following mobile phase
gradient: 50% CH3CN/50% H2O for 10 min; 10 min gradient to 100% CH3N; hold 10 min; 2 min
gradient to 50% CH3CN/50% H2O; hold 15 min.
8. Inject 100 fjL sample extract with a high-pressure syringe or a sampling loop. Record the
volume injected to the nearest 0.5 fjL. Under these conditions, the retention times are 3.6 min
for Bromoxynil and 33 min for Bromoxynil octanoate.
NOTE: If the peak area exceeds the linear range of the system, dilute with acetonitrile and
reanalyze. If the peak area measurement is hindered by the presence of interferences,
other chromatographic conditions may be required.
CALCULATIONS:
10. Read the mass of analytes (including appropriate aliquot factors) in the sample extract, W
and average media blank, B (/i/g), from the calibration graph.
11. Determine the concentrations, C (mg/m3), of each analyte in the air volume sampled, V (L)
C . W-I-I. mg/m'.
This method was developed with laboratory samples during the period June to September, 1983 [1].
PTFE-coated glass fiber filters were spiked with 50 //g Bromoxynil and 90 fjg Bromoxynil octanoate, after
which 90 L of clean air at 80% RH was drawn through the filters. Recoveries averaged 93% for
Bromoxynil and 100% for Bromoxynil octanoate with relative standard deviations, Sr, of 0.046 and 0.020,
respectively. Storage at ambient conditions for 14 days gave recoveries of 70 to 80% for both
compounds, while storage under refrigeration for 25 days or at ambient conditions for two days followed
by refrigeration for 23 days gave recoveries in the range 95 to 98%.
REFERENCES:
[1] Arthur D. Little, Inc., Backup Data Report prepared under NIOSH Contract 200-82-2528
(unpublished, October 7, 1983).
[2] Thrun, K., J. Harris, and V. Grady. "Sampling and Analysis Procedures for Pesticide
Manufacturing Wastes," Report, EPA Contract No. 68-02-3111 (1982).
METHOD WRITTEN BY:
K. T. Menzies, K. J. Beltis, A. C. Roche, Arthur D. Little, Inc.; and B. R. Belinky, NIOSH/DPSE.

1,3-BUTADIENE 1024
H2C = CHHC = CH2 MW: 54.09 CAS: 106-99-0 RTECS: EI9275000

OSHA : 1000 ppm PROPERTIES: gas; vapor density 1.9 (air = 1);
NIOSH: lowest feasible; suspect carcinogen BP -4.4 °C; explosive range 2.0 to
ACGIH: 10 ppm; suspect carcinogen 11.5% v/v in air
(1 ppm = 2.21 mg/m3 @ NTP)
SYNONYMS: butadiene; biethylene; divinyl

(coconut charcoal, 400- and 200-mg
in separate tubes) ANALYTE: 1,3-butadiene
FLOW RATE: 0.01 to 0.5 L/min DESORPTION: 4 mL methylene chloride; 30 min
VOL-MIN: 5 L@ 100 ppm INJECTION: 1 //L

-MAX: 25 L
SHIPMENT: separate front and back tubes, -DETECTOR: 250 °C
chill below -4 °C -COLUMN: see APPENDIX A
SAMPLE CARRIER GAS: helium

STABILITY: at least two months for quality
assurance blind spikes stored in a freezer MAKEUP GAS: nitrogen, 30 mL/min
BLANKS: 2 to 10 field blanks per set COLUMNS: fused silica, 10 m x 0.50-mm ID 1.8-//m CP
WAX 57 CB (backflushable pre-column), and
50 m x 0.32-mm ID AI2O3/KCI PLOT (see
APPENDIX A)
ACCURACY
CALIBRATION: vapor-spiked sampling media
RANGE STUDIED: 0.19 to 19 mg/m3
(25-L samples) RANGE: 1 to 480 //g per sample
BIAS: 0.1%
ESTIMATED LOD: 0.2 tig per sample
OVERALL PRECISION (SrT): 0.060
PRECISION (§,): 0.025
ACCURACY: ± 11.32%
APPLICABILITY: The working range is 0.02 to 100 ppm (0.04 to 220 mg/m3) for a 25-L air sample. At the higher levels,
desorbed samples may require dilution. Below 0.9 mg/m3 (0.4 ppm), the desorption efficiency falls below 75% and allowance
should be made for decreased accuracy.
INTERFERENCES: Pentane, methyl acetylene, or vinylidene chloride may chromatographically interfere at high levels. High
humidity (>80% RH) or other hydrocarbons present at permissible levels may significantly decrease the sampler's capacity for
1,3-butadiene.

1,3-BUTADIENE: METHOD 1024, Issue 2, dated 15 August 1994 - Page 2 of 8
1. Methylene chloride,* chromatographic quality 1. Sampler: Tandem charcoal tubes. Each tube
with hydrocarbon (cyclohexene) preservative. is flame-sealed glass (8.5 cm long, 8-mm OD,
2. 1 ,3-Butadiene,* 99.5%, in cylinder equipped 6-mm ID), has plastic caps for resealing, and
for gas withdrawal, with needle valve. contains activated coconut shell charcoal
3. Helium, purified. (such as SKC Lot 120) preceded by silylated
4. Hydrogen, purified. glass wool and followed by a 3-mm urethane
5. Air, purified. foam plug. The front tube holds 400 mg
6. Nitrogen, purified. charcoal. The back tube holds 200 mg.
7. Water, distilled. 2. Personal sampling pump, 0.01 to 0.5 L/min,
3. Refrigerant, bagged (e.g., Blue Ice or dry ice),
and insulated shipping container.
See SPECIAL PRECAUTIONS. integrator, and column (see APPENDIX A).
5. Ice, wet.
6. Vials, 5-mL, 2-mL, 1-mL, and other convenient
sizes, with PTFE-lined septum caps.
7. Pipettes, TD, 4-, 2-, and 1 -mL
8. Syringes, gas-tight, 250-, 100-, 25-, and 10-//L
9. Beaker, 150-mL
10. Gas drying tube with serum cap to fit stem
and 2-cm piece of plastic tubing to fit over
serum cap.
SPECIAL PRECAUTIONS: 1 ,3-Butadiene is a potential carcinogen, teratogen, and reproductive hazard

[2]. Methylene chloride is toxic, very volatile, and a suspect carcinogen [3]. Work should be performed
in a well-ventilated fume hood.
SAMPLING:

2. Immediately before sampling, break ends of sampler tubes. Connect smaller tube to personal
sampling pump with flexible tubing and to larger tube with a short piece of plastic tubing.
3. Sample at an accurately known flow rate of 0.01 to 0.5 L/min for a sample size of 5 to 25 L
4. Separate the tubes, cap, and pack securely for shipment. Chill below -4 °C during shipment
and storage.
SAMPLE PREPARATION:
5. Add 4.0 mL methylene chloride to 5-mL vials and 2.0 mL to 2-mL vials. Loosely cap vials and
thoroughly chill in ice.
6. Place front sorbent sections in 5-mL vials and back sections in 2-mL vials. Discard glass wool
and foam plugs. Immediately cap each vial.
7. Remove from ice and allow to stand 30 min with occasional agitation.
8. Transfer sample solution to appropriate vial and cap if using an autosampler. Thoroughly chill
solution and vial before making transfer.

NOTE: The accurate measurement of pure 1 ,3-butadiene gas by gas-tight syringe is a critical
step in the calibration. Even a slight obstruction (e.g., flakes of PTFE from the plunger
tip which obstruct the needle) can cause 1 ,3-butadiene to be liquified as the plunger is
depressed, making delivery incomplete. Bracketing gas samples with water, as
described below, allows the volume taken to be approximately verified, and assures
complete delivery. The precision of the analysis of multiple independent standards is
another indicator of the accuracy of the volumes taken.
9. Make up stock solutions in triplicate at three concentration levels, e.g., 200 //L of 1,3-butadiene
gas in 1 mL solution, and both 200 and 50 fji of gas in 4 mL solution:
a. Prepare a beaker and drying tube assembly as shown. Bubble 1,3-butadiene under the
lower edge of the drying tube so that water is displaced and the gas is trapped in the tube.
plastic tubing
water
serum cap
gas drying tube

filled with water
• beaker
•water
b. Pipet 1 or 4 mL of methylene chloride into a 1- or 5-mL vial, cap, and thoroughly chill.
c. Take a known amount (50 or 200 fjL) of 1,3-butadiene from the drying tube with a 100- or
250-fjL gas-tight syringe. Bracket the gas in the syringe with small amounts of water (5 to
10% of syringe volume) taken from the area above the serum cap before and after
withdrawing the gas. Do not take water from inside the drying tube, since it may contain a
significant amount of dissolved 1 ,3-butadiene.
d. Slowly inject the 1 ,3-butadiene and water below the surface of the methylene chloride.
e. Agitate and continue to chill the vial to complete dissolution.
10. Calibrate daily with media blanks and triplicate independent media standards of at least six levels
ranging from, e.g., 0.5 to 200 //L 1,3-butadiene gas per sample:
a. Break ends of larger sampler and attach to personal sampling pump with flexible tubing.
b. Take pure gas (50 or 200 //L, as in step 9.c) for the higher levels, or 40 fjL of stock solution
for lower levels.
c. Inject the gas and surrounding water plugs or the stock solution at a point inside the
sampler near the glass wool plug while drawing clean air through tube at 0.05 L/min.
Continue to draw air through the tube for 5 min or just until the stock solution evaporates.
d. Seal tube with plastic caps.
e. Store at temperature below -4 °C overnight, then desorb (steps 5 through 8).
f. Analyze media standards and blanks together with samples (steps 13 and 14).
g. Convert gas volumes to masses, correcting for compressibility and water vapor (see
APPENDIX B), and prepare a calibration graph (peak areas or heights vs. concentration of
1,3-butadiene taken in

11. Determine desorption efficiency (DE) at least once for each lot of charcoal used for sampling in
calibration range (step 10).
a. Dilute the stock solutions (step 9) with methylene chloride to extend the range of standards
down to 0.1 //g/mL Avoid including water in the portions diluted.
b. Transfer solutions as in step 8 if using an autosampler, and analyze together with media
standards (steps 13 and 14).
c. Convert gas volumes to masses, correcting for compressibility and water vapor (see
APPENDIX B), and prepare DE calibration graph of peak area or height vs. ^g/mL
1,3-butadiene.
d. Read the concentrations, //g/mL, in media standards and blanks from DE calibration graph
and multiply by the desorption volume to calculate the masses recovered.
e. Prepare a graph of DE vs. //g taken. DE = (mass found - blank mass)/(mass taken).
12. Analyze three quality control blind spikes to insure that calibration graph (step 10) is in control.
MEASUREMENT:
autosampler.
NOTE: If detector response is above range of working standards, dilute with methylene chloride,
reanalyze, and apply appropriate dilution factor in calculations.
14. Measure peak area or height.
NOTE: Vinylidene chloride, an impurity in methylene chloride, elutes just after 1,3-butadiene and
may be used as an internal standard.
CALCULATIONS:
15. Determine the concentration, //g/mL, of 1,3-butadiene found in each sample front (Wf) and back
(Wb) sorbent section from calibration graph (step 10), and multiply by desorption volume, D, mL,
and dilution factor, if any, to calculate the mass, //g, found.
NOTE 1: This calibration method corrects for media blank and DE. Do not duplicate
corrections.
NOTE 2: For any sampler with Wb > Wf/10, report breakthrough and possible sample loss.
^ - Wb) • D , .
C = — ——^- , mg/m3.
The detector responses determined for triplicate standard solutions at each of five levels were linear over
the range 0.3 to 440 //g per sample. The pooled Sr was 0.038. The estimated LOD was 0.02 //g/mL
The capacity of a 400-mg charcoal sorbent section was 31 L for a sample at 80% RH and approximately
56 ppm 1,3-butadiene. When exposed to 0.7 and 2.5 mL of pure 1,3-butadiene gas followed by 80% RH
air, breakthrough occurred after 35 L and 28.5 L, respectively. The corresponding respective
time-weighted average concentrations were 20 and 88 ppm.
For the analysis of media standards at levels of 1.1, 4.4, 18, 125, and 480 ^g per sample, the pooled Sr
was 0.025, and the desorption efficiencies were 67%, 68%, 75%, 102%, and 97%, respectively. Adding
water to media standards just after spiking or during desorption had no significant effect on desorption
efficiencies.

In a study of temperature effects on storage stability, 400-mg charcoal tubes were spiked with 26 //g
1,3-butadiene and stored either at ambient temperature or in a freezer below -4 °C. Recoveries were
measured relative to media standards stored overnight in the freezer. The recoveries (and days stored)
were 94% (7), 93% (14), and 98% (21) for the frozen samples, and 95% (1), 76% (7), 61% (14), and 65%
(21) for the ambient samples.
In a preliminary evaluation of precision and accuracy, charcoal tubes were spiked with 125 //g
1,3-butadiene via calibrated sampling valve. The recovery was 102.2% versus media standards
(corrected for desorption efficiency) and 96.8% versus standard solutions (uncorrected for desorption
efficiency); the Sr of the response was 0.016. Subsequently, simulated samples were exposed to known
amounts of approximately 10% 1,3-butadiene in helium, followed by 25 L of air at 80% RH. The
1,3-butadiene concentration was independently determined by packed column gas chromatography with
thermal conductivity detection. Media standards were prepared via calibrated sampling valves. The
recovery from six simulated samples at 463 //g per sample was 101.6% versus media standards and
91.3% versus standard solutions; the Sr of the response was 0.047. At 45.3 //g per sample, the recovery
was 112.3% versus media standards and 102.9% versus standard solutions; the Sr of the response was
0.048. At 4.64 //g per sample, the recovery was 80.3% versus media standards and 103.8% versus
standard solutions; the Sr of the response was 0.011. In the latter experiment, the two lowest levels of
media standards appeared to be high, possibly due to absorption and release of 1,3-butadiene by
internal parts of the sampling valve. The study was repeated at 4.71 //g, with the three lowest levels of
media standards prepared as in step 10. The recovery was 129.5% versus media standards and 91.2%
versus standard solutions; the Sr of the response was 0.023. The Sr of the response pooled for all levels
was 0.033. Assuming a sampling pump error of 0.05, the precision (SrT) of the total sampling and
analytical method was 0.060. For levels at and above 45 //g (0.8 ppm in 25 L), apparent biases may be
attributed to experimental errors in the preparation and analysis of standards and samples rather than a
true bias in the method. At lower levels, based on the linear response and near-zero intercept observed
for the standard solution calibrations and the higher than expected desorption efficiencies for the
samples, there appeared to be a positive bias in the preparation of the simulated samples.
The method has been used in six industrial hygiene surveys, for a total of 621 samples, most of which
were collected under conditions of high ambient temperature and humidity. Only two samples showed
significant breakthrough (Wb > Wf/10). Results for field samples at levels as high as 7.3 mg per sample
were not significantly changed by dilution and reanalysis. In all, over 2000 analyses were made over a
period of six months without any deterioration of the chromatographic columns. During the course of
the analyses, twenty sets of standard solutions and media standards were prepared and analyzed, each
set consisting of triplicates at each of five levels corresponding to 1.08 to 1.10, 4.32 to 4.40, 17.3 to 17.6,
108 to 110, and 432 to 441 //g per sample. For the five levels of standard solutions, the respective
pooled relative standard deviations of the observed responses were 0.093, 0.074, 0.059, 0.055, and
0.071 . For each set of standard solutions, the deviations of the responses were determined relative to
the line resulting from a weighted linear regression of response on concentration. The 95% confidence
intervals for the mean relative deviations from linearity for the five levels were -0.002 ± 0.003, 0.000 ±
0.003, -0.020 ± 0.002, 0.002 ± 0.002, and -0.019 ± 0.002, respectively. For the media standards,
the respective pooled Sr for the observed responses at the five levels were 0.109, 0.080, 0.050, 0.064,
and 0.037; the respective 95% confidence intervals for the mean percent recoveries relative to the
standard solution calibrations were 60.4 ± 0.4, 66.4 ± 0.3, 70.5 ± 0.2, 86.2 ± 0.3, and 91.2 ± 0.2.
The analysis of quality assurance blind spikes provided additional data indicating that samples were
stable when stored below -4 °C, and that average recoveries, calibrated against media standards,
ranged from 96 to 107%. Seventy-seven blind spikes were prepared at six levels, 19.9 to 21.9, 48.6 to
52.6, 104 to 110, 199 to 219, 398 to 438, and 663 //g per sample, stored in a freezer, and analyzed along
with the field samples. The storage times ranged from 3 to 134 days; the average was 59 days. For the
six levels of blind spikes, the respective relative standard deviations for recoveries were 0.210, 0.092,
0.054, 0.091, 0.126, and 0.056; the respective 95% confidence intervals for the mean recoveries were
0.986 ± 0.032, 0.961 ± 0.014, 0.994 ± 0.008, 1.029 ± 0.015, 1.064 ± 0.021, and 1.074 ± 0.021. Prior
to linear regression of the recoveries versus the amounts spiked and/or days stored, three results, two
high and one low, were determined to be outliers by application of one-sided Grubbs tests [4] at the

2.5% significance level and were dropped from the data set. Linear regression of percent recovery on
days stored for the data segregated by level resulted in respective slopes and 95% confidence intervals
Of 0.060 ± 0.080, 0.005 ± 0.128, -0.003 ± 0.092, 0.060 ± 0.179, 0.249 + 0.188, and 0.018 ± 0.247
percent per day. Thus, the only statistically significant correlation between recovery and days stored
was at the next to highest level, for a gain rather than loss over time. Over all levels, the slopes and
95% confidence intervals for recovery versus amounts spiked and days stored were 0.017 ± 0.009
percent per //g and 0.045 ± 0.051 percent per day, respectively. Thus, according to the latter model:
the recovery for the blind spikes increased at a rate corresponding to approximately 1 1 % over the range
prepared; as stored, the blind spikes appeared to be stable -- the 95% confidence interval of the slope
over time indicated a maximum gain of 5.7% or loss of 0.4% during the average 59-day storage period.
REFERENCES:
[1] NIOSH Manual of Analytical Methods, 2nd. ed., V. 2, S91, U.S. Department of Health Education, and
[2] NIOSH Current Intelligence Bulletin 41, "1,3-Butadiene," U.S. Department of Health and Human
Services, Publ. (NIOSH) 84-105 (1984).
[3] NIOSH Current Intelligence Bulletin 46, "Methylene Chloride," U.S. Department of Health and Human
[4] Grubbs, F. E. "Procedures for Detecting Outlying Observations in Samples," Technometrics. 11(1).
1-21, (February, 1969).
[5] MacCallum, R. N., and J. J. McKetta. "Low Pressure Zs of C4 Hydrocarbons," Hydrocarbon Process.
Petrol. Refiner. 42(5). 191-194 (1963).
METHOD WRITTEN BY:
R. Alan Lunsford, Ph.D., Yvonne T. Gagnon, NIOSH/DPSE and John Palassis, NIOSH/DTMD.
APPENDIX A. GAS CHROMATOGRAPH COLUMN SELECTION, INSTALLATION, AND OPERATION:
Any column which separates 1,3-butadiene from the other substances present, and which otherwise
provides satisfactory chromatographic performance, is acceptable. The column specified in NIOSH
Method S91 [1] is 6 m x 3-mm OD stainless steel, packed with 10% FFAP on 80/100 mesh Chromosorb
W AW-DMCS. It provides a convenient separation of 1 ,3-butadiene from the desorbing solvent.
However, if other C4 to C6 hydrocarbons are present, interferences are likely. For the development of
this method, a 50 m x 0.32-mm ID fused-silica porous-layer open-tubular (PLOT) column coated with
AI2O3/KCI (Cat. # 7515, Chrompack, Bridgewater, NJ) was chosen as the analytical column because it
provides a very efficient separation at temperatures above ambient. However, water from the samples
deactivates the aluminum oxide, reducing retention times, and high-boiling or polar substances may
accumulate on the column and irreversibly degrade the separation. The degradation was eliminated by
using a backflushable pre-column, i.e., 10 m x 0.5-mm ID fused-silica CP Wax 57 CB (Cat. # 7648,
Chrompack, Bridgewater, NJ). The pre-column allows light hydrocarbons to pass through, but water,
methylene chloride, and polar or high boiling components are retained and can be backflushed.
Eliminating the solvent peak significantly reduces the time required to complete the analysis.
Figures 1 and 2 schematically illustrate the installation and operation of the recommended columns in a
Hewlett-Packard 5880A gas chromatograph with split-splitless capillary inlet systems installed in the "B"
and "C" injector positions. The only change to the "B" system involves the normally closed (NC) port of
the "B" solenoid valve. Originally, it was connected to the capped port of the tee in the "B" septum
purge line. (If desired, switching between normal operation of the "B" system and backflushable
pre-column operation could be easily achieved by adding a manually operated three-way valve.)
Replumb the components of the "C" system as shown, and extend lines from the normally open (NO)
port of the "C" solenoid and the "C" backpressure regulator into the oven. Connect the lines and
columns with a zero-dead-volume cross (e.g., Part # ZX1, Valco, Houston, TX) and graphite ferrules.

_1,3-BUTADIENE: METHOD 1024, Issue 2, dated 15 August 1994 - Page 7 of 8_
Set the initial oven temperature to 50 °C and the "C" backpressure regulator to 185 kPa. With the
solenoid valves activated (inject mode), set the "C" flow control to 20 mL/min and the "B" controls so
that the effluent from the analytical column and the "C" split vent total 10 mL/min. Then, with the
solenoid valves deactivated (backflush or normal mode), adjust the "B" backpressure regulator until the
flow from the "C" split vent returns to the value previously measured. This establishes a reverse flow of
10 mL/min through the pre-column. Program the oven to hold the initial temperature (50 °C) for 2 min,
then rise to 120 °C at 20 °C/min, and hold for 8 min. Adjust the time from injection to backflush by
injecting standards and progressively decreasing the time from 2 min until the methylene chloride peak
is removed without attenuating the butadiene peak. It may be necessary to clear higher hydrocarbons
from the analytical column by programming the oven to 200 °C at 30 °C/min and holding 4 min.
Program the solenoid valves to be activated after each run to prepare for the next injection.
Using the backflushable pre-column, there remains a slight problem with retention drift. While in inject
mode, the pre-column strips residual water from the carrier gas. This activates the aluminum oxide
surface of the analytical column and causes retention to increase. The effect is most noticeable when
starting up after the system has been idle. When beginning a sequence of samples, it is advisable to
analyze solvent blanks until the retention drift (e.g., of vinylidene chloride) becomes tolerable.
APPENDIX B. CONVERSION OF 1,3-BUTADIENE VOLUME TO MASS:
MacCallum and McKetta [5] determined the compressibility factor, Z, which corrects for non-ideal
behavior, for 1,3-butadiene at temperatures, T, ranging from 10 to 75 °C, and pressures, P, from
approximately 420 to 1050 mm Hg. Multiple regression of the observed values against P, PT, and PT2,
yields the following equation (standard error of the estimated Z is 0.000635 for 13 degrees of freedom):
Z = a + bP + cPT + dPT2.
where: a = 1.00095, b = -4.84089 x 10~5, c = 4.44816 x 10~7, d = -1.15744 x 10"9
The mass, M, of 1,3-butadiene, corrected for compressibility and the presence of water vapor (when the
gas is stored above water), may be calculated by the following equation:
(P-PJ-V -54.09
M = -
Z -62.36 -(T + 273.2)
where: Pv = vapor pressure of water @ T °C (mm Hg)

V = volume of 1,3-butadiene
54.09 = molecular weight of 1,3-butadiene (g'mol"1)
62.36 = gas constant (mm HgLmol"1-K"1)
273.2 = absolute temperature of 0 °C (K)

.CARRIER
INLET
•B- •B"
INJECTION >SEPTUM
PORT PUROE
1 SOLENOID
VALVE " SPLIT
NO VENT
VALVES ON
•C- SOLENOID NC
VALVE .CARRIER
NO INLET
ANALYTICAL
PRE-COLUMN COLUMN
*—* FID
•C" BACK
PRESSURE CC" SPLIT
REGULATOR * VENT
Figure 1 . Flow diagram for pre-column system in inject mode.
CARRIER
INLET
•B- B"
NEEDLE 'Tl
INJECTION r VALVE
PORT I CAP PURGE
-*-l •B" SOLENOICI \S J
VALVE
T__ •B- BACK
)J PRESSURE - SPLIT
OFF H° Tcoy REGULATOR VENT
VALVES NC
•C' SOLENOIC1 NC
VAJ.VE L "C" U_ •C- FLOW - .CARRIER
4 NO Irnu FILTER p" CONTROL ' INLET
>
ANALYTICAL
1 PRE-COLUUN COLUMN
•C- BACK
PRESSURE »:c- SPLIT
REGULATOR ^ VENT
Figure 2. Flow diagram for pre-column system in backflush (normal) mode.

2-BUTOXYETHANOL
See ALCOHOLS IV (Method 1403) for procedure

n-BUTYL ACETATE

S6C-BUTYL ACETATE

t-BUTYL ACETATE

n-BUTYL ALCOHOL
See ALCOHOLS II (Method 1401) for procedure

sec-BUTYL ALCOHOL
See ALCOHOLS II (Method 1401) for procedure

tert-BUTYL ALCOHOL
See ALCOHOLS I (Method 1400) for procedure

n-BUTYLAMINE 2012
CH3(CH2)3NH2 MW: 73.16 CAS: 109-73-9 RTECS: EO2975000
OSHA : 5 ppm (skin) ceiling PROPERTIES: liquid, ammoniacal odor; MP -49 °C;
NIOSH: 5 ppm (skin) ceiling BP 77.8 °C; d = 0.7327 g/mL @ 25 °C;
ACGIH: 5 ppm (skin) ceiling VP 10.9 kPa (82 mm Hg) @ 20 °C;
(1 ppm = 2.99 mg/m3 @ NTP) vapor density 2.5 (air = 1)
SYNONYMS: butylamine, 1-aminobutane, NBA

(sulfuric acid-treated silica gel tube
150 mg/75 mg) ANALYTE: n-butylamine
FLOW RATE: 0.01 to 1.0 L/min EXTRACTION: 1 mL 50% methanol; neutralize a 500/jL
aliquot with 1 N KOH
VOL-MIN: 2L INJECTION
-MAX: 100 L VOLUME: 5 fjL
SHIPMENT: routine TEMPERATURE-INJECTOR: 175 °C

-DETECTOR: 195 °C
COLUMN: 4% Carbowax 20M + 0.8% KOH on 60/80
mesh Carbopack B, 6 ft x 1/4"-O.D.
ACCURACY CALIBRATION: standard solutions of butylamine

in aqueous methanol
RANGE STUDIED: 8.09 to 35,5 mg/m3 [1]
(15-L samples) RANGE: 0.03 to 1 mg per sample [1]
BIAS: - 5.1%
ACCURACY: ± 23.1% PRECISION (Sr): 0.0490 [1]
APPLICABILITY: The working range is 0.7 to 144 ppm (2 to 430 mg/m3) for a 15-L air sample. Using a nitrogen-specific
detector instead of a FID will greatly increase sensitivity. This alternate detector has been used for amines with a 30-m x 0.25-
mm x 0.25-fjm film DB-5 (5% methyl, phenyl-50% dimethyl-polysiloxane) fused-silica capillary column with a liner packed with
KOH-coated glass wool.
INTERFERENCES: Both concentrated sulfuric acid and silica gel are desiccants, so in sampling atmospheres above 60%
relative humidity the sorbent tube may have lowered capacity.[1]
OTHER METHODS: This revises Method S138 [3]. Method 2010 for aliphatic amines may also be used for determination of
n-butylamine.

n-BUTYLAMINE: METHOD 2012, Issue 1, dated 15 August 1994 - Page 2 of 4
1. n-Butylamine,* ACS reagent grade. 1. Sampler: 150 mg/75 mg sulfuric acid coated
2. Potassium hydroxide,* (KOH) 1N, ACS (20/40 mesh) silica gel tube. See Appendix
reagent grade. for instruction on preparation. (Tubes are
3. Water, deionized. commercially available, but have a designated
4. n-Butyl alcohol, for internal standard. shelf life).
5. Methanol, distilled in glass. 2. Personal sampling pump, 0.01 to 1 L/min, with
6. 50% methanol in water (v/v). flexible polyethylene or PTFE tubing.
7. Calibration stock solution. 3. Hygrometer or other suitable device for
measuring relative humidity.
4. Vials, glass, 2-mL with PTFE-lined caps.
5. Gas chromatograph with a flame ionization
detector, recorder, integrator and column
See Special Precautions (page 201 2-1).
6. Tweezers.
7. Syringes, 10- and 500-//L
9. Pipets, 1 - and 10-mL glass, delivery, with pipet
bulb.
SPECIAL PRECAUTIONS: Butylamine vapor can cause irritation to the eyes, nose, and throat.
Inhalation can cause headache and flushing of skin. Contact with the liquid may produce severe injury
to eyes and skin [4]. Potassium hydroxide is a strong caustic, corrosive to tissue. Handle with gloves.
Work in a hood.
SAMPLING:

2. Break the ends of the silica gel tube immediately prior to sampling. Attach outlet of tube to the
3. Sample 2 to 100 L of air at an accurately known flow rate in the range 0.01 to 1.0 L/min.
4. The temperature, pressure, and relative humidity of the atmosphere being sampled should be
recorded.
5. Cap and seal the sample tube for shipment and place in a suitable container in order to prevent
damage during transit.
6. Collect a bulk sample (ca. 1 g) in a glass vial and ship it separately.
SAMPLE PREPARATION:
wool plug to the front sorbent section's vial.
8. Add 1 mL 50% methanol to the vial. Tightly cap the vial. Agitate the vial for 2 hours.
9. Neutralization of the sample solution. Allow the silica gel particles to settle. Transfer a 500 //L
aliquot to a clean vial and add 500 //L of 1 .0 N KOH.
NOTE 1: If the internal standard is to be used, add the internal standard solution made up in
1.0 N KOH.
NOTE 2: Analyze samples immediately to avoid loss of amine as free base.

n-BUTYLAMINE: METHOD 2012, Issue 1. dated 15 August 1994 - Page 3 of 4
10. Prepare working standards (12 to 1000 //g/mL aqueous methanol) by adding appropriate
aliquots of calibration stock solution to 50% methanol. Follow neutralization procedure in step 9.
11. Analyze working standards together with samples and blanks (steps 14 through 16). Prepare a
calibration graph of area vs. //g of n-butylamine.
12. Determine recovery for each lot of silica gel used for sampling in the concentration range of
interest. Prepare four silica gel tubes at each of five levels plus three media blanks.
a. Remove and discard 75 mg back sorbent section of an unused sorbent tube.
b. Spike aliquot of calibration solution onto front section sorbent section of silica gel tube with
a microliter syringe.
c. Cap and let stand overnight.
d. Desorb following (steps 7 through 9) and analyze along with working standards and blanks
(steps 14 through 16).
e. Prepare graph of recovery vs. fjg n-butylamine.
13. Analyze three quality control spikes and three analyst spikes to ensure that calibration graph and
recovery graph are in control.
MEASUREMENT:
on page 2012-1.
15. Inject 5-//L sample aliquot.
NOTE: If peak area is above the linear range of the working standards, dilute with 50%
methanol, reanalyze, and apply the appropriate dilution factor in calculations.
CALCULATIONS:
17. Determine mass, //g (corrected for recovery), of n-butylamine found in the sample front (W() and
sections.
NOTE: If Wb > W,/10, report breakthrough and possible sample less.
18. Calculate concentration of n-butylamine in the air volume sampled, V (L):
0 ( Wf + Wb - B, - Bb ) ,3
C = -— — , mg/m3.
This method was evaluated over the range 8.09 to 35.5 mg/m3 at 24 °C and pressure of
769 mm Hg using 15-L samples [1,3]. Sampling and measurement precision, Sr, was 0.049, with
average recovery of 91 .4%, representing a non-significant bias. Sample stability during storage was
evaluated at 270 fjg n-butylamine per sample. Samples showed 98.4% recovery after one day of storage
at ambient conditions compared to 95.2% recovery for seven-day old samples.
REFERENCES:
[1] Backup Data Report for n-butylamine, prepared under NIOSH Contract 210-76-0123 (1978).
[2] NIOSH/DPSE Analytical Sequence #4975, Measurement Research Support Branch, NIOSH,
Cincinnati, Ohio (unpublished, 1986).

n-BUTYLAMINE: METHOD 2012, Issue 1, dated 15 August 1994 - Page 4 of 4
Health and Human Services, Publ. (NIOSH) 81-123 (1981), available as GPO Stock #017-033-
00337-8 from Superintendent of Documents, Washington, DC 20402.
METHOD REVISED BY:
Paula Fey O'Connor, NIOSH/DPSE.
APPENDIX: PREPARATION OF SULFURIC ACID-TREATED SILICA GEL.
Place a known amount of 20/40 mesh silica gel in a drying oven set at 125 °C for one hour. Cool the
silica gel to a constant weight (W). Add reagent grade concentrated sulfuric acid dropwise by means of
a pipet to 1 .25 (W) or 25% by weight of the acid. Return the treated silica gel to the drying oven for one
hour with intermittent mixing. Store the treated silica gel in an airtight container.

n-BUTYL GLYCIDYL ETHER 1616
C7H1402 MW: 130.19 CAS: 2426-08-6 RTECS: TX4200000
OSHA : 50 ppm PROPERTIES: liquid; d 0.9087 g/mL @ 20 °C; BP 164

NIOSH: C5.6 ppm; 15 min °C; VP 0.43 kPa (3.2 mm Hg, 4200 ppm)
ACGIH: 25 ppm @20 °C
(1 ppm = 5.32 mg/m3 @ NTP)
SYNONYMS: 1,2-epoxy-3-butoxypropane; butoxymethyloxirane; BGE

(coconut shell charcoal; 100 mg/50 mg)
ANALYTE: n-butyl glycidyl ether
DESORPTION: 0.5 mL CS2, 30 min
VOL-MIN: 15 L@25 ppm
-DETECTOR: 275 °C
SHIPMENT: routine (refrigerate at lab) -COLUMN: 130 °C
SAMPLE INJECTION
STABILITY: not determined VOLUME: 5 fJL
COLUMN: stainless steel, 3.2-mm ID x 3 m, packed

with 10% FFAP on 80/100 mesh
Chromosorb W-AW DMCS
ACCURACY
CALIBRATION: standard solutions of n-butyl glycidyl
RANGE STUDIED: 133to542rhg/m3 [1] ether in CS2
(10-L samples)
RANGE: 1 .6 to 6.4 mg per sample
BIAS: - 16.1% @ 133 mg/m3 [1]
- 1.0% @ 259 to 542 mg/m3
ESTIMATED LOD: not determined
ACCURACY: ±15.5% @ 259 to 592 mg/m3
±30.6% @ 133 mg/m3
APPLICABILITY: The working range is 15 to 60 ppm (80 to 320 mg/m3) for a 20-L air sample. Because of unexpected bias
at the lowest test level and the possibility of poor desorption efficiency at low loadings, a sample volume of at least 15 L is
recommended. This method has not been evaluated for short-term exposures at 5.6 ppm. An appropriate capillary column may
be used for better resolution and sensitivity.

n-BUTYL GLYCIDYL ETHER: METHOD 1616, Issue 1, dated 15 August 1994 - Page 2 of 3
1. Carbon disulfide* (CS2), chromatographic 1. Sampler: borosilicate tubes, 7.0 cm long, 6-

quality. mm OD, 4-mm ID; flame-sealed ends with
2. n-Butyl glycidyl ether*, reagent grade. plastic caps, containing two sections of 20/40
3. Nitrogen, purified. mesh activated (600 °C) coconut charcoal
4. Hydrogen, prepurified. (front = 100 mg; back = 50 mg) separated by
5. Air, compressed, filtered. a urethane foam plug. A silanized glass wool
plug held in place with a metal spring
precedes the front section and a urethane
* See SPECIAL PRECAUTIONS. foam plug follows the back section. Pressure
drop across the tube at 1.0 L/min air flow
must be less than 3.4 kPa. Tubes are
commercially available.
4. Vials, 2-mL, with PTFE-lined crimp caps.
5. Microliter syringes, 1 0-//L and convenient sizes
for making dilutions.
7. Pipets, 0.5-mL
SPECIAL PRECAUTIONS: Both n-butyl glycidyl ether and CS2 are toxic. In addition, CS2 is a serious
fire and explosion hazard (flash point = -30 °C). All work with these compounds must be done in a
hood.
SAMPLING:

3. Sample at an accurately known flow rate between 0.01 and 0.2 L/min for a total sample size
of 15 to SOL
SAMPLE PREPARATION:
6. Add 0.5 mL CS2 to each vial. Cap each vial.
8. Calibrate daily with at least six working standards over the range of 0.1 to 8 mg n-butyl glycidyl
ether per sample.
a. Add a known amount of n-butyl glycidyl ether to CS2 in 10-mL volumetric flask and dilute to
the mark. Use serial dilutions as needed for smaller concentrations.
c. Prepare calibration graph (n-butyl glycidyl ether peak area vs. mg n-butyl glycidyl ether).
the range of interest. Prepare three tubes at each of five levels plus three media blanks.

n-BUTYL GLYCIDYL ETHER: METHOD 1616, Issue 1, dated 15 August 1994 - Page 3 of 3

b. Inject known amount (1 to 20 //L) of n-butyl glycidyl ether or standard solution of n-butyl
glycidyl ether in CS2 directly onto front sorbent section with a microliter syringe.
e. Prepare a graph of DE vs. mg n-butyl glycidyl ether recovered.
MEASUREMENT:
autosampler.
desorbed liquid with CS2, reanalyze, and apply the appropriate dilution factor in
calculations.
CALCULATIONS:
13. Determine the mass, mg (corrected for DE) of n-butyl glycidyl ether found in the sample front
(Wf) and back (Wb) sorbent sections, and in the average media blank front (B() and back (Bb)
sorbent sections.
14. Calculate concentration, C, of n-butyl glycidyl ether in the air volume sampled, V (L):
C . '>'» . 103, mg/m
Method S81 was issued on February 14, 1975 [2] and validated over the range 133 to 542 mg/m3 for 10-
L air samples from dynamically generated test atmospheres [1]. The n-butyl glycidyl ether
concentrations were independently measured by means of a total hydrocarbon analyzer. The average
recoveries for sets of six samples taken at concentrations of 542 and 259 mg/m3 were 99.8% and 98.2%,
respectively. A different method was used to generate concentrations of about 133 mg/m3. For two
sets of six samples taken at the latter concentration, the average recovery was 83.9%. The reason for
the low recovery was not determined. Breakthrough was not observed after sampling 44 L from a test
atmosphere containing 30 mg/m3 of n-butyl glycidyl ether. The desorption efficiency decreased from
93.1 to 82.6% as loadings decreased of 6.4 to 1.6 mg per sample. Sample stability was not determined;
however, refrigeration of the samples upon receipt by the laboratory is recommended.
REFERENCES:
Welfare, Publ. (NIOSH) 77-185 (1977). Available as GPO Stock #017-033-00231-2 from
Education, and Welfare, Publ. (NIOSH) 77-1 57-C (1977).
METHOD REVISED BY:
R.A. Glaser, NIOSH/DPSE. Method S81 was originally validated under NIOSH Contract CDC-99-74-45.

n-BUTYL MERCAPTAN 2525
MW:90.19 CAS: 109-79-5 RTECS: EK6300000

Issue 2: 15 May 1996
OSHA: 0.5 ppm PROPERTIES: liquid; d 0.842 g/mL @ 25 °C; BP 98 °C; VP

NIOSH: CO. 5 ppm 4.7 kPa (35 mm Hg; 4.6% v/v) @ 20 °C
ACGIH: 0.5 ppm
(1 ppm = 3.69 mg/m3 @ NTP)
SYNONYMS: butanethiol; 1-butanethiol; 1-mercaptobutane
SAMPLER: SOLID SORBENT TUBE TECHNIQUE: GAS CHROMATOGRAPHY, FPD SULFUR

(Chromosorb 104, 150 mg/75 mg) MODE
FLOW RATE: 0.01 to 0.05 L/min ANALYTE: n-butyl mercaptan
VOL-MIN: 1 L DESORPTION: 1 mL acetone; stand 15 min

-MAX: 4L
INJECTION VOLUME: 5 uL
SHIPMENT: routine
STABILITY: at least 7 days @ 25 °C [1 ] -COLUMN: 140 °C
BLANKS: 2 to 1 0 field blanks per set COLUMN: glass, 1 .2 m x 2 -mm ID, packed with 60/80
mesh Chromosorb 104

ACCURACY
CALIBRATION: standard solutions of n-butylmercaptan in
RANGE STUDIED: 17 to 74 mg/m3 [1] acetone
(1.5-L samples)
RANGE: 20 to 200 ug per sample [2]
BIAS: -2%[1]
ESTIMATED LOD: 3 ug per sample [1]
OVERALL
PRECISION (SrT): 0.062 [1] PRECISION (Sr): 0.01 5 @ 30 to 1 1 0 ug per sample [1 ]
ACCURACY: ± 14.2%
APPLICABILITY: The working range is 5 to 50 mg/m3 (1.4 to 14 ppm) maximum sample size is based on the capacity of the
Chromosorb 104 to collect vapors of n-butyl mercaptan in air at high relative humidity (94%) [1]. Smaller concentrations may be
determined if desorption efficiency is adequate.
OTHER METHODS: This revises NIOSH Method S350 [2].

n-BUTYL MERCAPTAN: METHOD 2525, Issue 2, dated 15 May, 1996 - Page 2 of 3
1. Acetone, chromatographic quality. 1. Sampler: glass tube, 8.5 cm long, 6-mm OD,
2. n-Hexane, reagent grade. 4-mm ID, flame-sealed ends with plastic caps
3. n-Butyl mercaptan.* containing two sections of 60/80 mesh
4. Nitrogen, purified. Chromosorb 104 (front = 150 mg; back =
5. Hydrogen, prepurified. 75 mg) separated by a 2-mm urethane foam
6. Oxygen, purified. plug. A silylated glass wool plug precedes the
7. Air, filtered, compressed. front section and a 3-mm urethane foam plug
8. Calibration stock solution, 13.47 mg/mL Add follows the back section. Pressure drop across
160 uL of pure n-butyl mercaptan to acetone the tube at 0.025 L/min airflow must be less
and dilute to 10 ml_. Prepare in duplicate. than 3.4 kPa (25 mm Hg). The sampling tubes
are commercially available (SKC, Inc. Cat. #
* See SPECIAL PRECAUTIONS. 226-49-40-104).
3. Gas chromatograph, flame photometric
detector with sulfur filter, integrator, and column
(page 2525-1).
5. Syringes, 10-uL (readable to 0.1 uL) and 50-uL
7. Pipet, 1.0-mL
8. File, triangular.
SPECIAL PRECAUTIONS: Store n-butyl mercaptan away from oxidizing and flammable materials [3,4].
The analyte is highly flammable and irritating to the eyes and mucous membranes. Work in a hood.
SAMPLING:

2. Break the ends of the sampler immediately before sampling. Attach sampler to personal sampling pump
with flexible tubing.
3. Sample at an accurately known flow rate between 0.01 and 0.05 L/min for a total sample size of 1 to 4 L
4. Cap the samplers and pack securely for shipment.
SAMPLE PREPARATION:
5. Place the front and back sorbent sections of the sampler tube in separate vials. Discard the glass wool
and foam plugs.
6. Add 1 .0 mL acetone to each vial. Attach cap to each vial.
8. Calibrate daily with at least six working standards covering the range 0.3 to 20 ug/mL
a. Add known amounts of calibration stock solution to acetone in 10-mL volumetric flasks and dilute to
the mark.
c. Prepare calibration graph (peak area squared vs. ug n-butyl mercaptan).
9. Determine desorption efficiency (DE) at least once for the batch of Chromosorb 104 used for sampling
in the calibration range (step 8). Prepare three tubes at each of five levels plus three media blanks.

n-BUTYL MERCAPTAN: METHOD 2525, Issue 2, dated 15 May, 1996 - Page 3 of 3

b. Inject calibration stock solution (2 to 20 uL) containing a known amount of n-butyl mercaptan directly
onto front sorbent section with a microliter syringe.
e. Prepare a graph of DE vs. ug n-butyl mercaptan recovered.
10. Analyze three quality control blind spikes and three analyst spikes to ensure that the calibration graph
and DE graph are in control.
MEASUREMENT:
1 1 . Set gas chromatograph according to manufacturer's recommendations and to conditions given on page
2525-1 . Inject sample aliquot manually using solvent flush technique. Vent the acetone peak so that it will
not extinguish the flame in the detector.
NOTE: If peak area is above the linear range of the working standards, dilute with acetone, reanalyze
and apply the appropriate dilution factor in calculations.
CALCULATIONS:
13. Determine the mass, ug (corrected for DE) of n-butyl mercaptan found in the sample front (Wf) and back
(Wb) sorbent sections, and in the average blank front (Bf) and back (Bb) sorbent sections.
14. Calculate concentration, C, of n-butyl mercaptan in the air volume sampled, V (L):
w, + wb - B, - bb
C = — : , mg/m3.
v
This method was validated over the range 1 7 to 74 mg/m3 at 22 °C and 759 mm Hg using a 1. 5-L sample [1].
Overall precision, SrT, was 0.062 with an average recovery of 0.98. The concentration of n-butyl mercaptan
was independently determined from the syringe delivery rate and dilution flow rates. Desorption efficiency was
0.90 in the range 28 to 110 ug per sample. The breakthrough volume (effluent concentration = 5% of influent
concentration) was 4.0 L; this was determined by sampling humid air (94% relative humidity), containing
74 mg/m3 n-butyl mercaptan at 0.023 L/min.
REFERENCES:
[1] NIOSH [1977]. Backup data report for S350, prepared under NIOSH Contract 210-76-0123.
[2] NIOSH [1978]. n-Butyl mercaptan: Method S350. In: Taylor DG, Ed. NIOSH manual of analytical
methods, 2nd. ed., V. 4. Cincinnati, OH: National Institute for Occupational Safety and Health, DHEW
(NIOSH) Publication No.78-175.
[3] General Electric [1982]. Material safety data sheet, #504 Butyl Mercaptan, General Electric Co.,
Schenectady, N.Y. 12305.
[4] NIOSH [1981]. NIOSH/OSHA Occupational health guidelines for occupational hazards. U.S. Department
of Health and Human Services, DHHS (NIOSH) Publication No. 81-123, available as GPO Stock
METHOD REVISED BY:
James E. Arnold, NIOSH/DPSE. Method S350 was originally validated under NIOSH Contract
210-76-0123.

e-tert-BUTYLTOLUENE
See HYDROCARBONS, AROMATIC (Method 1501) for procedure

CADMIUM and compounds, as Cd 7048
Cd MW: 112.40 (Cd); CAS: 7440-43-9 (Cd); RTECS: EU9800000 (Cd)

128.40 (CdO) 1306-19-0 (CdO) EV1 930000 (CdO)

OSHA : 0.1 mg/m3, C 0.3 (fume); PROPERTIES: soft metal; valence +2; BP 765 °C;
0.2, C 0.6 (dust) MP 320.9 °C
NIOSH: lowest feasible; carcinogen
ACGIH: 0.01 mg/m3 (total dust); 0.002 mg/m3 (respirable);
carcinogen
SYNONYMS: Vary depending upon the compound.

ANALYTE: cadmium
ASHING: conc. HN03, 6 mL; 140 °C
VOL-MIN: 25 [email protected] mg/m3 conc. HCI, 6 mL; 400 °C
-MAX: 1500 L
FINAL
SHIPMENT: routine SOLUTION: 0.5 N HCI; 25 mL
SAMPLE FLAME: air-acetylene, oxidizing

STABILITY: stable
WAVELENGTH: 228.8 nm
BACKGROUND CORRECTION: D2 or H2 continuum
CALIBRATION: Standard solutions of Cd in 0.5 N HCI
ACCURACY RANGE: 2.5 to 30 //g per sample
RANGE STUDIED: 0. 12 to 0.98 mg/m3 [1] ESTIMATED LOD: 0.05 fjg per sample [2]
(25-L samples)
PRECISION (§r): 0.05 @ 3 to 23 //g per sample [1,3,4]
BIAS: - 1.57%
ACCURACY: ± 13.23%
APPLICABILITY: The working range is 0.1 to 2 mg/m3 for a 25-L air sample, and 0.01 to 0.2 mg/m3 for a 250-L air sample.
This is an elemental analysis and it will not distinguish Cd fume from Cd dust. Aliquots of the ashed samples can be analyzed
separately for many additional metals.
INTERFERENCES: Background correction is required to control molecular or flame absorption. Iron does not interfere at 20
parts Fe to 1 part Cd [1].
OTHER METHODS: This method combines and replaces P&CAM 173 [5], S312 [4], and S313 [6]. A similar method appears
in the criteria document [7]. Method 7300 (ICP-AES) is an alternate, multielement measurement method with approximately
the same sensitivity. Aliquots of the ashed samples can be analyzed by graphite furnace atomic absorption with greatly
increased sensitivity.

CADMIUM and compounds, as Cd: METHOD 7048, Issue 2, dated 15 August 1994 - Page 2 of 4
1. Nitric acid, conc., ultrapure. 1. Sampler: cellulose ester membrane filter,

2. Hydrochloric acid, conc., ultrapure. 0.8-^m pore size, 37-mm diameter; in cassette
3. Hydrochloric acid, 0.5 N. Add 41.5 mL conc. filter holder.
HCI to water; dilute to 1 L 2. Personal sampling pump, 1 to 3 L/min, with
4. Calibration stock solution, 100 //g Cd/mL* flexible connecting tubing.
Commercially available or dissolve 0.100 g Cd 3. Atomic absorption spectrophotometer with an
metal in minimum volume of (1:1) HCI. Dilute air-acetylene burner head , cadmium hollow
to 1 L with 0.5 N HCI. cathode lamp, and background correction.
5. Distilled-deionized water. 4. Regulators, 2-stage, for air and acetylene.
6. Air, filtered. 5. Beakers, Phillips, 125-mL, or Griffin, 50-mL,
7. Acetylene. with watchglass covers.*
7. Micropipets, 5 to 300 fjL.*
8. Hotplate, surface temperature 400 °C.
* Clean with conc, nitric acid and rinse
thoroughly before use.
Cadmium compounds are very toxic and should be considered carcinogens [3,7]. Handle with extra
care.
SAMPLING:

2. Sample at an accurately known flow rate between 2 and 3 L/min for 15 min (30 to 45 L) for
ceiling measurements, or at 1 to 3 L/min for a total sample size of 25 to 1500 L for TWA
measurements. Do not exceed a filter loading of ca. 2 mg total dust.
SAMPLE PREPARATION:
NOTE: The following sample preparation gave quantitative recovery (see EVALUATION OF
METHOD). Steps 4 through 9 of Method 7300 or other quantitative ashing techniques
may be substituted.
3. Open the cassette filter holders and transfer the samples and blanks to separate clean beakers.
4. Add 2 mL conc. HNO3, cover with a watchglass, and heat on hotplate (140 °C) until the volume
is reduced to ca. 0.5 mL Start reagent blanks at this point.
5. Repeat 2 more times using 2 mL conc. HNO3 each time.
6. Add 2 mL conc. HCI, cover with a watchglass, and heat on hotplate (400 °C) until the volume is
reduced to ca. 0.5 mL
7. Repeat 2 more times using 2 mL conc. HCI. Do not allow the solution to go to dryness at any
point.
8. Cool solution and add 10 mL distilled water.
10. Dilute to volume with distilled water.

11. Calibrate daily with at least six working standards. Add known amounts, covering the range 0 to
30 fjg Cd per sample, of calibration stock solution to 100-mL volumetric flasks and dilute to
volume with 0.5 N HCI.
12. Analyze the working standards together with the blanks and samples (steps 17 and 18).
13. Prepare a calibration graph of absorbance vs. solution concentration
14. Aspirate a standard after every 10 samples to check for instrument drift.
15. Check recoveries with at least 2 spiked media blanks per 10 samples.
MEASUREMENT:

page 7048-1 .
dilute the solutions with 0.5 N HCI, reanalyze, and use the appropriate dilution factor in
calculations.
CALCULATIONS:
19. Using the measured absorbances, calculate the corresponding concentrations U/g/mL) of
cadmium in the sample, Cs, and average media blank, Cb, from the calibration graph.
concentration, C (mg/m3), of cadmium in the volume of air sampled, V (L):
c . <P.V.-<W
Method S312 was issued on June 12, 1976 [4], and validated over the range 0.12 to 0.98 mg/m3 for a
25-L sample of CdO dust [1]. Method S313 was issued on November 26, 1976 [6], and validated over
the range 0.12 to 0.57 mg/m3 for a 25-L sample of Cd fume, and over the range 0.04 to 0.18 mg/m3 for
a 140-L sample of Cd fume [1].
REFERENCES:
[2] User check, UBTL, NIOSH Seq. #3990-M (unpublished, November 29, 1983).
[3] Current Intelligence Bulletin 42: Cadmium. U.S. Department of Health and Human Services, Publ.
(NIOSH) 84-116 (Sept. 27, 1984).
[4] NIOSH Manual of Analytical Methods, V. 3, Method S312, U.S. Department of Health, Education, and
Welfare, Publ. (NIOSH) 77-1 57-C (1977).
[5] Ibid, 2nd ed., V. 5, P&CAM 173, U.S. Department of Health, Education, and Welfare, Publ. (NIOSH)
79-141 (1979).

[6] Ibid, Method S313.

[7] Criteria for a Recommended Standard. ..Occupational Exposure to Cadmium, Appendix II, U.S.
METHOD REVISED BY:
Mark Millson, NIOSH/DPSE and R. DeLon Hull, Ph.D., NIOSH/DBBS; S312 and S313 originally validated
under NIOSH Contract CDC-94-74-45.

CALCIUM and compounds, as Ca 7020
Ca MW: Table 1 CAS: Table 1 RTECS: Table 1

OSHA : Table 1 PROPERTIES: soft, reactive metal; valence 2;

NIOSH: Table 1 MP 848 °C; VP not significant
ACGIH: Table 1
SYNONYMS: Quicklime (CaO); limestone (CaCO3); marble (CaCO3); hydrated lime (Ca(OH)2)

ANALYTE: calcium
ASHING: conc. HNO3, 6 mL; 140 °C
VOL-MIN: 20 L @ 5 mg/m3 60% (w/v) HCIO4, 2 mL; 400 °C
-MAX: 400 L
FINAL
SHIPMENT: routine SOLUTION: 5% HCI; 100 mL
1000 //g/mL Cs; 1000 /xj/mL La
SAMPLE
STABILITY: stable FLAME: air-acetylene, reducing
BLANKS: 2 to 10 field blanks per set WAVELENGTH: 422.7 nm
BACKGROUND
CORRECTION: none used
ACCURACY CALIBRATION: Ca2* in 5% HCI
RANGE STUDIED: 2.6 to 10.2 mg/m3 [1] RANGE: 0.08 to 1.7 mg per sample [2]
(85-L samples)
BIAS: - 0.39%
OVERALL PRECISION (SrT): 0.063 [1] PRECISION (Sr): 0.02 [1,3]
ACCURACY: ± 11.5%
APPLICABILITY: The working range is 1 to 20 mg/m for an 85-L air sample. This is an elemental analysis, not compound
specific. Verify that the compounds in the samples are soluble with the ashing procedure. Aliquots of the samples can be
analyzed separately for many additional metals.
INTERFERENCES: The use of 1000 fjg/mL Cs controls ionization in the flame caused by metals such as Na, K, Li, and Mg.
The presence of Si, Al, or H3P04 require the use of 1% (w/w) La as a releasing agent.
OTHER METHODS: This method combines and replaces P&CAM 173 [4] and S205 [2]. Method 7300 (ICP-AES) is an alternate
analytical method.

CALCIUM and compounds, as Ca: METHOD 7020, Issue 2, dated 15 August 1994- Page 2 of 4

2. Hydrochloric acid, conc. 0.8-//m pore size, 37-mm diameter; in cassette
3. Hydrochloric acid, 5% (v/v). Add 50 mL conc. filter holder.
HCI to 500 mL water; dilute to 1 L 2. Personal sampling pump, 1 to 3 L/min, with
4. Calibration stock solution, 1000 //g Ca/mL flexible connecting tubing.
Commercially available or add 50 mL 3. Atomic absorption spectrophotometer with an
deionized water and minimum volume of HCI air-acetylene burner head and calcium hollow
(20 mL) to dissolve 2.498 g CaCO3. Dilute to cathode lamp.
1 L with deionized water. 4. Regulators, 2-stage, for air and acetylene.
5. Cs solution, 50 mg/mL Dissolve 73.40 g 5. Beakers, Phillips, 125-mL, or Griffin, 50-mL,
CsNO3 in water to make 1 L solution. with watchglass covers.*
6. La solution, 50 mg/mL Dissolve 156 g 6. Volumetric flasks, 25- and 100-mL*
La(NO3)3 • 6H2O in water to make 1 L solution. 7. Micropipets, 5 to 500 //L*
7. Distilled or deionized water. 8. Hotplate, surface temperature 140 and
8. Air, filtered. 400 °C.
9. Acetylene.
10. Perchloric acid, 60% w/v.
CIean with conc. HNO3 and rinse
* See SPECIAL PRECAUTIONS. thoroughly with distilled or deionized water
before use.
SPECIAL PRECAUTIONS: Perform all perchloric acid digestions in a perchloric acid fume hood.
SAMPLING:

SAMPLE PREPARATION:
METHOD). Steps 4 through 9 of Method 7300 or other quantitative ashing techniques
may be substituted, especially if several metals are to be determined on a single filter.
3. Open the cassette filter holders and transfer the samples and blanks to separate clean beakers.
4. Add 5 mL conc. HNO3 and cover with a watchglass. Start reagent blanks at this point.
5. Heat on hotplate (140 °C) until most of the acid has evaporated.
6. Add 2 mL conc. HNO3 and 1 mL 60% HCIO4.
7. Heat on 400 °C hotplate until dense fumes of perchloric acid appear.
8. Remove watchglass and rinse into the beaker with distilled water.
9. Place the beakers on the 400 °C hotplate and allow to go to dryness.
10. Cool each beaker and dissolve the residues in 5 mL 5% HCI.
11. Transfer the solution quantitatively to a 100-mL volumetric flask containing 2 mL of 50 mg/mL
Cs solution and 2 mL of 50 mg/mL La solution.
NOTE: Dilute to a smaller volume (e.g., 10 mL) with proportionally less Cs and La if required for
sensitivity of analysis for other metals in the sample.
12. Dilute to volume with 5% HCI.

CALCIUM and compounds, as Ca: METHOD 7020, Issue 2, dated 15 August 1994 - Page 3 of 4
13. Add known amounts, covering the range 0 to 500 JJQ Ca per sample, of calibration stock
solution to 100-mL volumetric flasks containing 2 mL each of the 50 mg/mL Cs and La solutions
and dilute to volume with 5% HCI.
14. Analyze the working standards along with the samples and blanks (steps 19 and 20).
15. Prepare a calibration graph of absorbance vs. solution concentration
MEASUREMENT:

page 7020-1 .
dilute the solutions with 5% HCI and an appropriate amount of the 50 mg/mL Cs and La
solutions, reanalyze, and apply the appropriate dilution factor in the calculations.
CALCULATIONS:
21 . Using the measured absorbances, calculate the corresponding concentrations 0"g/mL) of

calcium in the sample, Cs, and average media blank, Cb, from the calibration graph.
concentration, C (mg/m3), of calcium in the volume of air sampled, V (L):
c - <c.\-w mg/m,
Method S205 [2] was issued on September 26, 1975, and validated over the range 2.6 to 10.2 mg/m3
using an 85-L air sample by lab testing with spiked filters and generated atmospheres of CaO, verified by
EDTA titration [1]. Collection efficiency of 1.00 was determined for the sampling device. Precision and
accuracy data are given on page 7020-1 . An additional check showed an estimated LOD of 1 //g Ca per
sample [3].
REFERENCES:
[2] V. 3, S205, U.S. Department of Health, Education, and Welfare, Publ. (NIOSH) 77-1 57-C (1979).
[3] User check, UBTL, NIOSH Seq. #3990-0 (unpublished, November 29, 1983).
[4] Ibid, NIOSH Manual of Analytical Methods, 2nd ed., Vol. 5, P&CAM 173, U.S. Department of Health,
METHOD REVISED BY:
Mark Millson, NIOSH/DPSE and R. DeLon Hull, Ph.D., NIOSH/DBBS; S205 originally validated under
NIOSH Contract CDC-99-74-45.

CALCIUM and compounds, as Ca: METHOD 7020, Issue 2, dated 15 August 1994 - Page 4 of 4
TABLE 1: General Information
FORMULA M.W. CAS # RTECS # EXPOSURE LIMITS (mg/m3)

OSHA NIOSH ACGIH
Ca 40.08 7440-70-2 EV8040000 ..
CaO 56.08 1305-78-8 EW3 100000 522
Ca(OH)2 74.10 1305-62-0 EW2800000 None 5 5
Ca(CO3)2 100.09 471-34-1 EV9580000 15 (total); 10 (total); 10

total dust 5 (resp.) 5 (resp.)

CAMPHOR
See KETONES II (Method 1301) for procedure

CAPSAICIN and DIHYDROCAPSAICIN 5041
(1)C18H27N03 MW: 305.40 CAS: 404-86-4 RTECS: RA8530000

(2) C18H29N03 307.48 19408-84-5 RA5998000
OSHA : no PELs PROPERTIES: (1) white solid; MP 65 °C; BP 210-220 °C

NIOSH: no RELs @ 0.01 mm Hg; VP not significant @
ACGIH: noTLVs 25 °C
(2) white solid; VP not significant @ 25 °C
NAMES & SYNONYMS: (1) capsaicin: frans-8-methyl-A/-vanillyl-6-nonenamide

(2) dihydrocapsaicin: 8-methyl-N-vanillylnonanamide
SAMPLER: FILTER TECHNIQUE: HPLC, FLUORESCENCE DETECTOR

(13-mm glass fiber)
ANALYTES: capsaicin and dihydrocapsaicin
FLOW RATE: 1 to 3 L/min EXTRACTION: 2 mL acetonitrile; ultrasonic bath,

10 min
VOL-MIN: (1)[email protected] mg/m3
(2) 7 L @ 0.01 mg/m3 INJECTION
-MAX: 1000 L VOLUME: 25/1/L
SHIPMENT: ship at 0 °C MOBILE PHASE: 48% acetonitrile/52% water v/v;

1 mL/min
SAMPLE
STABILITY: at least 26 days @ 5 °C [1 ,2] COLUMN: 3.9-mm ID x 15 cm stainless steel
packed with 10-//m/j-Bondapak C,8
DETECTOR: fluorescence: excitation 281 nm;
emission 312 nm
CALIBRATION: standard solutions of capsaicin and

dihydrocapsaicin in acetonitrile
RANGE: (1) 0.050 to 100/jg/sample

ACCURACY (2) 0.067to100/jg/sample
RANGE STUDIED: not studied ESTIMATED LOD: (1) 0.015 /jg/sample

(2) 0.02 /jg/sample
PRECISION (Sr): (1) 0.042 @ 0.1 3 to 17/jg/sample
OVERALL (2) 0.065 @ 0.11 to3//g/sample
PRECISION (S,T): not determined
APPLICABILITY: This method has been used to analyze samples collected at a pickle and pepper processing plant [1]. Analyte
concentrations in sample solutions are not expected to exceed 0.2 /jg/mL when samples are collected in this type of environment.
INTERFERENCES: Capsaicin and dihydrocapsaicin exhibit baseline separation at concentrations of 0.2/jg/mL and less. At higher
concentrations, baseline separation can be achieved by increasing the water in the mobile phase to about 55%.
Nordihydrocapsaicin causes little interference during measurement of capsaicin because its abundance is relatively small in
Capsicum fruit [3].
OTHER METHODS: HPLC methods for one or both analytes in solution have been published [3-8]. None have been published
for air analysis.

CAPSAICIN and DIHYDROCAPSAICIN: METHOD 5041, Issue 1, dated 15 May 1996 - Page 2 of 4
1. Capsaicin, *98% pure.* 1. Sampler: 13-mm glass fiber filter in 2-piece

2. Dihydrocapsaicin, ^90% pure.* filter holder (Swinnex, Millipore Corp., or
3. Water, distilled. equivalent).
4. Acetonitrile, chromatographic quality.* 2. Personal sampling pump, 1 to 3 L/min, with
5. Capsaicin calibration and recovery stock flexible connecting tubing.
solution, 0.8 mg/mL: Dissolve 20 mg of 3. HPLC, fluorescence detector, ex 281 nm, em
capsaicin in acetonitrile to make 25 mL solution. 312 nm; recorder, integrator, and column (page
Store at 5 °C. Prepare fresh bimonthly. 5041-1).
6. Dihydrocapsaicin calibration and recovery stock 4. Vials, 4-mL, with PTFE-lined caps,
solution, 0.8 mg/mL: Dissolve 20 mg 5. Graduated cylinder, 1-L, readable to 10 mL
dihydrocapsaicin in acetonitrile to make 25 mL 6. Volumetric flasks, 25- and 10-mL
solution. Store at 5 °C. Prepare fresh 7. Syringes: 10-mL; 500-uL, readable to 10 uL;
bimonthly. 100-(jL, readable to 1 |jL; 10 uL, readable to
0.1 ML
8. Ultrasonic water bath.
9. Film, plastic, flexible, water resistant.
* See SPECIAL PRECAUTIONS 10. Syringe filters, 3-mm PTFE membrane,
0.45-um pore size, in polypropylene housing.
1 1 . Tweezers.
12. Dust mask.
SPECIAL PRECAUTIONS: Capsaicin and dihydrocapsaicin are toxic, are classified as mutagens, and can
destroy certain sensory nerve cells [9,10]. Inhalation of aerosols of these compounds will result in
prolonged coughing or sneezing. Exposure by inhalation can take place during weighing operations; thus,
a dust mask is recommended. Skin contact will cause a burning sensation. Ingestion can cause intolerable
burning and gastrointestinal disorders.
Acetonitrile is toxic and is a fire hazard (flash point = 12.8 °C).
SAMPLING:
1 . Calibrate each personal sampling pump with a representative sampler in line.

2. Attach the sampler to the personal sampling pump with flexible tubing.
3. Sample at an accurately known flow rate between 1 and 3 L/min for a total sample size of 7 to 1000 L
NOTE: Limit the maximum loading of particulate matter on the filter to approximately 0.5 mg.
4. Seal ends of sampler with plastic film. Ship to laboratory in insulated container with bagged refrigerant.
SAMPLE PREPARATION:
5. Transfer the 1 3-mm glass fiber filter to a 4-mL vial.

6. Add 2 mL of acetonitrile to the vial and cap securely.
7. Place the sample vial into an ultrasonic bath and agitate for 10 min.
8. Filter the sample solution through a PTFE membrane filter.
9. Calibrate daily with at least six working standards over the range of interest: 0.008 to 10 ug/mL for
capsaicin; 0.01 to 10 ug/mL for dihydrocapsaicin.
a. Prepare working standards from calibration stock solution in acetonitrile.
NOTE: Working standards may be stored in tightly sealed vials at 5 °C for at least 9 weeks.
c. Prepare calibration graphs for capsaicin and dihydrocapsaicin (peak area or height vs. ug of analyte).

10. Determine recoveries (R) at least once for each lot of glass fiber filters in the calibration range (step
9). Prepare three filters at each of five concentration levels plus three media blanks.
NOTE: Use separate filters for each analyte unless chromatographic conditions have been modified
to permit baseline separation at concentrations >0.2 ug/mL (see APPLICABILITY and
INTERFERENCES, Page 5041-1).
a. Place 13-mm glass fiber filters into 4-mL vials.
b. With a microliter syringe, fortify each filter with recovery solution.
c. Allow the uncapped vials to stand overnight at room temperature.
d. Prepare and analyze with working standards (steps 5 through 8, and steps 12 and 13).
e. Prepare graph of R vs. ug of analyte recovered.
11. Analyze three quality control blind spikes and three analyst spikes for each analyte to ensure that the
respective calibration graphs are in control.
MEASUREMENT:
12. Set high performance liquid chromatograph according to manufacturer's recommendations and to
conditions given on page 5041-1. Inject 25-uL sample aliquot manually or with autosampler.
NOTE: If peak area is above the range of the working standards, dilute with acetonitrile, reanalyze,
and apply appropriate dilution factor in calculations.
1 3. Measure peak area or height for each analyte.
CALCULATIONS:
14. Determine the mass, ug (corrected for R), of each analyte found on the filter (W) and the average
media blank (B).
1 5. Calculate the concentration, C, of each analyte in the air volume sampled (L):
C = jl, mg/m
Average recoveries of capsaicin after fortification of 13-mm glass fiber filters with 0.1 3-, 0.28-, 0.58-, 1.1-, 2.9-,
and 17-ug quantities of the compound were 1.02, 0.95, 0.98, 0.99, 1.04, and 1.00, respectively; precision (S)
was 0.042 (35 samples, pooled). After 28 days storage at 5 °C, the average recovery of 0.99-ug quantities
of capsaicin from glass fiber filters was 0.96; Sr was 0.023 (6 samples). In addition, the average recovery of
0.99-ug quantities of capsaicin from glass fiber filters after 28 days storage at room temperature was 0.92;
Sr was 0.052 (6 samples). These data for stored samples suggest that recovery and precision of
measurement are improved when samples are stored at the lower temperature. Empty glass vials were
fortified with 0.90-ug quantities of capsaicin and stored uncapped for three days at room temperature. The
average recovery from the vials was 0.98; thus, the vapor pressure of capsaicin at room temperature is
insignificant.
A standard solution of capsaicin in acetonitrile at a concentration of 0.5 ug/mL was found to be stable during
9 weeks storage at 5 °C. The container was sealed tightly to prevent evaporation of solvent during
refrigeration.
Average recoveries of dihydrocapsaicin after fortification of 13-mm glass fiber filters with 0.1 1-, 0.28-, 1 .1-,
and 3.0-ug quantities of the compound were 0.94, 1.03, 0.99, and 0.93, respectively; precision (Sr) was 0.065
(23 samples, pooled). After 26 days storage at 5 °C, the average recovery from glass fiber filters fortified with
0.88 ug of dihydrocapsaicin was 0.88; Sr was 0.047 (6 samples).

This method was not evaluated with controlled atmospheres in a laboratory. However, the method was
employed for measurement of capsaicin and dihydrocapsaicin in air at a pickle pepper processing plant [1,11].
A curious phenomenon was the fact that in each of many of the samples the ratio of capsaicin to
dihydrocapsaicin was less than 1:1. Generally, capsaicin is the capsaicinoid that occurs in Capsicum fruit in
the greatest abundance [3].
REFERENCES:
[I] Tucker SP [in preparation). Determination of capsaicin and dihydrocapsaicin in air in a pickle and
pepper processing plant. Cincinnati, OH: National Institute for Occupational Safety and Health,
Division of Physical Sciences and Engineering (DPSE).
[2] Tucker SP [1995]. Backup data report for method 5041, Capsaicin and Dihydrocapsaicin. National
Institute for Occupational Safety and Health, DPSE, Unpublished report.
[3] Weaver KM, Luker RG, Neale ME [1984]. J Chromatogr 301: 288-291.
[4] Sticher O, Soldati F, Joshi RK [1978]. J Chromatogr 166:221-231.
[5] Weaver KM, Awde DB [1 986]. J Chromatogr 367: 438-442.
[6] Kawada T, Watanabe T, Katsura K, Takami H, Iwai K [1985]. J Chromatogr 329: 99-105.
[7] Saria A, Lembeck F, Skofitsch G [1981]. J Chromatogr 208: 41-46.
[8] Krajewska AM, Powers JJ [1986]. J Chromatogr 367: 267-270.
[9] Monsereenusorn Y, Kongsamut S, Pezalla PD [1982], CRC Crit Rev Toxicol 10: 321-339.
[10] NIOSH [1 994]. Registry of toxic effects of chemical substances (RTECS) data base: capsaicin and
dihydrocapsaicin. Cincinnati, OH: National Institute for Occupational Safety and Health, Education and
Information Division, Information Resources Branch. Data base accessed August, 1994.
[II] Tucker SP [1994]. Analytical report for Sequence #8015, DPSE/MRSB. Cincinnati, OH: National
Institute for Occupational Safety and Health. Unpublished report.
METHOD WRITTEN BY:
Samuel P. Tucker, Ph.D., NIOSH/DPSE

CARBARYL 5006
C10H7OC( = O)NHCH3 MW: 201.22 CAS: 63-25-2 RTECS: FC5950000

OSHA : 5 mg/m3 PROPERTIES: solid; crystal; d 1.230 g/mL @ 20 '

NIOSH: 5 mg/m3; BP decomposes; MP 142 °C;
Group II Pesticide VP <0.005 Pa (<4 x 10-5 mm Hg;
ACGIH: 5 mg/m3 <0.4 mg/m3) @ 20 °C
SYNONYMS: Sevin; 1-naphthalenol N-methylcarbamate; 1-Naphthyl-N-methylcarbamate
SAMPLER: FILTER TECHNIQUE: VISIBLE ABSORPTION

(glass fiber) SPECTROPHOTOMETRY
FLOW RATE: 1 to 3 L/min ANALYTE: jj-nitrobenzenediazonium

tetrafluoroborate complex
VOL-MIN: 20 L @ 5 mg/m3 ,
-MAX: 400 L SAMPLE WORKUP: 20 mL 0.1 M methanolic potassium
hydroxide; to 2-mL aliquot, add
SHIPMENT: ship filters in 25-mL 17 mL glacial acetic acid; add 1 mL
scintillation vials p_-nitrobenzenediazonium
SAMPLE tetrafluorobate
STABILITY: at least 7 days @ 25 °C [1]
WAVELENGTH: 475 nm
BLANKS: 2 to 10 field
blanks per set CALIBRATION: Carbaryl in methylene chloride
RANGE: 0.1 to 1.0 mg per sample [2]
ACCURACY ESTIMATED LOD: 0.03 mg per sample [3,4]
RANGE STUDIED: 2 to 13 mg/m3 [1] PRECISION (Sr): 0.015 [1]

(90-L samples)
BIAS: - 0.73%
ACCURACY: ± 11.3%
APPLICABILITY: The working range is 0.5 to 20 mg/m3 for a 200-L air sample.
INTERFERENCES: Phenols such as 1-naphthol will give a positive interference [2]. Interferences from other aromatic
carbamates and phenoxyacetic acid pesticides may occur but have not been documented.

CARBARYL: METHOD 5006, Issue 2, dated 15 August 1994 - Page 2 of 4
1. Carbaryl, reagent grade.* 1. Sampler: 37-mm filter cassette with 37-mm

2. Methanol, absolute.* Type A/E glass fiber filter (Gelman Sciences,
3. Methylene chloride, distilled in glass.* or equivalent).
4. 0.1 MKOH in absolute methanol. Dissolve 0.1 NOTE: The filter must be free of organic
mole (5.612 g) in 10 ml_ methanol in a 1-L binders.
volumetric flask; dilute to mark with methanol. 2. Personal sampling pump, 1 to 3 L/min, with
5. Glacial acetic acid.* flexible connecting tubing.
6. rj-Nitrobenzenediazoniumtetrafluoroborate. 3. Spectrophotometer capable of measuring at
Dissolve 25 mg in 5 mL methanol. Add 20 mL 475 nm with matched glass cuvettes (1-cm
glacial acetic acid. Prepare just before use. path length).
Keep in an ice bath (4 °C) during use. 4. Vials, scintillation, 25-mL, with PTFE-lined
Discard if the solution becomes deep yellow. screw caps.
7. Calibration stock solution, 2 mg/mL* Dissolve 5. Tweezers.
an accurately weighed 20-mg portion of 6. Syringe, Luer-Lok glass, 10-mL, with 13-mm
Carbaryl in methylene chloride to make 10 mL stainless steel filter holder and PTFE filters,
solution. 7. Shaker, mechanical wrist-action.
8. Flasks, volumetric, 10-mL and 1 L
9. Pipets, 1-, 2-, 17- and 20-mL with pipet bulb.
* See SPECIAL PRECAUTIONS. 10. Syringes or micropipets, 10-, 25- and 50-//L
11. Timer, 5- and 20-min.
12. Ice bath.
SPECIAL PRECAUTIONS: Carbaryl is a cholinesterase inhibitor; use precautions to prevent skin

contamination [5,6]. Methylene chloride is toxic; use only in a hood. Methylene chloride is a suspect
human carcinogen. Methanol is flammable and toxic (flash point = 11 °C); use only in a hood. Glacial
acetic acid is corrosive; handle only with gloves and facial splash protection.
SAMPLING:

2. Sample at an accurately known flow rate between 1 and 3 L/min for a sample size of 20
to 400 L
3. Within 1 h after sampling, remove the filter carefully to prevent sample loss and place it in a vial.
Handle filter only with tweezers.
SAMPLE PREPARATION:
NOTE: Process the samples, blanks, recovery spikes, and working standards in small groups (e.g., two
to four) to maintain consistent timing for all analyses. Include a reagent blank in each small
group for use in the reference cell of the spectrophotometer.
4. Add 20 mL methanolic 0.1 M KOH to the vial containing the filter.
5. Place the vial on a shaker for 5 min.
6. Transfer 2 mL sample solution to another vial. Start reagent blank at this step.
NOTE: For filter samples containing > 1 g Carbaryl, dilute the sample solution with methanolic
0.1 M KOH prior to this step.
7. Add 17.0 mL glacial acetic acid to the 2 mL of sample solution and cover vial with a PTFE-lined
screw cap. Mix by swirling.
8. Add 1 mL Q-nitrobenzenediazonium tetrafluoroborate solution. Mix by swirling. Start a 20-min
timer for each vial at this point.
9. Use a syringe fitted with a PTFE in-line filter to transfer the solution from the sample vial to the
cuvette. Proceed directly to step 15 after exactly 20 min from step 8.

NOTE 1 : The color degrades steadily with time. All samples, blanks, recovery spikes, and
working standards must have exactly the same time for color development.
NOTE 2: The PTFE in-line filter removes glass fibers from the samples. (Standards do not have
to be filtered.)
10. Calibrate with at least six working standards over the range 0.05 to 1.0 mg Carbaryl per sample.
a. Add known amounts of calibration stock solution to methanolic 0.1 M KOH in vials to make
20 mL of solution.
b. After 5 min, transfer 2.0 mL of each solution into a clean vial.
c. Prepare as in steps 7 through 9.
d. Analyze together with samples and blanks (steps 13 through 15).
e. Prepare calibration graph (absorbance vs. mg Carbaryl).
1 1 . Check recovery with at least three spiked media blanks per sample set.
a. Add aliquot of calibration stock solution with a microliter syringe directly to a representative
filter. Air dry.
b. Prepare and analyze together with working standards (steps 4 through 9 and 13 through 15).
c. Calculate recovery [(mg recovered - mg blank)/mg added].
MEASUREMENT:
13. Set spectrophotometer at 475 nm.

14. Adjust baseline to zero with distilled water in both cells.
15. Read the absorbance of the sample against the absorbance of the reagent blank.
NOTE 1 : Prepare a fresh reagent blank with each small group of samples. The absorbance of
reagent blanks increases with time [5].
NOTE 2: If absorbance of the sample is >1.0, dilute the filter extract (step 4) with methanolic
0.1 M KOH, reanalyze, and apply the appropriate dilution factor in calculations.
CALCULATIONS:
16. Determine the mass, mg of Carbaryl found on the filter, W, and average media blank, B, from
the calibration graph.
17. Calculate the concentration, C (mg/m3), of Carbaryl in the air volume sampled, V (L):
C -
Method S273 [2] was issued on February 27, 1976, and validated over the range of 1.96 to 13.4 mg/m3
at 24 °C and 763 mm Hg [1]. Overall precision, SrT, was 0.057 with an average recovery of 102%,
representing a non-significant bias. The concentration of Carbaryl was independently verified by a
Thermo Systems particle mass monitor. Generated atmospheres were produced by nebulization of a
toluene solution of a commercial formulation of Sevin containing 15% Carbaryl by weight. No Carbaryl
was detected in bubblers (containing 0.1 M KOH in methanol) placed behind the glass fiber filters when
90-L air samples were taken of an atmosphere containing 15 mg/m3 Carbaryl. Thus, it was concluded
that Carbaryl vapor was not a significant factor.

REFERENCES:
[1] Documentation of NIOSH Validation Tests, S273, U.S. Department of Health, Education, and Welfare,
Publ. (NIOSH) 77-185 (1977).
[3] User check, UBTL, Inc., NIOSH Sequence #421 3-V (unpublished, August 16, 1984).
[4] User check, Kettering Laboratory, University of Cincinnati (NIOSH, unpublished, Novembers, 1984).
[5] NIOSH Criteria for a Recommended Standard. ..Occupational Exposure to Carbaryl, U.S. Department
of Health, Education, and Welfare, Publ. (NIOSH) 77-107 (1976).
[6] NIOSH Criteria for a Recommended Standard. ..Occupational Exposure During the Manufacture and
Formulation of Pesticides, U.S. Department of Health, Education, and Welfare, Publ. (NIOSH) 78-174
(July, 1978).
METHOD REVISED BY:
P. Fey O'Connor, NIOSH/DPSE; S273 originally validated under NIOSH Contract 99-74-45.

CARBON BLACK 5000
MW: 12.01 CAS: 1333-86-4 RTECS: FF5800000

OSHA : 3.5 mg/m3 PROPERTIES: solid; may contain polynuclear aromatic

NIOSH: 3.5 mg/m3 (in presence of PAHs: carcinogen/PAHs hydrocarbons (PAH)
to 0.1 mg/m3, cyclohexane extractable fraction)
ACGIH: 3.5 mg/m3
SYNONYMS: acetylene black; amorphous carbon; furnace black; lamp black
SAMPLER: FILTER TECHNIQUE: GRAVIMETRIC (FILTER WEIGHT)

(tared 5-fjm PVC membrane)
ANALYTE: airborne particulate material
BALANCE: 0.001 mg sensitivity; use
VOL-MIN: 30 L @ 3.5 mg/m3 same balance before and after
-MAX: 570 L sample collection
SHIPMENT: routine CALIBRATION: National Institute of Standards and

Technology, Class S-1.1 weights or
SAMPLE ASTM Class 1 weights
STABILITY: indefinitely
PRECISION (Sr): 0.025 @ 3.5 mg/m3 [1,2]
ACCURACY
RANGE STUDIED: 2 to 8 mg/m3

(100-L samples)
BIAS: 0.01%
ACCURACY: ± 11.0%
APPLICABILITY: The working range is 0.5 to 10 mg/m3 for a 200-L air sample. This method is not applicable for the
determination of "cyclohexane-solubles" [3]. This analysis is simple but the method is nonspecific. Information on any other
particulate materials present should be assessed. The method may be extended to higher air concentrations (e.g., nuisance
dust levels) by collecting a smaller sample volume [4].
INTERFERENCES: The presence of any other particulate material in the air being sampled will be a positive interference since
this is a gravimetric method.
OTHER METHODS: This is Method S262 [5] in a revised format. It is similar, except for collecting device, to the method
described in the carbon black criteria document [3].

CARBON BLACK: METHOD 5000, Issue 2, dated 15 August 1994 - Page 2 of 4
EQUIPMENT:
1 . Sampler: 37-mm, 5-fjm pore size PVC filter and stainless steel support screen in 37-mm, cassette
filter holder (preferably, conductive).
2. Personal sampling pump, 1 to 2 L/min, with flexible connecting tubing.
3. Microbalance capable of weighing to 0.001 mg.
4. Static neutralizes e.g. Po-210; replace nine months after production date.
5. Forceps (preferably nylon).
6. Environmental chamber or room for balance (e.g. 20 ± 1 °C and 50 ± 5% RH).
SPECIAL PRECAUTIONS: Carbon black containing polynuclear aromatic hydrocarbons (cyclohexane

extractable materials) in excess of 0.1% (w/w) should be treated as a suspect carcinogen [3].
PREPARATION OF FILTERS BEFORE SAMPLING:
1. Equilibrate the filters in an environmentally controlled weighing area or chamber for at least 2 h.
NOTE: An environmentally controlled chamber is desirable, but not required.
2. Number the backup pads with a ballpoint pen and place them, numbered side down, in filter
cassette bottom sections.
3. Weigh the filters in an environmentally controlled area or chamber. Record the filter tare
weights, W,, (mg).
a. Zero the balance before each weighing.
b. Handle the filter with forceps. Pass the filter over an antistatic radiation source. Repeat this
step if filter does not release easily from the forceps or if filter attracts balance pan. Static
electricity can cause erroneous weight readings.
4. Assemble the filters in the filter cassettes and close firmly so that leakage around the filter will
not occur. Place a plug in each opening of the filter cassette. Place a cellulose shrink band
around the filter cassette, allow to dry, and mark with the same number as the backup pad.
SAMPLING:

6. Sample at 1 to 2 L/min for a total sample volume of 30 to 570 L Do not exceed a filter loading
of approximately 2 mg total dust. Take two to four replicate samples for each batch of field
samples for quality assurance on the sampling procedures.
SAMPLE PREPARATION:
7. Wipe dust from the external surface of the filter cassette with a moist paper towel to minimize
contamination. Discard the paper towel.
8. Remove the top and bottom plugs from the filter cassette. Equilibrate for at least 2 h in the
balance room.
9. Remove the cassette band, pry open the cassette, and remove the filter gently to avoid loss of
dust.
NOTE: If the filter adheres to underside of cassette top, gently lift using the dull side of scalpel
blade. Take care not to tear the filter.

10. Zero the microbalance before all weighings. Use the same microbalance for weighing filters
before and after sample collection. Calibrate the balance with National Institute of Standards
and Technology Class S-1.1 or ASTM Class 1 weights.
11. The set of replicate samples should be exposed to the same dust environment, either in a
laboratory dust chamber [6] or in the field [7]. The quality control samples must be taken with
the same equipment, procedures and personnel used in the routine field samples. Calculate
precision from these replicates and record Sr on control charts. Take corrective action when the
precision is out of control [6].
MEASUREMENT:
12. Weigh each filter, including field blanks. Record the post-sampling weight, W2 (mg). Record
anything remarkable about a filter (e.g., overload, leakage, wet, torn, etc.).
CALCULATIONS:
13. Calculate the concentration, C (mg/m3), of carbon black in the air volume sampled, V (L):
C . (W.-VM-tB.-B.) . 103, mg/m3.
where: W, = tare weight of filter before sampling (mg)

W2 = post-sampling weight of sample-containing filter (mg)
B, = tare weight of blank filter (mg)
B2 = post-sampling weight of blank filter (mg)
Method S262 [5] was issued on January 30, 1976, and validated over the range 1.9 to 7.7 mg/m3 for a
200-L sample and over the range 7.8 to 28 mg/m3 for a 100-L sample using Vulcan XC72 (0.03-//m
particle size; Cabot Corp.) in a Wright Dust Feeder [1]. Overall precision, SrT, was 0.056. Collection
efficiency was between 99 and 100%.
REFERENCES:
[2] Unpublished data from Non-textile Cotton Study, NIOSH/DRDS/EIB.
[3] NIOSH Criteria for a Recommended Standard ... Occupational Exposure to Carbon Black, U.S.
Department of Health, Education, and Welfare, Publ. (NIOSH) 78-204, 80-88 (1978).

[6] Bowman, J.D., D.L Bartley, G.M. Breuer, LJ. Doemeny, D.J. Murdock. Accuracy Criteria
Recommendation for the Certification of Gravimetric Coal Mine Dust Personal Samplers. U.S.
Department of Health and Human Services, NTIS Pub. No. 85-222446 (1984).
[7] Breslin, J.A., S.J. Page, R.A. Jankowski. Precision of Personal Sampling of Respirable Dust in
Coal Mines, U.S. Bureau of Mines Reports of Investigations #8740 (1983).
METHOD REVISED BY:
Frank Heart, P.E., NIOSH/DRDS; S262 and S349 originally validated under NIOSH Contract
CDC-99-74-45.

CARBON DIOXIDE 6603
CO2 MW: 44.01 CAS: 124-38-9 RTECS: FF6400000
METHOD: 6603 EVALUATION: FULL Issue 1: 15 May 1989

OSHA : 5000 ppm; STEL 30000 ppm PROPERTIES: gas; sublimes @ - 78.5 °C
NIOSH: 5000 ppm; STEL 30000 ppm
ACGIH: 5000 ppm; STEL 30000 ppm
(1 ppm = 1.8 mg/m3 @ NTP)
SYNONYMS: carbonic acid; dry ice
SAMPLER. GAS SAMPLING BAG TECHNIQUE: GAS CHROMATOGRAPHY (PORTABLE),

TCD
FLOW RATE: 0.02 to 0.1 L/min; fill bag £ 80% of
capacity; spot samples (step 2.a.) or TWA ANALYTE: carbon dioxide
samples (step 2.b.)
TEMPERATURE-INJECTION: ambient
STABILITY: at least 7 days @ 25 °C [1] -COLUMN: ambient
FIELD BLANKS: in bag from a non-work area CARRIER GAS: He, 100 mL/mm
COLUMN: 1.5m x 6-mm ID stainless steel, packed

with 80/100 mesh Poropak QS
DETECTOR: thermal conductivity
CALIBRATION: bag standards or calibrated gas mixtures
ACCURACY RANGE: 500 - 15000 ppm [2]
RANGE STUDIED : 2270 - 10000 ppm [3] ESTIMATED LOD: 1 ppm

(3.5-L samples)
ACCURACY: ± 5.3% [1] PRECISION (Sr): 0.005 [1]
BIAS: -2.5% [3]
APPLICABILITY: The working range is 500 to 15000 ppm (900 to 2700 mg/m3) in relatively non-complex atmospheres.
INTERFERENCES: Any compound having the same or nearly the same retention time as carbon dioxide on the column in use.
OTHER METHODS: This is method S249 in a revised format [2].

CARBON DIOXIDE: METHOD 6603, Issue 2, dated 15 August 1994 - Page 2 of 3
1. Carbon dioxide,* 99% or higher purity 1. Portable gas chromatograph (GC), with
2. Nitrogen,* purified thermal conductivity detector, column (p.
3. Helium,* purified 6603-1), and 5-mL gas sampling loop.
4. Air*, filtered, compressed 2. Strip chart recorder, if appropriate. (Many GCs
have built-in data-handling capabilities)
3. Personal sampling pump, 0.02 to 0.1 L/min or
other rate suitable for filling sample bag, with
* See SPECIAL PRECAUTIONS. 4. Sample bags, five-layer, 2- to 20- L, or other
appropriate sizes, fitted with a metal valve and
hose bib (Calibrated Instruments, 731 Saw Mill
Rd., Ardsley, NY 10502, or equivalent).
5. Gas-tight syringes, 10 mL and other
convenient sizes for making standards and GC
injections if GC is not equipped with gas
sampling loop.
6. Calibrated rotameters, for standards
preparation.
7. Label tape and marking pens for labelling
bags.
SPECIAL PRECAUTIONS: Shipment of compressed must comply with 49 CFR 171-177, DOT
regulations regarding shipment of hazardous materials.
SAMPLING AND MEASUREMENT:
1. Start GC and recorder (if applicable) and allow to warm up according to manufacturer's
instructions.
NOTE: A straight baseline should be attained at the highest sensitivity likely to be used.
2. Select one of the following sampling modes:
a. Spot sample. Draw air sample into the gas sampling loop of the GC with the on-board
sampling pump, if supplied. Alternatively, inject an aliquot of air to be sampled into the GC
with a gas-tight syringe.
NOTE: A large contributor to random error in the method is imprecision of replicate
injections. To improve precision:
(1) use a gas sampling loop for injections if available;
(2) make at least three replicate determinations per sample;
(3) use an injection volume large enough to be precisely readable, and consistent with that
used in calibration.
b. Integrated air sample for TWA determination.
(1) Evacuate a clean sample bag using the inlet port of a personal sampling pump.
NOTE: To reduce memory effects and contamination, use only previously unused
sample bags.
(2) Attach the sample bag to the outlet port of the personal sampling pump with a minimum
length of flexible tubing.
(3) Pump the air sample into the bag at a rate calculated to fill <80% of the sample bag
capacity over the sampling period.
NOTE: The flow rate must be known to ±5% throughout the sampling period.
(4) Within 24 hours after completion of sampling, introduce an aliquot of the sample into the
GC (as in step 2a).
3. Obtain the carbon dioxide peak height of the injected sample.
NOTE: Under these conditions, carbon dioxide elutes at about 2 min, after oxygen and nitrogen.

CARBON DIOXIDE: METHOD 6603, Issue 2, dated 15 August 1994 - Page 3 of 3
4. Perform the following in the laboratory before field work begins:

a. Establish a laboratory calibration graph with at least three replicate determinations of at least
five working standards. Plot peak height vs. mass of carbon dioxide.
b. Determine detector drift, averaged over the time period(s) expected to be used in the field.
c. Determine the ability of the GC column to separate the carbon dioxide peak from other
substances known or predicted to be present in the field samples.
5. Establish a daily field calibration graph (peak height vs. mass of carbon dioxide with triplicate
determinations of working standards under the same conditions as for samples (step 2.a).
Alternate analyses of samples and working standards, if possible.
CALCULATIONS:
6. Calculate mass, W (ng), of carbon dioxide in the sample by comparison of the sample peak
height with the daily calibration graph (step 5). Determine the concentration, C, of carbon
dioxide in the injected sample, V (mL):
C = W/V (mg/m3)
NOTE: Some GCs will perform this calculation electronically.
This method for carbon dioxide was evaluated in accordance with the criteria for validation described in
Reference [3]. Evaluation was over the range 2270-10000 ppm using a Fisher-Hamilton Gas Partitioner
Model 29 gas chromatograph with a thermal conductivity detector and a 5-mL gas sampling loop [1,2].
Recovery after storage of CO2 at 5800 ppm for 7 days was 92.5% (Saran or Tedlar bags), and 99.5% (5-
layer bags). Other GCs and columns other than the one used this evaluation are available for use for
the determination of carbon dioxide.
REFERENCES:
Welfare Publ. (NIOSH) 77-185 (1977).
Education, and Welfare (NIOSH) Publ. 77-157-C (1977).
80-133 (1980).
METHOD WRITTEN BY:
M. L Woebkenberg, NIOSH/DPSE

CARBON DISULFIDE 1600
cs, MW: 76.14 CAS: 75-15-0 RTECS: FF6650000

OSHA : 20 ppm; C 30 ppm; P 100 ppm PROPERTIES: liquid; d 1.263 g/mL @ 20 °C

NIOSH: 1 ppm; STEL 10 ppm (skin) BP 46.5 °C; MP - 1 12 °C; VP 40 kPa
ACGIH: 10 ppm (skin) (300 mm Hg; 40% v/v) @ 20 °C;
(1 ppm = 3.11 mg/m3@NTP) explosive range 1 to 50% v/v in air
SYNONYMS: dithiocarbonic anhydride
SAMPLER: SOLID SORBENT TUBE + DRYING TUBE TECHNIQUE: GAS CHROMATOGRAPHY, SULFUR FPD
(coconut shell charcoal, 100 mg/50 mg,
and sodium sulfate, 270 mg) ANALYTE: sulfur
FLOW RATE: 0.01 to 0.2 L/min DESORPTION: 1 mL toluene; stand 30 min

-MAX: 25 L VOLUME: 5fjL
SHIPMENT: dryer attached to charcoal, refrigerated TEMPERATURE-INJECTION: 150 °C

-DETECTOR: 145 °C
STABILITY: 1 week @ 25 °C
6 weeks @ 0 °C CARRIER GAS: N2 or He, 20 mL/min
BLANKS: 2 to 10 field blanks per set COLUMN: glass, 2 m x 6-mm OD, 5% OV-17 on
80/100 mesh GasChrom Q or equivalent
ACCURACY CALIBRATION: standard solutions of CS? in toluene
RANGE STUDIED: 46 to 183mg/m3 [2] RANGE: 0.05 to 0.5 mg per sample

(6-L samples)
BIAS: - 0.78%
OVERALL PRECISION 0.059 [1] PRECISION (§r): 0.052 @ 0.28 to 1.1 mg per sample [1]
ACCURACY: ± 12.9%
APPLICABILITY: The working range is 10 to 200 mg/m3 (3 to 64 ppm) for a 5-L air sample and is applicable to ceiling
determinations. Better sensitivity may be obtained by using higher sampling rates if high humidity is not present [3,4]. This
method has been used extensively in the viscose rayon industry and at carbon disulfide production facilities.
INTERFERENCES: No interference occurs from hydrogen sulfide [4]. Water vapor is a potential sampling interferant [4] which
is removed by the drying tube. Alternate GC columns, e.g., 5% OV-210 on Chromosorb G-HP or DB-5 fused silica capillary, aid
in resolution of chromatographic interferences.
OTHER METHODS: This revises Method S248 [5] and Method 1600 (dated 2/15/84). The criteria document method [3] uses
a higher sampling rate. This method replaces P&CAM 179 which uses a similar collection method but extraction-atomic
absorption for measurement [6].

CARBON DISULFIDE: METHOD 1600, Issue 2, dated 15 August 1994 - Page 2 of 4
1. Carbon disulfide, chromatographic quality.* 1. Sampler:

2. Toluene, chromatographic quality. a. Drying tube: glass tube, 7 cm long, 6-mm
3. Calibration stock solution, 0.0253 mg/fjL. OD, 4-mm ID; single 270-mg section of
Dilute 0.253 g CS2 (0.200 mL at 20 °C) to 10 granular anhydrous sodium sulfate
mL with toluene. Prepare in duplicate. between two silylated glass wool plugs.
4. Oxygen, purified. This removes moisture equivalent to 6 L of
5. Nitrogen or helium, purified. air at 100% RH and 22 °C.
6. Hydrogen, prepurified. b. Sorbent tube: glass tube, 7 cm long,
7. Air, filtered compressed. 6-mm OD, with flame-sealed ends and
plastic caps, containing two sections of
activated (600 °C) coconut shell charcoal
(front = 100 mg; back = 50 mg)
* See SPECIAL PRECAUTIONS. separated by a 2-mm urethane foam plug.
A silylated glass wool plug precedes the
front section and a 3-mm urethane foam
plug follows the back section. Pressure
drop across the tube at 1 L/min airflow
must be less than 3.4 kPa. Available
commercially.
3. PTFE tubing, 5-mm ID.
4. Refrigerant, bagged (0 °C).
5. Gas chromatograph, FPD with sulfur filter,
integrator and column (see page 1600-1).
NOTE: A valve to vent the solvent peak when
it elutes from the column is useful to
protect the detector.
6. Vials, glass, 25-mL, PTFE-lined caps.
9. Delivery pipets, 1- to 100-/A. and 1-mL, with
pipet bulb.
SPECIAL PRECAUTIONS: Carbon disulfide is toxic and an acute fire and explosion hazard (flash
point = -30 °C) [3,7]; work with it only in a hood.
SAMPLING:

sampling pump with flexible tubing. Connect the drying tube to the front section of the charcoal
tube with a 20-mm section of PTFE tubing.
to 25 L
NOTE: Samples may be taken up to 1 L/min if ambient humidity is low [3,4].
4. Keep the drying tube connected to the charcoal tube during shipping. Refrigerate (0 °C) to
prevent CS2 migration to the back section. Cap the open ends. Pack securely for shipment.
NOTE: Store samples away from any source of CS2 to avoid contamination.

SAMPLE PREPARATION:
5. Detach and discard drying tube. Place front and back sorbent sections of sampler tube in
separate vials. Discard glass wool and foam plugs.
6. Pipet 1.0 ml_ toluene into each vial. Cap each vial.
NOTE: Keep desorbed samples and standards away from sources of CS2 to avoid
contamination.

a. Add known amounts of calibration stock solution to toluene in 10-mL volumetric flasks and
dilute to the mark to prepare solutions in the range 0.02 to 0.5 mg CS2/mL
c. Prepare calibration graph ([peak area]1/2 vs. mg CS2).
NOTE: The FPD has a small linear range. Additional working standards may be required [9].
b. Inject a known amount (1 to 20 fjL) of calibration stock solution directly onto front sorbent
e. Prepare a graph of DE vs. mg CS2 recovered.
NOTE: At low levels (<0.1 mg CS2 per sample), DE may be low and variable.
MEASUREMENT:
autosampler.
NOTE 1: The retention time for toluene is ca. 30 min, which may be shortened by temperature
programming.
NOTE 2: If peak area is above the linear range of the working standards, dilute an aliquot of
desorbed sample with toluene, reanalyze, and apply the appropriate dilution factor in
calculations.
CALCULATIONS:
13. Determine the mass (corrected for DE), mg, of CS2 found in the sample front (Wf) and back (Wb)
sorbent sections, and in the average media blank front (Bf) and back (Bb) sorbent sections.
14. Calculate concentration, C, of CS2 in the air volume sampled, V (L):
C . W - Wb - B, -

This method modifies S248, in that 1 mL toluene (instead of 10 mL benzene) is used to desorb samples,
resulting in a better desorption efficiency at low levels and safer working conditions for the analyst [8].
Method S248 [5] was issued on January 30, 1976, and validated over the range 15 to 59 mg/m3 using a
6-L sample with spiked samplers and atmospheres generated by syringe pump/triple air dilution and
verified by total hydrocarbon analyzer [1]. Overall precision, SrT, was 0.059 with "found" concentrations
0.8% lower than "true" concentrations for 18 samples tested, representing a non-significant bias.
Breakthrough (with drying tube preceding charcoal tube) occurred at 162 min (100% RH, 40 ppm CS2,
0.2 L/min sampling rate) = 32.4 L; DE (0.28 to 1.12 mg/sample) = 0.86; storage stability
(0.56 mg/sample) = 85% recovery after one week at 25 °C. At a 1 L/min sampling rate, breakthrough
occurred at 19 L at 100 mg/m3 [4]. A user check of this method gave an estimated LOD of 0.02 mg
CS2 per sample [2].
REFERENCES:
[2] User check, UBTL, Inc., NIOSH Sequence #3990-L (unpublished, November 9, 1983).
[3] Criteria for a Recommended Standard. ..Occupational Exposure to Carbon Disulfide, U.S. Department
of Health, Education, and Welfare, Publ. (NIOSH) 77-156 (1977), available as GPO Stock
[4] McCammon, C.S., P.M. Quinn and R. Kupel. A Charcoal Sampling Method and a Gas
Chromatographic Analytical Procedure for Carbon Disulfide, Am. Ind. Hyg. Assoc. J., 36, 618-624
(1975).
77-1 57-A (1977).
Human Services, Publ. (NIOSH) 81-123, available as GPO Stock #017-033-00337-8 from
[8] Foley, G. D. NIOSH/DPSE (internal memo, April 17, 1985).
[9] Quincoces, C.E. and M.G. Gonzaleg. Characterization of the Flame Photometric Detector in the
Sulfur Mode, Chromatoqraphia 20:371 (1985).
METHOD REVISED BY:
Mary Lynn Woebkenberg, NIOSH/DPSE; S248 originally validated under NIOSH Contract CDC-99-74-45.

CARBON MONOXIDE 6604
CO MW: 28.00 CAS: 630-08-0 RTECS: FG3500000
OSHA: 50 ppm PROPERTIES: gas; BP -192 °C; MP -207 °C; vapor density
NIOSH: 35 ppm; C 200 ppm (air=1) 0.967; flammable (explosive) limits in
ACGIH: 25 ppm air 12.5 to 74.2%
(1 ppm = 1.14mg/m3)
SYNONYMS: monoxide; carbon oxide; carbonic oxide; flue gas
SAMPLER: PORTABLE DIRECT-READING CO TECHNIQUE: ELECTROCHEMICAL SENSOR

MONITOR
ANALYTE: carbon monoxide (CO)

VOL-MIN: instrument dependent
-MAX: none
CALIBRATION:
SHIPMENT: routine shipment of instrumentation - ZERO: CO-free air
-SPAN: standard cylinders of span gas in the
SAMPLE desired range
(aluminized air bags)
RANGE: 0 to 200 ppm
BLANKS: fresh air or compressed CO-free air from
cylinder ESTIMATED LOD: 1 ppm
ACCURACY PRECISION (Sr): 0.035 @ 20 ppm

0.012 @ 50 ppm
RANGE STUDIED: 0 to 200 ppm 0.008 @ 100 ppm [2]
BIAS: -1.7% [2]
ACCURACY: ± 6.0%
APPLICABILITY: Portable, direct-reading carbon monoxide monitors are applicable to any work environment for personal or area
monitoring.
INTERFERENCES: Several gaseous pollutants (e.g., NO2, SO2 ) may cause an interference at levels over 5 ppm. If these or other
pollutants are known or suspected to be present , use a monitor with a chemical interference scrubber over the sensor. Unknown
pollutants may require further experimentation to determine their effect on the sensor. As tested, SO2 (5 ppm), C02 (5000 ppm),
methylene chloride (500 ppm), diesel fuel (6/A./L , about 0.3 ppm benzene), and gasoline vapor (1 /jL/L. about 1 ppm benzene)
had no impact on most monitor readings [2]. Some monitors are equipped with a chemical interference scrubber while others
offer this as an option.
OTHER METHODS: Bag samples may be collected in aluminized bags (2-Lor larger) and analyzed later by placing the calibration
cap over the sensor and pumping the sample across the sensor at a nominal rate of 0.250 L/min with a personal sampling pump.
NIOSH Manual of Analytical Methods(NMAM), Fourth Edition, 5/15/96

CARBON MONOXIDE: METHOD 6604, Issue 1, dated 15 May 1996 - Page 2 of 3
1. CO*calibration gas, 20 to 50 ppm, compressed 1 . Carbon monoxide monitor: Envirocheck I single

gas cylinder, appropriate pressure regulator, sensor CO Monitor (Quest Technologies);
and other items as recommended by CO262 or STX70 (Industrial Scientific); MiniCO
manufacturer for field check of monitor (MSA); or other electrochemical CO monitor
response. with equivalent performance specifications.
2. Personal sampling pump, 0.250 L/min, with inlet
and outlet, used for bag filling and sample
analysis when off-site analysis is needed.
3. Air bags, aluminized, 2-L, or other appropriate
sizes (optional).
* See SPECIAL PRECAUTIONS 4. Replacement batteries or battery recharger, as
appropriate for monitor.
SPECIAL PRECAUTIONS: Carbon monoxide is a highly flammable, dangerous fire and explosive risk, and
is toxic by inhalation. Shipments of compressed calibration gases must comply with 49 CFR 1992
regulations.
SAMPLING AND MEASUREMENT:
1. Zero monitor with CO-free air at the same temperature and relative humidity as the work environment,
if possible.
NOTE: Monitors are more sensitive to temperature variations than to humidity variations. Most
monitors have temperature compensating circuitry.
2. For personal monitoring, locate the monitor as near the worker's breathing zone as possible.
3. For area monitoring, locate monitor in an area with good air circulation about 60 to 70 inches above
the floor.
NOTE: Make sure the sensor is not obstructed in either application.
4. Calibrate with a standard calibration mixture of CO in air from a pressurized cylinder at the CO level
recommended by the monitor manufacturer (Normally, 20 to 50 ppm CO). The monitor should be
calibrated at the temperature and relative humidity as near as possible to that of the work environment
in which it will be used.
5. Check the calibration daily and recalibrate whenever the monitor reading varies from the span gas by
5% or more, or as the manufacturer recommends.
CALCULATIONS:
6. Read concentration directly from the monitor display.
Some monitors (data logger models) will maintain a continuous record of the data as it is accumulated
and will calculate the Average, TWA, Peak, etc. concentrations. These data may be read from the
display at any time. Some monitors will also store this information for downloading to a computer or
printer at the end of the monitoring period. Other monitors only display the current reading, requiring
the operator to manually record the data. All monitor models are equipped with alarms that will warn

CARBON MONOXIDE: METHOD 6604, Issue 1, dated 15 May 1996 - Page 3 of 3
the user (audibly, visually or both) whenever the concentration of CO exceeds the preset level of the
alarm. Many are equipped with two-level alarms [3].
The performance of six direct-reading carbon monoxide monitors was evaluated over a period of 12 months
at CO concentrations up to 200 ppm and a range of ambient temperatures and relative humidities. Most of the
tests were conducted at or near the PEL For mean recovery studies, six different monitors were used and
readings were taken approximately 1 h apart. Recovery at 20 ppm was 105% (n = 42); at 50 ppm, 99.6% (n
= 36); and at 100 ppm, 99.9% (n = 30). Thus, the overall mean bias was calculated at - 1 .7%. The precision
(§r) at 20 ppm was 0.035 (35 readings from 5 monitors over a 7-h period). At 50 ppm, §r was 0.012 (30
readings from 5 monitors over a 6-h period), and at 100 ppm, §r was 0.008 (36 readings from 6 monitors over
a 6-h period). Tests also were conducted to determine response time, zero and span drift, alarm decibel level,
battery life, life of the sensors, as well as the effects of selected interferences (gases, vapors, and RF) and the
effects of handling and transporting to remote sites.
REFERENCES:
[1] NIOSH [1977]. Backup data report no. S340, prepared under NIOSH Contract No. 210-76-0123.
[2] Woodfin WJ, Woebkenberg ML [in preparation]. An evaluation of portable direct-reading carbon
monoxide monitors.
[3] Ashley K [1994]. Electroanalytical applications in occupational and environmental health.
Electroanalysis 6:805-820.
METHOD WRITTEN BY:
W. James Woodfin, NIOSH, DPSE, MRB

CARBON TETRACHLORIDE

CHLORDANE 5510
CinHfiClo
'10 MW: 409.80 CAS: 57-74-9 RTECS: PB9800000

OSHA : 0.5 mg/m3 (skin) PROPERTIES: liquid; d 1 .59 to 1 .63 g/mL @ 25 °C;
NIOSH: 0.5 mg/m3 (skin); carcinogen; BP 175 °C; VP 0.0013 Pa
Group I Pesticide (1.0 x 10'5 mm Hg) @ 20 °C
ACGIM: 0.5 mg/m3 (skin), suspect human carcinogen
SYNONYMS: 1,2,4,5,6,7, 8, 8-octachloro-3a,4,7,7a-tetrahydro-4,7-methanoindane and isomers; Toxichlor; Octachlor
SAMPLER: FILTER AND SOLID SORBENT TUBE TECHNIQUE: GAS CHROMOTOGRAPHY, ELECTRON
(0.8-//m cellulose ester membrane; CAPTURE DETECTOR (GC/ECD)
Chromosorb 102, 100/50 mg)
ANALYTE: Chlordane
EXTRACTION: 10 mL toluene, stand 30 min
VOL-MIN: 10 L @ 0.5 mg/m3
-MAX: 200 L INJECTION VOLUME:

-DETECTOR: 300 °C
SAMPLE STABILITY: > 1 week @ 25 °C [1] -COLUMN: 205 °C
FIELD BLANKS: 2 to 10 field blanks per set CARRIER GASES: 95% argon/5% methane @ 75 mL/min
MEDIA BLANKS: 2 per set COLUMN: 2 m x 4-mm ID glass packed with 1.5%,
SP2250/1.95% SP2401 on 100/120 mesh
BULK SAMPLE: required
CALIBRATION: solution of analyte in toluene or hexane
with internal standard

ACCURACY
RANGE STUDIED: 0.16 to 1.17 mg/m3 [1.2]
(120-L samples) PRECISION (Sr): 0.02 @ 6 to 120 fjg per sample [2]
BIAS: 3.0%
OVERALL PRECISION (S,T): 0.070 [1,2]
ACCURACY: ± 15.3%
APPLICABILITY: The working range is 0.04 to 1.2 mg/m3 for a 120-L sample. Chlordane, accompanied by a mixture of penta-,
hexa-, hepta-, and nonachlorinated compounds, is defined by a group of five chromatographic peaks. It is necessary to
determine the percentage of Chlordane and its isomers in the standards used.
INTERFERENCES: None identified; an alternate column is 2 m x 2-mm ID glass packed with 3% QF-1 on 100/120 mesh
Chrom Q.
OTHER METHODS: This is NIOSH method S278 in a revised format. [2]

CHLORDANE: METHOD 5510, Issue 2, dated 15 August 1994 - Page 2 of 4
1. Toluene, distilled in glass. 1. Sampler: 37-mm, 0.8-//m pore size cellulose

2. Hexane, distilled in glass. ester membrane filter supported by a stainless
3. Chlordane, 95%.* steel screen in a two-piece filter cassette
4. Calibration stock solution, ca. 6 mg/mL holder plus a 10 cm x 8-mm OD x 6-mm ID,
Dissolve 10 mg Chlordane in 1 mL toluene. 20/40 Chromosorb 102 tube (front = 100 mg;
NOTE: Since Chlordane is available only as a back = 50 mg), separated by 3-mm silanized
mixture, standardize the solution as follows: glass wool plug, flame sealed ends with plastic
a. Dilute 10 //L calibration stock solution caps. Pressure drop across the tube at 1
to 10 mL L/min must not exceed 2.5 mm Hg. Filters
b. Analyze by steps 11-13. and tubes are commercially available.
c. Divide combined area of Chlordane peaks 2. Personal sampling pump, 0.5 to 1 L/min, with
(Fig. 1 ) by total area of all peaks to flexible connecting tubing.
determine fraction Chlordane, f. 3. Gas chromatograph, electron capture
5. Internal standard, p,p'-DDT, 98%.* detector, integrator and column (page 551 0-1 ).
6. 95% Argon/5% methane mixture, purified. 4. Vials, scintillation, 20-mL, PTFE-lined caps.
6. Flasks, volumetric 10-mL
7. Bottles, 60 mL, 40-mm ID, straight-sided with
a PTFE-lined cap for extracting filter holder
* See SPECIAL PRECAUTIONS. and screen.
8. Stopwatch.
9. Manometer.
1 0. Pipets, 1 - and 1 0-mL an other convenient sizes
for preparing standards.
11. Tweezers.
SPECIAL PRECAUTIONS: Chlordane and p,p'-DDT are toxic and rapidly absorbed through the skin [4].
Use gloves and eyeglasses to avoid direct contact with these compounds. Handle these chemicals and
organic solvents with care in the laboratory hood. Chlordane is a potential human carcinogen [5].
SAMPLING:

2. Assemble the sampler and connect the sorbent tube (ends broken just before the connection) to
the sampling pump with backup section nearest the sampling pump. Keep the sampler in a
vertical position during sampling.
to 200 L
4. Remove the sorbent tube from the outlet of the cassette and connect it to the inlet side of the
cassette. Cap the open end of the sorbent tube and plug the outlet of the cassette. Ship
sampler with appropriate blanks to laboratory.
5. In separate package, ship bulk sample of the suspected material.
SAMPLE PREPARATION:
6. Separate the sampler components for extraction as follows:

a. Into a bottle, transfer the filter, front sorbent section and glass wool plugs. Add 10.0 mL
toluene. After desorption is complete, dilute a 1-mL aliquot to 10 mL for analysis.
b. Into a second bottle, transfer the stainless steel screen. Using a 10-mL volumetric pipet,
rinse the inner surfaces of the cassette into the bottle with hexane.
c. Into a scintillation vial, transfer the back sorbent section. Add 10.0 mL toluene.
7. Cap each container and allow to stand 30 min. with occasional swirling.
NOTE: A suitable internal standard such as p,p'-DDT may be added, at 0.4 fjg/mL, at this point.


a. Add known amounts of calibration stock solution to toluene containing internal standard in
10-mL volumetric flasks and dilute to the mark. Use serial dilutions as needed to obtain
Chlordane concentrations in the range 0.01 to 15 //g/mL
b. Analyze the samples and blanks (steps 11 through 13).
c. Prepare a calibration graph (ratio of the total Chlordane peak areas to peak area of internal
standard vs. //g Chlordane).
9. Determine recovery at least once for each lot of filters and Chromosorb 102 used. Prepare three
samplers at each of five levels plus three media blanks.
a. Place cellulose ester membrane filter and 100 mg of Chromosorb 102 in a bottle.
b. Add calibration stock solution to the filter and Chromosorb 102 in the container with a
microliter syringe. Prepare parallel blank samples with no added analyte.
c. Cap the bottle. Allow to stand overnight.
d. Desorb (steps 6 and 7) and analyze with working standards (steps 11 through 13).
e. Prepare a graph of recovery vs. //g Chlordane recovered.
10. Check recovery at two levels for each sample set in duplicate. Repeat recovery graph
determination if checks do not agree to within 5% of recovery graph.
MEASUREMENT:
on page 5510-1.
12. Inject 2-//L sample aliquot using solvent flush technique or with autosampler. Make duplicate
injections of samples and standards.
solution, reanalyze and apply the appropriate dilution factor in calculations.
13. Measure peak areas. Divide the total Chlordane peak area (sum of five peaks; see Fig. 1) by the
peak area of internal standard on the same chromatogram.
CALCULATIONS:
14. Determine the mass, //g (corrected for recovery), of Chlordane found in the filter plus front
sorbent section (Wf), back sorbent section (Wb), extract from cassette and screen (Wc), and
average media blank filter plus front sorbent section (Bf) and back sorbent section (Bb).
15. Calculate the concentration, C, of Chlordane in the volume of air sampled, V (L):
C - W*W«--
Method S278 was validated on June 8, 1979, [1,2,6]. The substance used to dynamically generate test
atmospheres at 25 °C and 760 mm Hg was Ortho-Klor-72 (40% Chlordane), Velsicol Chemical
Corporation. Collection efficiencies and recoveries were close to 1.00 in the range 6 to 120 //g per
sample. No significant breakthrough was observed after 240 min of sampling an atmosphere of 1.1
mg/m3 Chlordane at a flow rate of approximately 1 L/min. Samples spiked with Chlordane, extracted
with toluene, and stored one week at room temperature gave recoveries of 96 to 100%. Overall
precision (SrT) was 0.07. No significant bias was found.

REFERENCES:
[1] NIOSH Backup Data Report S278 (June 8, 1979) for Chlordane prepared under NIOSH Contract No.
210-76-0123 (1979).
[2] NIOSH Manual of Analytical Methods, 2nd. ed., V. 6, S278, U.S. Department of Health and Human
[3] UBTL, Inc. NIOSH Seq. Report 4-999-K (July 19, 1985, unpubl).
[4] NIOSH/OSHA Occupational Health Guidelines for Chemical Hazards. U.S. Department of Health and
Human Services Publ. (NIOSH) 81-123 (1981), available as stock #PB 83-154609 from NTIS,
Springfield, VA22161.
(1980).
METHOD REVISED BY:
Gangadhar Choudhary, Ph.D., ATSDR; S278 originally validated under NIOSH Contract No. 210-76-0123.
Figure 1 . Chromatogram of Chlordane analytical standard.
K
8

CHLORINATED CAMPHENE 5039
C10H,0CI8 (average) MW: 414 (average) CAS: 8001-35-2 RTECS: XW5250000
OSHA : 0.5 mg/m3 (skin) PROPERTIES: solid; MP 70 °C to 95 °C; BP (760 mm Hg)

NIOSH: lowest feasible (skin), carcinogen. Class I Pesticide decomposes; sp. gr. 1.63; VP 0.03 to 0.05
ACGIH: 0.5 mg/m3 (skin); STEL 1 mg/m3 (skin) kPa (0.2 to 0.4 mm Hg) @ 20 °C
(1 ppm = 16.9 mg/m3 @ NTP)
SYNONYMS: toxaphene
SAMPLER: FILTER TECHNIQUE: GAS CHROMATOGRAPHY, 63Ni ECD

(0.8-jum cellulose ester membrane)
ANALYTE: chlorinated camphene
DESORPTION: 10 mL petroleum ether
VOLUME: 5fjL
SHIPMENT: place filter and backup pad in screw cap vial;
ship separate bulk sample TEMPERATURE-INJECTION: 230 °C
-DETECTOR: 250 °C
CARRIER GAS: nitrogen, 50 mL/min
COLUMN: glass, 1 .8 m x 6-mm OD, packed with 3%
OV-1 on 100/120 mesh Gas Chrom Q
ACCURACY CALIBRATION: chlorinated camphene in petroleum ether
RANGE STUDIED: 0.225 to 1.16 mg/m3 [1] RANGE: 0.7 to 14 fjg per sample [1]
(15-L samples)
ESTIMATED LOD 0.14pg per sample [1]
OVERALL PRECISION (SrT): 0.076 [1] PRECISION (Sr): 0.024 (3 to 14//g per sample) [1]
APPLICABILITY: The working range is 0.05 to 1.5 mg/m3 for a 15-L air sample.
INTERFERENCES: Other pesticides such as aldrin, parathion, dieldrin, DDT and its metabolites, and polychlorinated biphenyls
elute in the retention time band for chlorinated camphene.
OTHER METHODS: This is Method S67 [2] in a revised format. Toxaphene in air has been collected on Chromosorb 102 with
acceptable recovery [3].

CHLORINATED CAMPHENE: METHOD 5039, Issue 1, dated 15 August 1994 - Page 2 of 3
1. Chlorinated camphene* (toxaphene). 1. Sampler: 37-mm cellulose ester membrane

2. Petroleum ether*, 30 to 60 °C, suitable for filter (0.8-//m pore size) supported by a
pesticide residue analysis. cellulose backup pad in a three-piece filter
3. Nitrogen, purified. holder. Do not use tenite filter holders.
4. Calibration stock solution, 0.1 mg/mL 2. Personal sampling pump, 0.2 to 1 L/min, with
Dissolve 5 mg of chlorinated camphene in flexible connecting tubing.
50 mL petroleum ether. 3. Gas chromatograph, 83Ni BCD, integrator, and
4. Vials, 20-mL with PTFE-lined screw caps for
shipping filters and pads.
5. Syringes, 10-/A. and larger sizes for
* See SPECIAL PRECAUTIONS. preparation of standard solutions.
6. Pipet, 10-mL
8. Tweezers, stainless steel.
SPECIAL PRECAUTIONS: Petroleum ether is highly flammable. Prepare samples and standards in
well-ventilated hood. Overexposure to chlorinated camphene may cause nausea, mental confusion, and
unconsciousness; contact with chlorinated camphene solutions may cause skin irritation [4].
SAMPLING:

2. Sample at an accurately known flow rate between 0.2 and 1 L/min for a sample size of 2 to
SOL
3. Carefully transfer the filter and backup pad to a screw cap vial by means of tweezers.
SAMPLE PREPARATION:
4. Pipet 10 mL petroleum ether into each vial and seal.

5. Gently swirl the vial to wet the filter and backup pad. Allow to stand 30 min.

a. Add known amounts of calibration stock solution to petroleum ether in 10-mL volumetric
flasks and dilute to the mark to obtain concentrations in the range 0.14 to 14 //g chlorinated
camphene/10 mL
c. Prepare calibration graph (sum of peak areas in the retention time band vs. //g chlorinated
camphene).
7. Determine recovery (R) at least once for each batch of filters used for sampling in the working
range. Prepare three filters at each of five levels plus three media blanks.
a. Deposit a known amount of calibration stock solution onto the filter. Allow filters to air dry.
b. Store samples overnight in vials.
c. Prepare (steps 4 and 5) and analyze with samples (steps 8 and 9).
d. Prepare a graph of R vs. fjg chlorinated camphene recovered.
graph and R graph are in control.

CHLORINATED CAMPHENE: METHOD 5039, Issue 1, dated 15 August 1994 - Page 3 of 3
MEASUREMENT:

on page 5039-1. Inject 5-^L aliquots manually using solvent flush technique or with autosampler.
NOTE: If peak areas are outside the calibration range, make dilution of sample or standard
solution, analyze and apply the dilution factor in calculations.
10. Sum the peak areas in the retention time band. Use bulk sample to identify the appropriate
retention time band.
CALCULATIONS:
11. Determine the mass, fjg (corrected for R), of chlorinated camphene found in each sample (W)
and average media blank (B).
12. Calculate concentration, C, of chlorinated camphene in the air volume sampled, V (L):
c -
V
This method was evaluated over the range 0.22 to 1.2 mg/m3 at 22 °C and 761 mm Hg using 15-L
samples [1]. No reference method was used. The collection efficiency for the filters was found to be
1 .0 using a challenge concentration of 1 .3 mg/m3 for 30 L Average recoveries of chlorinated camphene
from cellulose ester filters were 91% to 98% in the range 0.7 to 14 fJQ per sample. Cassettes were found
to be unsuitable for storage of 0.7 fjg chlorinated camphene on filters for 1 day at room temperature.
REFERENCES:
Welfare, Publ. (NIOSH) 77-185 (1977), available as Stock No. PB 274-248 from NTIS, Springfield,
VA22161.
[3] Thomas, Thomas C.; Nishioka, Yoshimi A., "Sampling of Airborne Pesticides using Chromosorb
102," Bull. Environ. Contam. Toxicol., 35(4), 460-5 (1985).
and Human Services, Publ. (NIOSH) 81-123 (1981), available as Stock No. PB 83-154609 from
METHOD REVISED BY:
James E. Arnold, NIOSH/DPSE; Method S67 originally developed under NIOSH Contract CDC-99-74-45.

CHLORINATED DIPHENYL OXIDE 5025
C12H4CI60 MW: 376.88 CAS: 55720-99-5 RTECS: KO4200000

OSHA : 0.5 mg/m3 PROPERTIES: Table 1

NIOSH: 0.5 mg/m3
ACGIH: 0.5 mg/m3
SYNONYMS: chlorinated diphenyl ether; hexachlorodiphenyl oxide
SAMPLER: FILTER (O.B-fjm cellulose ester membrane) TECHNIQUE: GAS CHROMATOGRAPHY, ELECTROLYTIC
CONDUCTIVITY DETECTION
FLOW RATE: 0.5 to 1 .5 L/min
ANALYTE: chlorinated diphenyl oxide
-MAX: 200 L DESORPTION: 10 mL isooctane, stand 2 hours
SHIPMENT: within 1 h of sampling, transfer filter INJECTION VOLUME: 15 //L

and backup pad to screw-cap bottle;
otherwise, routine TEMPERATURE-FURNACE: 760 °C
-TRANSFER LINE: 225 °C
SAMPLE STABILITY: not determined -VENT: 250 °C
-COLUMN: 210 °C
BLANKS: 2 to 10 field blanks per set GASES-FURNACE: H2, 150 mL/min
-CARRIER: N2, 150 mL/min
BULK SAMPLE: required; for proper identification
of analytes COLUMN: 1.5 m x 2-mm ID glass; 5% SE-30 on
80/100 mesh Chromosorb WHP
ACCURACY CALIBRATION: standard solutions of chlorinated

diphenyl oxide in isooctane
(90-L samples) RANGE: 4 to 150 //g per sample [2]
BIAS: - 0.21%
ESTIMATED LOD: 0.2 /ug per sample [1]
PRECISION (Sr): 0.019 @ 0.02 to 0.09 mg
ACCURACY: ±13.76%
per sample [1]
APPLICABILITY: The working range is 0.05 to 1.5 mg/m3 for a 90-L air sample. The method has been evaluated only for the
hexachloro derivative. The sampler may not be adequate for the monochloro or dichloro derivatives, which have higher vapor
pressures.

CHLORINATED DIPHENYL OXIDE: METHOD 5025, Issue 2, dated 15 August 1994 - Page 2 of 4
1. Isooctane, chromatographic quality. 1. Sampler: cellulose ester membrane filter,

2. Calibration stock solution, 2//g///L chlorinated 0.8-//m pore size, 37-mm diameter, supported
diphenyl oxide* in isooctane. Prepare in by cellulose backup pad in two-piece
duplicate. polystyrene filter holder.
3. Nitrogen, purified. 2. Personal sampling pump, 0.5 to 1.5 L/min,
4. Hydrogen, prepurified. with flexible connecting tubing.
3. Gas chromatograph, electrolytic conductivity
detector, effluent vent, integrator and column
(page 5025-1).
4. Vials, 20-mL, PTFE-lined caps, for shipping
filters.
5. Syringes, 25-//L, readable to 0.1 fjL.
* See SPECIAL PRECAUTIONS. 6. Volumetric flasks, 10-mL
7. Pipet, 10-mL
8. Tweezers.
SPECIAL PRECAUTIONS: Prolonged skin contact with chlorinated diphenyl oxide can cause chloracne;
acute and chronic exposure can cause liver damage [3,4].
SAMPLING:

to 200 L
3. Within 1 h of sampling, using tweezers, carefully transfer the filter and backup pad to a vial.
SAMPLE PREPARATION:
4. Pipet 10.0 mL isooctane into each vial containing a sample or blank filter and backup pad. Seal
and gently swirl the vial to wet the filter and backup pad. Allow to stand 2 h.

a. Add known amounts of calibration stock solution to isooctane in 10-mL volumetric flasks
and dilute to the mark to obtain concentrations in the range 0.4 to 15 fjg chlorinated
diphenyl oxide/mL
c. Prepare calibration graph (sum of areas of selected peaks vs. //g chlorinated diphenyl
oxide).
6. Determine recovery (R) at least once for each batch of filters used for sampling in the calibration
range. Prepare three filters at each of five levels plus three media blanks.
a. Deposit a known amount of calibration stock solution onto the filter. Allow filters to air dry.
b. Store samples overnight in vials.
c. Prepare (step 4) and analyze with working standards (steps 8 and 9).
d. Graph R vs. fjg chlorinated diphenyl oxide.
graph and R graph are in control.

MEASUREMENT:

autosampler. Open the effluent vent to keep the solvent from passing into the detector. Close
the effluent vent after the solvent peak has eluted.
NOTE: Under conditions given, the solvent elutes in about 20 sec. The large quantity of solvent
injected may cause malfunction of the conductivity cell, unless it is vented.
9. Sum the areas of selected peaks.
NOTE: Use a bulk sample if necessary to identify the appropriate chromatographic peaks.
CALCULATIONS:
10. Determine the mass, fjg (corrected for R) of chlorinated diphenyl oxide found in the sample (W)
and in the average media blank (B) from the calibration graph.
11. Calculate concentration, C, of chlorinated diphenyl oxide in the air volume sampled, V (L):
C . W__B_, mg/m3.
Method S119 was evaluated over the range 0.1 to 1 mg/m3 hexachlorodiphenyl oxide at 22 °C and 767
mm Hg using 90-L samples [1]. Overall precision, SrT, was 0.070; no reference method was used. The
test atmospheres were generated from solutions (0.25 to 0.5% w/v) of chlorinated diphenyl oxide (Chem
Samples) in toluene, using a fluid aspirator, cyclone and an impactor. Sampling with two filters in series
was conducted in an atmosphere containing 1 mg/m3 chlorinated diphenyl oxide. Chlorinated diphenyl
oxide was found only on the front filters (with LOD = 0.002 mg/m3). Filters enriched with 100 //g
chlorinated diphenyl oxide were analyzed after passing 100 L of air through them. The resulting
recovery of the analyte was 99.75% with Sr = 0.017%. The recovery of chlorinated diphenyl oxide from
enriched filters through which no air was drawn was 1.012 in the range 23 to 90 fjg per sample. Storage
stability of the sample was not tested.
REFERENCES:
Welfare, Publ. (NIOSH) 77-185 (1977), available as Stock No. PB 274-248 from NTIS, Springfield, VA
22161.
Human Services, Publ. (NIOSH) 81-123 (1981), available as Stock #PB83-1 54609 from NTIS,
Springfield, VA 22161.
[4] Occupational Diseases. A Guide to Their Recognition, revised ed., 255-256, U.S. Department of
[5] Patty, F. A. Industrial Hygiene and Toxicology. 2nd ed, Vol. 2, 1706-1707, Interscience, New York
(1963).
METHOD REVISED BY:
James E. Arnold, NIOSH/DPSE; S119 originally developed under NIOSH Contract CDC-99-74-45.

Table 1. Properties of chlorinated diphenyl oxide [3,5].
BP, °C d, g/mL Vapor Pressure @ 25 °C

Compound (8 mm Ha) 25 °C Pa mm Ha ma 7m3 1 ppm in ma/m3 & NTP
Monochloro- 153 1.19 0.93 0.007 77 8.37
Dichloro- 168.2 1.32 0.08 0.0006 8 9.78
Hexachloro- 230 to 260 1.57 < 0.008 < 0.00006 <1 15.41
@20 °C

CHLORINATED TERPHENYL (60% CHLORINE) 5014
'l9.35 MW: 552 (average) CAS: 1 1 126-42-4 RTECS: TQ1 390000

OSHA : no PEL PROPERTIES: solid; d 1.67 g/mL @ 25 °C; BP 280 to

NIOSH: no REL 335 °C @ 5 mm Hg (0.67 kPa); softening
ACGIH: no TLV point 98 to 105.5 °C
(1 ppm = 23 mg/m3 @ NTP)
SYNONYMS: chlorinated triphenyl, polychloroterphenyl, PCT, Aroclor 5460
SAMPLER: FILTER TECHNIQUE: GAS CHROMATOGRAPHY, 63Ni ECD

(glass fiber)
ANALYTE: chlorinated terphenyl
DESORPTION: 4 mL isooctane, 30 min ultrasonic
VOL-MIN: 100 L @ 10 fjg/m3 agitation
-MAX: 1500 L
INJECTION
SHIPMENT: routine VOLUME: 2 //L
SAMPLE TEMPERATURE-INJECTION: 240 °C

STABILITY: at least 7 days @ 25 °C [1] -DETECTOR: 300 °C
-COLUMN: 240 °C
GASES-CARRIER: nitrogen, 40 mL/min
-PURGE: nitrogen
COLUMN: 2.0 m x 2-mm ID glass; 3% QF-1 on

ACCURACY 80/100 mesh Gas Chrom Q or equivalent
RANGE STUDIED: 0.01 to 1.0 mg/m3 [1] CALIBRATION: chlorinated terphenyl in isooctane
(100-L samples)
OVERALL PRECISION (S,T): not evaluated ESTIMATED LOD: not determined
INTERFERENCES: Presence of other chlorinated terphenyls, e.g., Aroclor 5442 (42% chlorine), or other substances with similar
retention and detection characteristics may interfere with the analysis.
OTHER METHODS: None evaluated by NIOSH.

CHLORINATED TERPHENYL (60% CHLORINE): METHOD 5014, Issue 2, dated 15 August 1994 - Page 2 of 3
1. Isooctane (2,2,4-trimethylpentane), distilled in 1. Sampler: 37-mm glass fiber filter (Gelman

glass.* #64877 or equivalent) supported by a backup
2. Hexane, distilled in glass.* pad in a closed-face polystyrene cassette
3. Chlorinated terphenyl (60% chlorine).* (Gelman #4338 or equivalent).
4. Calibration stock solution, 1 mg/mL Dilute 2. Personal sampling pump, 1 to 3 L/min, with
an accurately weighed 100-mg portion of flexible connecting tubing.
chlorinated terphenyl to 100 mL with hexane. 3. Gas chromatograph, 63Ni BCD, integrator and
5. Nitrogen, 99.999%. column (page 5014-1).
4. Tweezers, stainless steel.
5. Vials, glass, 5-mL, crimp seals or caps,
silicone rubber septa lined with
polyperfluoroethylene.
* See SPECIAL PRECAUTIONS. 6. Pipets, 1-, 2- and 4-mL, with pipet bulb.
7. Ultrasonic bath.
8. Balance, readable to 0.1 mg.
9. Volumetric flasks, 5-, 10-, 25- and 100-mL
10. Syringe, 10-//L
SPECIAL PRECAUTIONS: Hexane (flash point = -22 °C) and isooctane (flash point = 4 °C) are
highly flammable. Prepare samples and standards in well-ventilated hood.
Chlorinated terphenyls may be similar to chlorinated biphenyls in toxicity. Use protective clothing to
avoid skin contact.
SAMPLING:

2. Sample at an accurately known flow rate between 1 and 3 L/min for a total sample size of 100
to 1500 L
SAMPLE PREPARATION:
3. Transfer filter to 5-mL vial using tweezers. Discard backup pad.

4. Pipet 4.0 mL of isooctane into vial and seal immediately.
5. Agitate vial in ultrasonic bath for 30 min to complete extraction.
6. Calibrate daily with at least six working standards over the range 1 to 100 fjg chlorinated
terphenyl per sample.
a. Add known amounts of calibration stock solution to hexane in 10-mL volumetric flasks and
dilute to the mark.
c. Prepare calibration graph (detector response vs. //g chlorinated terphenyl per sample).
7. Prepare two control samples at each of two levels for checking analysis of field samples.
a. For each control sample, inject calibration stock solution directly onto filter. Mount filter in
cassette and draw ca. 30 L of analyte-free air through (to evaporate hexane). Seal cassette
and store overnight.

CHLORINATED TERPHENYL (60% CHLORINE): METHOD 5014, Issue 2, dated 15 August 1994 - Page 3 of 3
b. Desorb filters as in steps 3 through 5, and analyze as in steps 9 and 10.

8. Check for possible contamination during shipment of field samples by comparing results from
field blanks and media blanks.
MEASUREMENT:
9. Set gas chromatograph to conditions given on page 5014-1 and optimize detector performance
per manufacturer's instructions. Using given conditions, retention time of largest and most
distinct peak in cluster was about 6.1 min.
10. Inject sample aliquot and measure detector response, e.g., height from base of cluster to top of
most prominent peak.
CALCULATIONS:
11. Read the mass, //g, of chlorinated terphenyl found in each sample (W) and average media blank
(B) from calibration graph.
12. Calculate concentration, C (mg/m3), of chlorinated terphenyl in the air volume sampled, V (L):
c.
Measurement precision was determined by analyzing spiked sampling media [1]. The average recovery
was 1 .006. There appeared to be no effect on recovery when up to 2700 L of charcoal-filtered air (40
°C and 40% relative humidity) was passed through filters spiked at the 1-//g level. Recoveries from
100-L samples collected from generated aerosol were 1.05 (Sr = 0.162) after seven days storage, and
0.875 (S, = 0.206) after 14 days storage, relative to the amount found after one day. Generated
concentrations were not reproducible, and independent methods for determining the true concentration
appeared to provide lower and more imprecise results than this method. Because of the difficulty in
determining the true concentration, overall precision and bias were not determined. References [1] and
[2] provide additional information.
REFERENCES:
[1] Graham, M. M., and H. K. Dillon. Analytical Methods Evaluation and Validation for
1,2,4-Trichlorobenzene, 1 ,2,4,5-Tetrachlorobenzene, Pentachlorobenzene, and Polychlorinated
Terphenyls: Research Report for Polychlorinated Terphenyls, NIOSH Contract No. 210-79-0102,
Southern Research Institute, Birmingham, AL, available from NTIS (1982) as PB-83-1 40-087.
[2] Kimbrough, R. D., ed. "Halogenated Biphenyls, Terphenyls, Naphthalenes, Dibenzodioxins and
Related Products," Topics jn Environmental Health. V. 4, Elsevier/North-Holland Biomedical Press,
Amsterdam, 20-21 (1980).
METHOD WRITTEN BY:
R. Alan Lunsford, Ph.D., NIOSH/DPSE; data obtained under NIOSH Contract 210-79-0102.

CHLORINE 6011
CI5 MW: 70.91 CAS: 7782-50-5 RTECS: F021 00000
METHOD: 6011, Issue 2 EVALUATION: FULL Issue 1: 15 May 19B9

OSHA : C 1 ppm PROPERTIES: gas; d 3.214 g/L at 0 °C; BP -34.6 °C;

NIOSH: 0.5 ppm; STEL 1 ppm vapor density (air = 1) 2.5
ACGIH: 0.5 ppm; STEL 1 ppm
(1 ppm = 2.90 mg/m3 @ NTP)
SYNONYMS: None.
SAMPLER: PREFILTER + FILTER TECHNIQUE: ION CHROMATOGRAPHY,

(PTFE, 0.5-fjm + silver membrane, CONDUCTIVITY
25-mm, 0.45-//m)
ANALYTE: chloride ion (Cl') or bromide ion (Br )
EXTRACTION: 3 mL 6 mM Na2S203, 10 min
SHIPMENT: routine, protect from light COLUMN: Dionex HPIC-AG4A guard, HPIC-AS4A
separator MFC- 1 precolumn, AMMSanion
SAMPLE suppressor
STABILITY: £30 days at 25 °C [1]
DETECTOR SETTING: 10 fjS full scale
ELUENT: 0.25 mM NaHCO3/4 mM Na^COÔ.78
mM p-cyanophenol, 2 mL/min
ACCURACY CALIBRATION: standard solutions of Cl in deionized

water
RANGE STUDIED: 0.35 to 6.77 mg/m3
(15-L samples) RANGE: 2 to 50 fjg Cl ' per sample [1 ]
BIAS: - 1.4%
ESTIMATED LOD: 0.6 /jg Cl per sample [1]
OVERALL PRECISION (§„): 0.075 [1]
PRECISION (Sr): 0.067 @ 5.3 to 1 00 //g per sample [1]
ACCURACY: ± 14.8%
APPLICABILITY: The working ranges for Br2 and CI2 are 0.008 to 0.4 ppm (0.06 to 2.6 mg/m3) and 0.007 to 0.5 ppm (0.02 to
1 .5 mg/m3) respectively for a 90-L air sample. The method has sufficient sensitivity for STEL samples.
INTERFERENCES: Hydrogen sulfide gives a negative interference. HCI gives a positive interference up to a maximum of 15
fjg per sample. HBr gives a positive interference as it is sampled continuously [1].
OTHER METHODS: P&CAM 209 (colorimetric) [2], OSHA Methods ID-101 [3] and ID-108 [4] are alternative methods.

CHLORINE AND BROMINE: METHOD 601 1, Issue 2, dated 15 August 1994 - Page 2 of 5
1. Sodium thiosuifate, reagent grade. 1. Sampler: Silver membrane filter,* 25-mm,

2. Water, deionized. 0.45-//m, (Costar/Nuclepore, Poretics, or
3. Extraction solution: 6 mM NaÔ3. Dissolve equivalent) with porous plastic support pad
0.474 g NaÔa in 500 ml_ deionized water. (Costar/Nuclepore); prefilter, PTFE with PTFE
4. Eluent: 0.25 mM NaHCO3/4 mM support, 0.5-//m (Gelman Zefluor, SKC, or
NajCOa/O.7a mM p.-cyanophenol. Dissolve equivalent), or polyester, 0.4-//m
0.041 g NaHCO3, 0.848 g NajCOa and (Costar/Nuclepore) with porous plastic
0.186 g p-cyanophenol in 2 L filtered support pad; three-piece, 25-mm carbon-filled
deionized water. polypropylene cassette (opaque) with 50-mm
5. Suppressor regenerant, 0.025 N H2SO4. extension (Costar/Nuclepore or Gelman)
Dilute 2.8 mL conc. H2SO4 to 4 L with (Fig. 1).
deionized water.* a. In the outlet piece of cassette, place
6. Calibration stock solutions, 1 mg/'mL (as porous plastic support pad and cleaned
anion). silver filter. Insert 50-mm extension (cowl)
(1) Dissolve 0.149 g KBr in 100 mL securely.
deionized water b. At the inlet (top) of the extension, place
(2) Dissolve 0.21 g KCI in 100 mL deionized porous plastic support pad and prefilter.
water. Insert inlet cassette piece securely.
c. Seal each connection with shrinkable
bands or tape.
See SPECIAL PRECAUTIONS. 2. Personal sampling pump, 0.3 to 1 L/min, with
3. Ion chromatograph with Dionex MFC-1 , HPIC-
AG4A, HPIC-AS4A columns, AMMS anion
micromembrane suppressor, conductivity
detector and integrator (page 6011-1).
4. Bottles, 30-mL, wide mouth with screw caps,
amber or opaque polyethylene.
5. Micropipettes, with disposable tips.
7. Repipet reagent dispensers, 0 to 10-mL
8. Syringes, 10-mL, polyethylene, luer-tip.
9. Forceps.
* Silver membrane filters must be cleaned

prior to use (see APPENDIX A).
NOTE: Some lots of silver membrane
filters contain excessively high
chloride background levels.
Please screen before field use.
SPECIAL PRECAUTIONS: Sulfuric acid is extremely corrosive to skin, eyes, and mucous membranes.
Wear protective clothing. Handle in a fume hood.
SAMPLING:

2. Attach sampler to personal sampling pump with flexible tubing.
3. Sample at an accurately known flow rate between 0.3 and 1 L/min for a total sample size of 8 to
360 L for bromine or 2 to 90 L for chlorine.
4. Seal ends of sampler with plugs. Pack securely for shipping.

CHLORINE AND BROMINE: METHOD 6011, Issue 2, dated 15 August 1994 - Page 3 of 5
SAMPLE PREPARATION:
NOTE: Silver halides are photosensitive. Protect from light during transfer and desorption.
5. Under very dim or red light, open cassette and transfer the silver filter with forceps to amber
bottle. Add 3 mL 6 mM Na2S2O3 and cap.
NOTE: Prefilter may be analyzed for particulate halides, or discarded.
6. Allow samples to stand a minimum of 10 min with occasional swirling.
NOTE: Once desorbed, samples are no longer photosensitive.
7. Uncap the sample bottles and add 7 mL deionized water for a total solution volume of 10 mL
8. Pour sample into 10-mL plastic syringe for manual injection or into autosampler vials.
9. Calibrate daily with at least six working standards covering the range of 0.2 to 15 //g bromide
and/or 0.05 to 5 //g chloride per mL of sample.
a. Add known aliquots of calibration stock solution to deionized water in 10-mL volumetric
flasks and dilute to the mark with deionized water.
b. Prepare fresh working standards biweekly.
c. Analyze working standards together with samples and blanks (steps 1 1 through 13).
d. Prepare a calibration graph (peak height vs. //g of anion per sample).
10. Analyze three quality control spikes, three analyst spikes and media blanks to ensure that
calibration graph is in control.
MEASUREMENT:
11. Set ion chromatograph according to manufacturer's instructions and to conditions given on
page 6011-1.
NOTE: Excessive amounts of Ag+ and Ag(S2O3)23" deteriorate column preformance. Use a
metal free column (MFC-1) prior to the chromatographic columns and recondition the
column every 100 to 150 analyses (See APPENDIX B).
12. Inject 50-fjL sample aliquot manually or with autosampler. For manual operation, inject 2 to 3
mL of sample from syringe to ensure complete rinse of the sample loop.
13. Measure peak height. If sample peak height exceeds linear calibration range, dilute with
deionized water, reanalyze, and apply the appropriate dilution factor in the calculations.
CALCULATIONS:
14. From the calibration graph, determine the mass of Br or CI" in each sample, W (/ug), and in the
average blank, B (//g).
15. Calculate the concentration, C (mg/m3), of Br2 or CI2 in the air volume sampled, V (L):
C . W^B. mg/m3.
The method was evaluated by sampling generated atmospheres of Br2 and CI2 at both high (80%) and
low (20%) relative humidities [1]. Samples were taken at four concentration levels ranging from 0.007 to
1 .42 mg/m3 for Br, and 0.354 to 6.77 mg/m3 for CI2. Overall recovery for Br2 was 98.8% with total
overall precision, SrT, of 6.8%. Overall recovery for CI2 was 98.6% with total overall precision, SrT, of
6.7%. Samples for CI2 were stable at least 30 days at 25 °C (103 ± 4% Recovery) and up to 60 days at
5 °C (101 ± 3% Recovery). The Br2 samples were stable up to 60 days at 25 °C (99.2 ± 10.1%
Recovery).

REFERENCES:
[1] Cassinelli, M.E. Development of Solid Sorbent Monitoring Method for Chlorine and Bromine with
Determination by Ion Chromatography, Appl. Occup. Environ. Hvg.. 6:215-226 (1991).
[2] NIOSH Manual of Analytical Methods. 2nd ed.; Taylor, D.G., Ed.; V. 1, P&CAM 209; U.S.
Department of Health Education and Welfare, Public Health Service, Centers for Disease Control,
National Institute for Occupational Safety and Health; DHEW (NIOSH) Publication No. 77-157,
1977.
[3] Occupational Safety and Health Administration Analytical Laboratory: OSHA Analytical Methods
Manual. Method No. ID-101). American Conference of Governmental Industrial Hygienists:
Cincinnati, OH, 1985; Publ. No. ISBN: 0-93671 2-66-X.
[4] Occupational Safety and Health Administration Analytical Laboratory: OSHA Analytical Methods
Manual. (Method No. ID-108). American Conference of Governmental Industrial Hygienists:
Cincinnati, OH, 1985; Publ. No. ISBN: 0-93671 2-66-X.
METHOD WRITTEN BY:
Mary Ellen Cassinelli, NIOSH/DPSE
APPENDIX A: CLEANING PROCEDURE FOR SILVER MEMBRANE FILTERS
NOTE: Some lots of silver membrane filters contain extremely high chloride background levels. If
excessively high this cleaning procedure will not remove all of the chloride, even if repeated
several times. Screening is necessary for each lot before being used for this method.
Screening may be done by following this procedure at least twice, or by analyzing by XRD.
1. Place each filter in a 30-mL, wide-mouth bottle, and add 3 mL 6 mM Na2S2O3.

2. Allow to stand for a minimum of 10 min with occasional swirling.
3. Discard solution and rinse thoroughly with deionized water. Allow the filters to stand in last rinse for
a few minutes.
4. Remove filters from bottles and dry between layers of absorbent laboratory towels.
5. Store cleaned filters between paper disks in manufacturer's container. Filters are stable for at least 8
months.
APPENDIX B: COLUMN RECONDITIONING PROCEDURE
In the following order, pump through the analytical columns at 2 mL/min:

a. 30 mL deionized water to rinse;
b. 60 mL 1 M HNO3 to remove contaminants;
c. 30 mL 0.1 M Na2CO3 to remove the NO3 ;
d. Eluent to equilibrate.
Reconditioning is recomended after 100 to 150 analyses.

INLET
PREFILTER
TE -PLASTIC SUPPORT
E o
" 1
00 1- 25-mm
SILVER MEMBRANE
PLASTIC SUPPORT
OUTLET
Figure 1. Silver Filter Sampler

CHLOROACETALDEHYDE 2015
CH,CICHO MW: 78.50 CAS: 107-20-0 RTECS: AB2450000
OSHA : C 1 ppm PROPERTIES: liquid; d 1.236 g/mL @ 20 °C; sp. gr. (40%
NIOSH: C 1 ppm aq. soln.) 1.19; BP 85 °C; MP -16.3 °C;
ACGIH: C 1 ppm VP 13.3 kPa (100 mm Hg)
(1 ppm = 3.21 mg/m3 @ NTP)
SYNONYMS: 2-chloroacetaldehyde; 2-chloroethanal
SAMPLER: SOLID SORBENT TUBE TECHNIQUE: GAS CHROMATOGRAPHY, 63Ni ECD

ANALYTE: chloroacetaldehyde
(0.2 L/min for 15-min ceiling sample) DESORPTION: 25 mL 50% aqueous methanol, 30 min
VOL-MIN: 0.3 L @ 1 ppm INJECTION

-MAX: 16 L VOLUME: 2 ul with 3 //L water as flush
SHIPMENT: routine; submit separate bulk sample TEMPERATURE-INJECTION: 250 °C

-DETECTOR: 300 °C
CARRIER GAS: 5% argon in methane, 50 mL/min
COLUMN: glass, 1.8 m x 6 mm OD, packed with
60/80 mesh Chromosorb 101
ACCURACY CALIBRATION: standard solutions of chloroacetaldehyde

in 50% aqueous methanol
(3-L samples) RANGE: 1 to 19 //g per sample [1]
BIAS: -0.4% ESTIMATED LOD: 0.1 fjg per sample [1]
OVERALL PRECISION (SrT): 0.060 [1] PRECISION (Sr): 0.036 [1]
ACCURACY: ±12.2%
APPLICABILITY: The working range is 0.1 to 2 ppm (0.33 to 6.3 mg/m3) for a 3-L air sample. The method is not able to
distinguish between chloroacetaldehyde and the monomer or dimer hydrate forms of chloroacetaldehyde.
OTHER METHODS: This is method S11 [2] in a revised format. Chloroacetaldehyde in air has also been determined by
differential pulse polarography [3].

CHLOROACETALDEHYDE: METHOD 2015, Issue 1, dated 15 August 1994 - Page 2 of 4
1. Chloroacetaldehyde*, -50% (w/w) solution 1. Sampler: glass, 8 cm long, 6-mm ID,

in water. containing two sections of 20/40 mesh silica
2. Water, deionized, distilled. gel (front = 520 mg; back = 260 mg),
3. 50% Aqueous methanol. separated by 2 mm of urethane foam.
4. 5% Hydrazine sulfate solution. Dissolve Pressure drop across the tube at 1 L/min
12.5 g hydrazine sulfate in 250 mL deionized airflow must be less than 3.4 kPa. Tubes are
distilled water. commercially available.
5. Ferric ammonium sulfate solution, saturated, 2. Personal sampling pump, 0.05 to 0.2 L/min
in 1 M HNO3. with flexible connecting tubing.
6. Ammonium thiocyanate, 0.100 N. Accurately 3. Gas chromatograph, MNi electron-capture
weigh 7.6139 ammonium thiocyanate and detector, integrator and column (page 2015-1).
dilute to 1 L with deionized distilled water. 4. Volumetric flasks, 25-mL, 1-L and other
7. Silver nitrate solution, 0.100 N. Accurately convenient sizes for preparing standards.
weigh 16.987g silver nitrate and dilute to 1 L 5. Erlenmeyer flasks, 50-mL, 250-mL
with deionized distilled water. 6. Buret, 10-mL
8. Nitric acid solution. Add 25 mL conc, nitric 7. Pipets, glass, 25-mL and other convenient
acid to 25 mL water. Boil until colorless to sizes for making dilutions.
remove nitrous acid. 8. Syringes, 10-, 50-, and 100-//L
9. Nitrobenzene.
10. 5% Argon/methane.
1 1 . Calibration stock solution. Dilute 1 mL 50 %
Chloroacetaldehyde solution to 250 mL with
deionized distilled water. See APPENDIX for
standardization method.
SPECIAL PRECAUTIONS: Chloroacetaldehyde is corrosive to the skin and an eye irritant in low vapor
concentrations. In storage, Chloroacetaldehyde forms a water-insoluble polymer [4].
SAMPLING:

to 16 L
SAMPLE PREPARATION:
5. Transfer the glass wool plug and front section of silica gel to a 50-mL Erlenmeyer flask. Transfer
the backup sorbent section to another flask.
6. Pipet 25 mL 50% aqueous methanol into each flask.
7. Shake each flask occasionally over a 30-min period. Analyze samples within 1 day.
8. Calibrate daily with at least six working standards over the range 0.1 to 19 //g
chloroacetaldehyde per sample.

a. Add known amounts of calibration stock solution to 25-mL volumetric flasks and dilute to the
marks with 50% aqueous methanol. Use serial dilution as necessary to prepare lower
concentrations.
b. Analyze together with samples and blanks (steps 11 through 13).
c. Prepare calibration graph of //g chloroacetaldehyde/25 mL vs. peak area.
9. Determine desorption efficiency (DE) at least once for each batch of silica gel used for sampling
in the calibration range (step 8). Prepare three tubes at each of five concentrations plus three
media blanks.
a. Remove and discard the back sorbent section of a media blank sampler.
b. Inject a known amount of standard (< 100 //L) directly onto front sorbent section with a
microliter syringe.
d. Desorb (steps 5 through 7) and analyze together with working standards (steps 1 1 through
13).
e. Prepare a graph of DE vs. ;/g chloroacetaldehyde recovered.
10. Analyze three quality control blind spikes and five analyst spikes to ensure that the calibration
MEASUREMENT:
11. Set gas chromatograph according to manufacture's recommendations and to conditions given
on page 2015-1.
12. Inject 2-//L sample aliquot along with 3 fjL of water as solvent flush.
desorbed liquid, reanalyze, and apply the appropriate dilution factor in the calculations.
CALCULATIONS:
14. Determine the mass, JJQ (corrected for DE), of chloroacetaldehyde found in the sample front
sorbent sections.
15. Calculate concentration, C, of chloroacetaldehyde in the air volume sampled, V (L):
C . mg/m
This method was evaluated over the range 1.8 to 6.4 mg/m3 at 20 °C and 761 mm Hg using 3-L
samples [1]. The concentration of chloroacetaldehyde in the test atmospheres was independently
monitored using bubblers containing 15 mL deionized distilled water. Breakthrough from front sorbent
sections occurred after sampling for 92 min at 0.2 L/min in an atmosphere containing 5.16 mg/m3. The
relative humidity was 80%. Samples collected at 1X the OSHA standard and stored at room temperature
for 1 week lost 8.3% and 5.3% when the relative humidity was 20% and 80%, respectively. No
correction for desorption efficiency was needed for loadings at 0.5-, 1-, and 2X the OSHA standard.
Recoveries of samples collected at 80% RH had a positive bias of 3.4%, and samples collected at 20%
RH had a negative bias of -4.2%. The overall mean bias was -0.4%.

REFERENCES:
[1] Backup Data Report No. S11 for Chloroacetaldehyde, prepared under NIOSH Contract No. 210-
76-0123.
[2] NIOSH Manual of Analytical Methods, 2nd. ed., V. 5, S11, U.S. Department of Health, Education, and
[3] Williams, R.G., Determination of Chloroacetaldehyde in Air by Differential Pulse Polarography, Anal.
Chem.. 54(12). 2121-2 (1982).
METHOD REVISED BY:
James E. Arnold, NIOSH/DPSE; S11 originally developed under NIOSH Contract 210-76-0123.
APPENDIX: STANDARDIZATION OF CALIBRATION STOCK SOLUTION.
Pipet 10-mL aliquots of the stock solution into two separate 250-mL Erlenmeyer flasks. Add 10 mL 2.5%
hydrazine sulfate to one of the flasks and allow to stand 10 minutes with occasional swirling. The other
flask serves as a blank and determines any free halide ion already present.
Add 10 mL 0.100 N silver nitrate solution, 5 mL nitric acid solution, and 2 mL ferric ammonium sulfate
solution to each flask. Swirl and add 2 mL nitrobenzene. The nitrobenzene forms an oily coating on the
particles of precipitated silver chloride and prevents their undesired reaction with the thiocyanate ion.
Titrate contents of each flask with 0.1 N ammonium thiocyanate to a faint orange-brown color that is
permanent on shaking. The endpoint color is due to the formation of the Fe(SCN)6"3 ion.
Compute the volumes, Vs, of standard silver solution in excess of that used by the chloride in each flask.
Vs - VT x 1, mL
where: VT = volume, mL, of standard thiocyanate solution titrated

NT = normality of NH4SCN solution
Ns = normality of AgNO3 solution
Compute the net volume, VN, of silver solution required for the precipitation of the chloride liberated from
Chloroacetaldehyde.
VN = Vs (blank) - Vs (stock), ml
Calculate the concentration, C, of Chloroacetaldehyde in calibration stock solution.
C = VN x Ns x 7.85, mg/mL

CHLOROACETIC ACID 2008
CICH,COOH MW: 94.50 CAS: 79-11-8 RTECS: AF8575000

OSHA : no PEL PROPERTIES: solid; MP 61 to 63 °C; BP 189 °C;

NIOSH: no REL VP 0.1 kPa (0.75 mm Hg) @ 20 °C; flash
ACGIH: noTLV point 126 °C; lower explosive limit in
(1 ppm = 3.87 mg/m3 @ NTP) air 8% v/v
SYNONYMS: chloroethanoic acid; monochloroacetic acid
SAMPLER: SOLID SORBENT TUBE TECHNIQUE: ION CHROMATOGRAPHY,

(silica gel, 100 mg/50 mg) CONDUCTIVITY DETECTION
FLOW RATE: 0.05 to 0.2 L/min ANALYTE: chloroacetate ion
VOL-MIN: 1 L @ 0.25 ppm DESORPTION: 2 mLdeionized water

-MAX: 100 L
INJECTION
SHIPMENT: routine LOOP VOLUME: 500 fji
SAMPLE ELUENT: 1.5 mM NaHCO3; 1.0 mL/mm

STABILITY: at least 7 days @ 25 °C; 32 days
refrigerated [1] COLUMNS: Ion Pac AS4A Separator, AG4A Guard,
micromembrane suppressor (see OTHER
BLANKS: 2 to 10 field blanks per set METHODS)
CALIBRATION: standard solutions of chloroacetic acid in

deionized water
ACCURACY
RANGE STUDIED: 0.35 to 29 mg/m3 [1,2]
(3-L samples) ESTIMATED LOD: 0.04 tig per sample [2]
BIAS: - 2.0% PRECISION (Sr): 0.016 [1]
ACCURACY: ± 17.7%
APPLICABILITY: The working range is 0.09 to >85 ppm (0.3 to 30 mg/m3) for a 3-L air sample.
INTERFERENCES: Chloroacetyl chloride is a positive interferent since it is hydrolyzed to monochloroacetic acid by the
measurement procedure and is efficiently collected by silica gel [3]. Particulate salts of the acid are positive interferents. The
chromatographic conditions given will separate acetate, chloride, dichloroacetate, fluoride, glycolate, and trichloroacetate ions
from chloroacetate ion.
OTHER METHODS: This revises P&CAM 332 [2]. The columns used in P&CAM 332 are no longer available. The newer
columns indicated here show improvements in the analytical range and sensitivity.

CHLOROACETIC ACID: METHOD 2008, Issue 2, dated 15 August 1994 - Page 2 of 4
1. Water, filtered, deionized. Specific 1. Sampler: glass tube, 7 cm long, 6-mm OD,
conductance <10//S/cm. 4-mm ID, with plastic caps, containing two
2. Sodium bicarbonate (NaHCO3), reagent grade. sections of 20/40 mesh silica gel (front = 100
3. Chloroacetic acid, >99%.* mg; back = 50 mg) contained and separated
4. Eluent: 1.5 mM NaHCO3. Dissolve 0.504 g by three silanized glass wool plugs. Pressure
NaHCO3 in 4 L filtered, deionized water. drop across the tube at 0.2 L/min is ca. 0.6
5. Calibration stock solution, 1000 //g/mL kPa (2.6 in. H2O). Tubes are commercially
Dissolve 100 mg chloroacetic acid in 100 mL available (SKC, Inc. 226-47-01, or equivalent).
filtered, deionized water. NOTE: Chloroacetic acid is irreversibly
adsorbed on urethane plugs. Use
* See SPECIAL PRECAUTIONS. sorbent tubes with glass wool plugs.
3. Ion chromatograph (IC), anion separator and
guard column, anion suppressor (page
2008-1), conductivity detector, integrator, and
strip chart recorder.
4. Ultrasonic bath.
5. Vials, 20-mL, glass, with aluminum-lined plastic
screw caps.
6. Syringes, 3-mL, polyethylene with luer tip.
7. Filter holder, luer tip, 13-mm, with PTFE filter,
5-//m pore size, or PTFE syringe filter.
8. Pipets, 1 0-//L to 2-mL
9. Flasks, volumetric, 10- and 100-mL
SPECIAL PRECAUTIONS: Chloroacetic acid is irritating to skin and mucous membranes [4]. Work with
the concentrated material only in a hood.
SAMPLING:

3. Sample at an accurately known flow rate between 0.05 to 0.2 L/min for a total sample size of 1
to 100 L
NOTE: Store samples in the dark. Refrigerate samples if stored longer than 7 days.
SAMPLE PREPARATION:
5. Allow refrigerated samples to equilibrate to room temperature.

6. Transfer front sorbent section with front glass wool plug to vial. Place back sorbent section and
other two glass wool plugs in separate vial.
7. Add 2.0 mL deionized water to each vial. Cap immediately.
8. Agitate vials in ultrasonic bath for 30 min at room temperature.
9. Draw sample extract through 13-mm PTFE filter with 3-mL syringe.

CHLOROACETIC ACID: METHOD 2008, Issue 2, dated 15 August 1994 - Page 3 of 4

a. Add known aliquots of calibration stock solution to deionized water in 10-mL volumetric
flasks and dilute to the mark. Use serial dilutions as needed to obtain chloroacetic acid
concentrations in the range 0.02 to 40 //g/mL
b. Analyze together with samples and blanks (steps 13 through 15).
c. Prepare calibration graph [peak height (mm or//S) vs. //g chloroacetic acid per sample].
11. Determine desorption efficiency (DE) for each batch of silica gel used for sampling in the
calibration range. Prepare at least three tubes at each of five levels.
a. Place silica gel from unused front section in vial.
b. Inject a known amount (2 to 20 //L) of calibration stock solution, or a serial dilution thereof,
c. Cap the vial. Allow to stand overnight.
d. Desorb (steps 7 through 9) and analyze together with working standards (steps 13 through
15).
e. Prepare graph of DE vs. //g chloroacetic acid recovered.
12. Analyze three quality control spikes and three analyst spikes to ensure that the calibration graph
MEASUREMENT:
13. Set ion chromatograph according to manufacturer's recommendations and to conditions given
on page 2008-1 .
14. Inject sample aliquot manually or use autosampler.
a. Flush sample loop with 0.5 mL sample extract, then inject 0.5 mL sample.
b. Rinse sample loop with 1 to 2 mL deionized water between determinations of separate
samples.
NOTE: All samples, eluents, and water flowing through the lC must be filtered to avoid
plugging the system valves or columns.
NOTE: If sample peak height exceeds linear calibration range, dilute with deionized water,
reanalyze, and apply appropriate dilution factor.
CALCULATIONS:
16. Determine mass, //g (corrected for DE), of analyte found in the sample front (Wt) and back (Wb)
17. Calculate concentration, C, of chloroacetic acid in the air volume sampled, V (L):
C . W' * W» - B" - B>, mg/m'.
This method was developed and evaluated by Southern Research Institute [1] using dynamically-
generated atmospheres of chloroacetic acid over the concentration range of 0.35 to 29 mg/m3 at 25 to
27 °C and at relative humidity >80%. Average recovery based on 18 samples, six at each of three
levels, was 98% representing a negligible bias. Precision at 0.35 mg/m3 was inhomogeneous with those
of higher levels; therefore, precisions were not pooled. Using this poorest precision (Sf = 0.064), the
overall precision (SrT) was estimated to be < 0.081.

CHLOROACETIC ACID: METHOD 2008, Issue 2. dated 15 August 1994 - Page 4 of 4
The breakthrough volume of the 100-mg sorbent section was found to be > 100 L at 0.2 L/min when
sampling chloroacetic acid concentrations of 60 mg/m3 at 42 °C and RH of 10 and 80% and 35 mg/m3
at 27 °C and 10 and 90% RH. Samples stored at ambient temperature for 7 days had a mean recovery
of 91% and a precision, Sr, of 0.047. Samples refrigerated after day 7, and stored for 32 days exhibited
a mean recovery of 100% with a precision, Sr, of 0.085 based on samples analyzed on day 1.
REFERENCES:
[1] Dillon, H. K., D. W. Mason, and K. W. Boyd. Development of Air Sampling and Analytical
Methods for Toxic Chlorinated Organic Compounds: Research Report for Monochloroacetic
Acid, NIOSH Contract 210-78-0012, Southern Research Institute, Birmingham, AL (1980).
[2] NIOSH Manual of Analytical Methods, 2nd ed., Vol. 6, P&CAM 322, U.S. Department of Health
[3] McCullough, P. R. and J. W. Worley. "Sampling of Chloroacetyl Chloride in Air on Solid Support
and Determination by Ion Chromatography," Anal. Chem., 51, 1120-1122 (1979).
[4] Merck Index, 11th ed., Merck & Co., Rahway, NJ (1989).
METHOD REVISED BY:

CHLOROBENZENE

CHLOROBENZENE

See DICHLORODIFLUOROMETHANE (Method 1018) for procedure
CHCIF, MW: 86.47 CAS: 75-45-6 RTECS: PA6390000
OSHA : no PEL PROPERTIES: gas; BP -40.8 °C; MP -160 °C;

NIOSH: 1000 ppm; STEL 1250 ppm nonflammable
ACGIH: 1000 ppm
(1 ppm = 3.54 mg/m3 @ NTP)
SYNONYMS: difluorochloromethane; Refrigerant 22.
SAMPLER: SOLID SORBENT TUBES TECHNIQUE: GAS CHROMATOGRAPHY, FID

(two coconut shell charcoal tubes in
series, 400/200 mg and 100/50 mg) ANALYTE: chlorodifluoromethane
FLOW RATE: 0.01 to 0.05 L/min DESORPTION: 20 mL methylene chloride

-MAX: 4 L VOLUME: 1//L
SHIPMENT: refrigerated TEMPERATURE-INJECTOR: 200 °C

-DETECTOR: 260 °C
SAMPLE -COLUMN: 35 °C for 3 min,
STABILITY: at least 7 days @ 25 °C 15 °C/min to
75 °C, hold 6 min
CARRIER GAS: He, 1.5 mL/min
COLUMN: DB-1 fused silica capillary, 30 m x

0.32-mm ID, 1-jum film thickness or
equivalent
ACCURACY
CALIBRATION: standard solutions of analyte in
RANGE STUDIED: 1800 to 6970 mg/m3 [3] methylene chloride
BIAS: 0% RANGE: 0.1 to 14 mg per sample [3]
OVERALL PRECISION (SrT): 0.074 [3] ESTIMATED LOD : 0.01 mg per sample [3]
ACCURACY: ±14.5% PRECISION (Sr): 0.051 @ 0.53-10 mg per sample [3]
APPLICABILITY: The working range is 280 to 4000 ppm chlorodifluoromethane (1000 to 14,000 mg/m3) for a 1-L air
sample. This method was first evaluated for dichlorodifluoromethane and 1 ,2-dichlorotetrafluoroethane with packed column
gas chromatography [1]. The method was recently evaluated specifically for chlorodifluoromethane using capillary
chromatography [3].
OTHER METHODS: This combines and revises Methods S111 and S108 [2].

CHLOROFORM

4-CHLORONITROBENZENE
See NITROBENZENES (Method 2005) for procedure

e-CHLOROPHENOL 2014
C6H4CIOH MW: 128.56 CAS: 106-48-9 RTECS: SK2800000
METHOD: 2014, Issue 2 EVALUATION: FULL Issue 1: 19 September 1980

OSHA : no PEL PROPERTIES: crystals; d 1.224 g/mL @ 20 °C; MP

NIOSH: no REL 43.2-43.7 °C; BP 220 °C; VP 0.013 kPa
ACGIH: no TLV (0.1 mm Hg) @ 20 °C; flash point
(1 ppm = 5.26 mg/m3 @ NTP) 121 °C (closed cup)
SYNONYMS: 4-chlorophenol; 4-chloro-1-hydroxybenzene
SAMPLER: SORBENT TUBE TECHNIQUE: HPLC/UV

ANALYTE: g-chlorophenol
FLOW RATE: 0.05 - 0.2 L/min
EXTRACTION: 1 mL acetonitrile
VOL-MIN: 1.5 L @ 1 ppm
VOLUME: 100 M-
SHIPMENT: Routine
MOBILE PHASE: 30% acetonitrile, 70% water to 80%
SAMPLE 7 days @ 25 °C acetonitrile/20% water in 20 minutes, 1
STABILITY: at least 29 days @0 °C [1] mL/min
COLUMN: C18. (5 fjm particle size, 4-mm ID by 30-

BLANKS: 2 to 10 field blanks per set cm long stainless steel)
ACCURACY CALIBRATION: p-chlorophenol in 30% (v/v) acetonitrile in

water
(3-L samples) RANGE: 8 to 64//g/sample [1]
ESTIMATED LOD: 2. 5 //g/sample [1]
OVERALL PRECISION (§,,): 0.061 for range studied [1]
ACCURACY: ± 15% (12-28%)
INTERFERENCES: None identified. The chromatographic conditions described will separate phenol ; o-chlorophenol; 2,3-,
2,4-, 2,5-, 2,6-, 3,4-, and 3,5- dichlorophenol; o- and g-nitrophenol; 2,4-dimethylphenol; 2,4,5-trichlorophenol; 4-chloro-o-
methylphenol; 2,4-dinitrophenol; 4,6-dinitro-2-methylphenol; and pentachlorophenol.
OTHER METHODS: This method replaces P&CAM 337 [2]. The other columns for the analysis of g-chlorophenol have been
reported in the literature [3-5].

p_-Chlorophenol: METHOD 2014, Issue 2, dated 15 August 1994 - Page 2 of 4
1 p_-Chlorophenol 99%.* 1. Sampler: Pyrex tubes, 7 cm long with a 6-mm

2. Acetonitrile, distilled in glass. OD and a 4-mm ID, flame sealed at both ends.
3. Hexane, distilled in glass. Each tube contains two sections of 20/40
4. Water, HPLC quality. mesh silica gel (a 150-mg sorbing section and
5. E-Chlorophenol stock solution, 20 mg/mL a 75-mg backup section separated and held in
Dissolve 500 mg g-chlorophenol in 30% (v/v) place with glass wool plugs). Tubes are
acetonitrile in water to make 25 mL solution. commercially available (SAC, Inc. 226-10 or
Stable at least 3 months in airtight container. equivalent.)
6. DE stock solution, 5 mg/mL Dissolve 125 mg 2. Personal sampling pump, calibrated, capable
p_-chlorophenol in hexane to make 25 mL of operating 8 hours at 0.05 to 0.2 L/min with
solution. flexible connecting tubing.
3. HPLC with UV detector (280 nm), C18 column
(Variant MicroPak MCH-5 or equivalent),
* See SPECIAL PRECAUTIONS. injector, and electronic integrator.
4. Microliter syringes, various sizes.
5. Volumetric flasks, various sizes.
6. Centrifuge tubes, 12-mL, glass with screw
caps.
7. Pipette, 1 - and 2-mL, and convenient sizes for
making dilutions.
8. Vials, 1-mL, with caps containing PTFE-lined
silicone septa.
9. Ultrasonic bath.
SPECIAL PRECAUTIONS: g-Chlorophenol is toxic by skin absorption, inhalation, or ingestion. It also

is a strong irritant to tissue and is combustible with a flash point of 121 °C.
SAMPLING:
2. Immediately before sampling, break open the ends of the tube to provide openings that are at
least 2-mm in diameter. Attach sampler to personal sampling pump with flexible tubing.
3. Sample at an accurately known flowrate between 0.05 and 0.2 L/min for a total sample size of 1
to 40 liters.
4. Cap the tubes, record sample identity and all relevant sample data (duration, ambient
temperature and pressure). Pack securely for shipment.
NOTE: Refrigerate all samples at 0 °C when stored longer than 7 days.
SAMPLE PREPARATION:
5. If refrigerated, allow tube to equilibrate to room temperature.

6. Transfer each section of silica gel in a sorbent tube to a separate 12-mL centrifuge tube.
Combine the glass wool plug near the inlet with the front sorbent section. Combine the two
urethane foam plugs with the back section.
7. Add 1 mL of acetonitrile, cap, and desorb in an ultrasonic bath for 30 minutes.
8. Add 2 mL of distilled, deionized water to each tube, cap, and mix the solutions.
9. Centrifuge the samples and transfer about 1 mL of the supernatant in each tube to a separate
vial and seal with a PTFE-lined septum.

p_-Chlorophenol: METHOD 2014, Issue 2, dated 15 August 1994 - Page 3 of 4
10. Calibrate daily with at least six working standards in the range 2.5 to 64 //g per sample.
a. Dilute aliquots of g-chlorophenol stock solution with 30% (v/v) acetonitrile in water in
volumetric flasks to encompass the range of interest. Prepare fresh daily.
b. Analyze working standards with samples and blanks steps.
c. Prepare calibration graph (peak area or peak height vs. //g of p_-chlorophenol per sample.
11. Determine desorption efficiency (DE) for each lot of silica gel used for sampling in the calibration
range. Prepare three tubes at each of five levels.
a. Remove backup section. Inject known amounts of DE stock solution (2 to 10 fjL) onto the
silica gel with a microliter syringe.
b. Cap the tubes and allow to stand overnight.
c. Desorb (steps 7 through 9) and analyze together with standards and blanks (steps 13 and
14).
d. Prepare a graph DE vs. JJQ p_-chlorophenol recovered.
12. Analyze three quality control spikes and three analyst spikes to ensure that the calibration graph
MEASUREMENT:
13. Set HPLC according to manufacturer's recommendations and to conditions on page 2014-1.
Inject sample aliquot manually or with autosampler.
NOTE: If peak is above the linear range of the working standards, dilute with 30% (v/v)
acetonitrile in water, reanalyze, and apply the appropriate dilution factor.
CALCULATIONS:
15. Determine the mass, //g (corrected for DE), of analyte found on the sample front (Wf) and back
16. Calculate concentration of p-chlorophenol in the air volume sampled, V (L):
C . WW.-B.-BJ mg/m,
The overall method was evaluated by collecting 3-L samples of test atmospheres containing
g-chlorophenol in the range of 0.91 - 23.4 mg/m3 at 29 °C and a relative humidity of greater than 80%.
The amounts collected ranged from 2.6 - 64 //g per 150-mg bed of silica gel. The breakthrough volume
of the sorbent tube was found to be approximately 60 L with a sampling rate of 0.2 L/min at a
g-chlorophenol concentration of about 70 mg/m3, a sampling temperature of 43 °C, and a relative
humidity of greater than 80%. Samples of £>-chlorophenol on silica gel were found to be stable at 25 °C
for 7 days and for 29 days if stored at 0 °C after the seventh day. Silica gel gave an average desorption
efficiency of 96% with a Sr 2.4% for loadings of 2.54 - 48.0 //g of p.-chlorophenol on 150-mg beds of
sorbent material.
REFERENCES:
[1] Dillon, H.K., Emory, M.B. Development of Air Sampling and Analytical Methods for Toxic Chlorinated
Organic Compounds: Research Report for p-Chlorophenol. NIOSH Contract 210-78-0012, Southern
Research Institute, Birmingham, Alabama (1980).

B-Chlorophenol: METHOD 2014, Issue 2, dated 15 August 1994 - Page 4 of 4
[2] NIOSH Manual of Analytical Methods, 2nd ed., V. 7, P&CAM 337, U.S. Department of Health and
[3] Korhonen, I.O. "Separation of Chlorophenol Isomers on Quartz Columns." J. Chromatogr.. 303 (1),
197-205 (1980).
[4] Buisson et al., "Determination of Chlorinated Phenols by Capillary GC/ECD." J. Chromatogr. Sci.,
22 (8). 399-42 (1984).
[5] Lee, H.B. et al, "Determination of Chlorinated Phenolics in Pulp and Paper Effluents." J. Assoc. of
Anal. Chem.. 72 (6). 979-984 (1989).
METHOD REVISED BY:
Charles Neumeister, NIOSH/DPSE.

0-CHLOROPRENE 1002
= CCICH = MW: 88.54 CAS: 126-99-8 RTECS: EI9625000

OSHA : 25 ppm (skin) PROPERTIES: liquid; d = 0.958 g/mL @ 20 °C;

NIOSH: C 1 ppm/15 min; carcinogen BP59.4 °C; MP -130 °C;
ACGIH: 10 ppm (skin) VP 25 kPa (188 mm Hg; 25% v/v)
(1 ppm = 3.62 mg/m3 @ NTP) @ 20 °C; explosive range 4 to
20% v/v in air
SYNONYMS: chloroprene; 2-chloro-1,3-butadiene; chlorobutadiene

ANALYTE: chloroprene
DESORPTION: 1 mL CS2; stand 30 min
VOL-MIN: 1.5 L@25 ppm
-MAX: 8L INJECTION VOLUME: 1 to 2 fjL, splitless

-DETECTOR: 280 °C
SAMPLE -COLUMN: 35 °C, 2 min; 15 °C/min
STABILITY: at least 8 days @ 25 °C [1,2] to 300 °C, hold 5 min
BLANKS: 2 to 10 field blanks per set CARRIER GAS: N2 or He, 1-3 mL/min
MAKEUP GAS: nitrogen, 30 ml/min
COLUMN: DB-1 fused capillary, 30 m x 0.25-mm ID,

ACCURACY 1.0-//m film [3]
RANGE STUDIED: 44 to 174 mg/m3 [2] CALIBRATION: solutions of distilled chloroprene in CS;;
(3-L samples) hexane reference standard
BIAS: - 1.1%
ESTIMATED LOD: 0.03 mg per sample [2,3]
ACCURACY: ± 13.9%
APPLICABILITY: The working range is 10 to 60 ppm (40 to 200 mg/m3) for a 3-L air sample. The method is sensitive enough
to determine concentrations as low as 12 ppm in 15-min samples taken at 0.2 L/min. NIOSH has sampled for chloroprene at
two polychloroprene processing plants.
OTHER METHODS: This is Method S112 with improved GC column in a new format [4]. A similar method appears in the
chloroprene criteria document [1].

/7-CHLOROPRENE: METHOD 1002, Issue 2, dated 15 August 1994 - Page 2 of 4
1. Carbon disulfide, chromatographic quality.* Sampler: glass tube, 7 cm long, 6-mm OD, 4-
2. Chloroprene*, freshly distilled from xylene mm ID, flame-sealed ends, containing two
solution at reduced pressure; BP = 31 °C at sections of activated (600 °C) coconut shell
354 mm Hg (47 kPa). charcoal (front = 100 mg; back = 50 mg)
3. n-Pentane, reagent grade. separated by a 2-mm urethane foam plug. A
4. n-Hexane, reagent grade. silylated glass wool plug precedes the front
5. Calibration stock solution, 47.9 mg/mL section and a 3-mm urethane foam plug
Deliver 0.500 mL (0.479 g at 20 °C) freshly follows the back section. Pressure drop
distilled chloroprene from a delivery pipet across the tube at 1 L/min airflow must be
under the surface of pentane in a partially filled less than 3.4 kPa. Tubes are commercially
10-mL volumetric flask. Dilute to the mark available.
with pentane. Stable one day at - 15 °C. Personal sampling pump, 0.01 to 0.1 L/min,
6. Nitrogen, purified. with flexible connecting tubing.
7. Hydrogen, prepurified. 3. Gas chromatograph, FID, integrator and
8. Air, filtered. column (page 1002-1).
4. Micro-distillation apparatus for vacuum
distillation of chloroprene.
See SPECIAL PRECAUTIONS. 5. Vials, 2-mL, glass with PTFE-lined septa and
crimp seals.
8. Pipets, 1-mL, graduated in 0.1 mL, with pipet
bulb.
SPECIAL PRECAUTIONS: Carbon disulfide is toxic and flammable. Work with it only in a hood.
Chloroprene incompatibilities by contact with oxidizers (e.g., peroxides) may cause polymerization with
evolution of heat and rupture of containers. Chloroprene attacks some plastics, rubber, and coatings.
It will autoxidize very rapidly, even at 0 °C, producing an unstable peroxide (mixed 1 ,2- and 1 ,4-addition
copolymer with oxygen) which catalyzes exothermic polymerization. Therefore, immediately after
distilling, store at -15 °C.
SAMPLING:

1 .5 to 8 L
SAMPLE PREPARATION:
6. Add 1.0 mL CS2 to each vial. Attach crimp cap to each vial.
7. Allow to stand 30 min with occasional agitation. Decant the liquid into a clean vial.
NOTE 1 : Desorbed samples are unstable in the presence of charcoal, losing significant
amounts over several hours.

ff-CHLORQPRENE: METHOD 1002, Issue 2, dated 15 August 1994 - Page 3 of 4
8. Calibrate daily with at least six working standards over the range 0.03 to 0.5 mg chloroprene per
sample.
a. Add known amounts of calibration stock solution below the surface of CS2 in 10-mL
c. Prepare calibration graph (peak area vs. mg chloroprene).
in the calibration range (step 8). Prepare three tubes at each of five concentrations plus three
media blanks.
microliter syringe.
e. Prepare a graph of DE vs. mg chloroprene recovered.
MEASUREMENT:
on page 1002-1. Inject sample aliquot either with autosampler or manually using solvent flush
technique.
NOTE: If peak area is above the linear range of the working standards, dilute with CS2,
CALCULATIONS:
13. Determine the mass, mg (corrected for DE) of chloroprene found in the sample front (Wf) and
sections.
14. Calculate concentration, C, of chloroprene in the air volume sampled, V (L):
C . (W,-Wb-B,-Bt)
Method S1 12 was issued on October 29, 1976, and validated over the range 44 to 175 mg/m3 with
eighteen 3-L samples from dynamically-generated test atmospheres, as well as a set of six samples at
one times the OSHA standard concentration stored at room temperature for eight days to establish
stability [2,5]. Eighteen more samples were spiked (six each at one-half, one and two times the OSHA
standard, 0.14 to 0.54 mg) directly. The pooled precision (Sr) for these three sets of analytical samples
was 0.021 . The average recovery for all three concentrations was 98.8%, representing a non-significant
bias. The value for the taken concentration was obtained by monitoring during generation with a gas
chromatograph with a 2-mL sampling loop. Bag standards were used to calibrate the gas
chromatograph. The stored samples results were within 1% of samples analyzed after one day,
indicating adequate storage stability for eight days. Six parallel breakthrough tubes were run at a time.
The generated atmosphere was pulled through the charcoal tubes (critical orifices to control flow).

jg-CHLOROPRENE: METHOD 1002, Issue 2, dated 15 August 1994 - Page 4 of 4
Several breakthrough studies were done. With 94% relative humidity, breakthrough occurred at 30 min
when sampling 0.194 L/min of 195 mg/m3 (5.8 L). With 91% relative humidity, no breakthrough
occurred after 240 min when sampling 0.045 L/min of 197 mg/m3 (10.8 L).
REFERENCES:
[1] Criteria for a Recommended Standard-Occupational Exposure to Chloroprene, Appendices I and III,
U.S. Department of Health, Education, and Welfare, Publ. (NIOSH) 77-210 (1977).
[2] NIOSH Backup Data Report, S112, prepared under NIOSH Contract 210-76-0123, available as 'Ten
NIOSH Analytical Methods, Set 1," Order No. PB 271-712 from NTIS, Springfield, VA 22161.
[3] Grote, A. Sequence 7239 and 7316 Reports, DPSE/MRSB internal reports (unpublished) (1991).
(1980).
METHOD REVISED BY:
Y. T. Gagnon, NIOSH/DPSE; S112 originally validated in NIOSH Contract 210-76-0123.

CHROMIUM and compounds, as Cr 7024
Cr MW: 52.00 (Cr) CAS: 7440-47-3 (Cr metal) RTECS: (Cr) GB4200000
22541-79-3 [Cr(ll)] Cr(ll) GB6260000
16065-83-1 [Cr( Cr(lll) GB6261000

OSHA : 1.0mg/m3 (metal); PROPERTIES: metal; d 7.14 g/cm3; MP 1890 °C;

0.5 mg/m3 [Cr(ll). Cr(lll)] valences +1 to +6 in salts
NIOSH: 0.5 mg/m3 [Cr metal, Cr(ll), Cr(lll)]
ACGIH: 0.5 mg/m3 [Cr metal, Cr(ll), and Cr(lll)]; see
Method 7600 for Cr(VI)
SYNONYMS: vary depending on the compound

(0.8-fjm cellulose ester membrane)
ANALYTE: chromium
ASHING: conc. HCI, 9mL; 140 °C
VOL-MIN: 10 L @ 0.5 mg/m3 conc. HNO3, 9 mL; 400 °C
-MAX: 1000 L
FINAL SOLUTION: 5% HNO3, 20 mL
SHIPMENT: routine
FLAME: nitrous oxide-acetylene, reducing
SAMPLE
BLANKS: 2 to 10 field blanks per set CALIBRATION: standard solutions of Cr in 5% HNO3
RANGE: 5 to 250 fjg per sample [2,3]
ACCURACY ESTIMATED LOD: 0.06 //g per sample [4]
RANGE STUDIED: 0.4 to 1.8 mg/m3 (insoluble) PRECISION (Sr): 0.04 to 0.06 [5]
0.3 to 1 mg/m3 (soluble) [1]
(90-L samples)
BIAS: - 0.64%
OVERALL PRECISION (SrT): 0.076 (insoluble) [1]
0.085 (soluble [1]
ACCURACY: ± 20.91%
APPLICABILITY: The working range is 0.05 to 2.5 mg/m3 for a 1 00-L air sample. This is an elemental analysis for total Cr, not
compound specific. Some compounds of Cr may not be dissolved by this method. Aliquots can be analyzed separately for
approximately four additional metals.
INTERFERENCES: Interferences from iron and nickel are minimized by using a high temperature flame (reducing nitrous
oxide-acetylene or oxidizing air-acetylene).
OTHER METHODS: This method combines and replaces P&CAM 173 [4], P&CAM 152 [5], S323 [2], and S352 [3]. Method
7300 (Elements by ICP-AES) is an alternate analytical method. Hexavalent chromium, sampled on PVC filters, may be
determined colorimetrically by Method 7600 or Method 7604.

CHROMIUM and compounds, as Cr: METHOD 7024, Issue 2, dated 15 August 1994 - Page 2 of 4

2. Hydrochloric acid, conc. 0.8-^m pore size, 37-mm diameter; in cassette
3. Nitric acid, 5%. Add 50 mL conc. HNO3 to filter holder.
water; dilute to 1 L 2. Personal sampling pump, 1 to 3 L/min, with
4. Calibration stock solution, 1000 //g/mL Cr. flexible connecting tubing.
Dissolve 3.735 g K2CrO4 or 2.829 g K2Cr2O7 in 3. Atomic absorption spectrophotometer with a
distilled or deionized water to make 1 L nitrous oxide-acetylene burner head and
solution. chromium hollow cathode lamp.
5. Distilled or deionized water. 4. Regulators, two-stage, for nitrous oxide and
6. Nitrous oxide. acetylene.
7. Acetylene. 5. Beakers, Phillips, 125-mL, or Griffin, 50-mL,
7. Graduated centrifuge tubes, 15-mL*
See SPECIAL PRECAUTIONS. 8. Assorted volumetric pipets, as needed.*
9. Hotplate, surface temperature to 140 °C.
* Clean all glassware with nitric acid and

rinse thoroughly with distilled or deionized
water before use.
SAMPLING:

1000 L Do not exceed a filter loading of ca. 2 mg total dust.
SAMPLE PREPARATION:
METHOD) [2,3]. Steps 4 through 9 of Method 7300 or other quantitative ashing
techniques may be necessary for some samples, especially if several metals are to be
determined on a single filter.
3. Open the cassettes and filter holders and transfer the samples and blanks to clean beakers.
4. Add 3 mL conc. HCI, cover with a watchglass, heat on hotplate (140 °C) until the volume is
reduced to ca. 0.5 mL Repeat two more times using 3 mL conc. HCI.
NOTE: Start reagent blanks at this step.
5. Add 3 mL conc. HNO3, cover with a watchglass, heat on hotplate (140 °C) until the volume is
reduced to ca. 0.5 mL Repeat two more times using 3 mL conc. HNO3.
6. Cool solution and dissolve the residues in 1 mL conc. HNO3.
7. Transfer the solution quantitatively to a 15-mL graduated centrifuge tube.
8. Dilute to volume with distilled water.

9. Calibrate with at least six working standards. Add known amounts of calibration stock solution,
covering the range 0 to 1000 fjg Cr (0 to 200 pg Cr per sample) to 100-mL volumetric flasks and
dilute to volume with 5% HNO3.
11. Prepare a calibration graph of absorbance vs. solution concentration Oug/mL).
MEASUREMENT:
15. Set spectrophotometer as recommended by the manufacturer and to conditions on page 7024-1.
NOTE: Air-acetylene flame may also be used. In a fuel-lean air-C2H2 or reducing (fuel-rich)
N2O-C2H2 flame, interference by Fe or Ni is minimized or eliminated, but sensitivity for Cr
is reduced. A reducing air-C2H2 flame provides the best sensitivity, but the greatest
susceptibility to interference [5].
16. Aspirate standards and samples. Record absorbance readings
dilute the solutions with 5% HNO3, reanalyze, and apply the appropriate dilution factor in
the calculations.
CALCULATIONS:
17. Using the measured absorbances, calculate the corresponding solution concentrations (/ug/mL)
of chromium in the sample, Cs, and average media blank, Cb, from the calibration graph.
concentration of chromium, C (mg/m3), in the air volume sampled, V (L):
C . 1^
Lab testing with spiked filters and generated atmospheres of soluble chromium (potassium dichromate)
was done at one-half, one and two times the OSHA standard for chromium compounds other than Cr(VI)
of 0.5 mg/m3. The range studied was 0.28 to 0.95 mg/m3. The precision was 0.082 and a bias was not
observed [1,2].
Lab testing with spiked filters and generated atmospheres of insoluble chromium, (produced from
thermal decomposition of chromium hexacarbonyl) was done at one-half, one and two times the OSHA
standard for chromium metal of 1.0 mg/m3 [1,3]. Collection efficiency was 1.00 and analytical
recoveries averaged 98% in the range 45 to 190 //g Cr per sample.
REFERENCES:
[1] Documentation of the NIOSH Validation Tests, U.S. Department of Health, Education, and Welfare,
Publ. (NIOSH) 77-185 (1977).

[3] Ibid, S352.

[4] Ibid, V. 5, P&CAM 173, U.S. Department of Health, Education, and Welfare, Publ. (NIOSH) 79-141
(1979).
[5] Analytical Methods for Atomic Aborption Spectrophotometry, Perkin-Elmer (1976).
METHOD REVISED BY:
Mark Millson, NIOSH/DPSE and R. DeLon Hull, Ph.D., NIOSH/DBBS; Methods S323 and S352
developed under NIOSH Contract CDC-99-74-45.

CHROMIUM, HEXAVALENT 7600
Cr(VI) MW: 52.00 (Cr); 99.99 (CrO3) CAS: 18540-29-9 RTECS: GB6262000

OSHA : 0.1 mg/m3 (as Cr03) PROPERTIES: oxidizing agent

NIOSH: 0.001 mg/m3/10 h; carcinogen
ACGIH: 0.050 mg/m3 (as Cr, soluble); some insoluble
chromates are human carcinogens
SAMPLER: FILTER TECHNIQUE: VISIBLE ABSORPTION

(5.0-fim PVC membrane) SPECTROPHOTOMETRY
FLOW RATE: 1 to 4 L/min ANALYTE: CrO42~-diphenylcarbazide

complex
VOL-MIN: 8 L @ 0.025 mg/m3
-MAX: 400 L EXTRACTION SOLUTION: 0.5 N H2SO4 or 2% NaOH-
3% Na2CO3 (see steps 4 and 5)
SHIPMENT: routine
WAVELENGTH: 540 nm; 5-cm path length
SAMPLE
STABILITY: analyze within 2 weeks [1] CALIBRATION: standard solutions of K2CrO4
in 0.5 N H2SO4
RANGE: 0.2 to 7 fjg per sample
ACCURACY PRECISION (Sr): 0.029 @ 0.3 to 1.2fjg

per sample [3]
(22-L samples)
BIAS: - 5.48%
ACCURACY: ± 18.58%
APPLICABILITY: The working range is 0.001 to 5 mg/m3 for a 200-L air sample. This method may be used for the
determination of soluble Cr(VI) (using 0.5 N H2SO4 as extraction solution or insoluble Cr(VI) (using 2% NaOH - 3% Na2C03) [3],
INTERFERENCES: Possible interferences are iron, copper, nickel, and vanadium; 10//g of any of these causes an absorbance
equivalent to about 0.02 fjg Cr(VI) due to formation of colored complexes. Interference due to reducing agents (e.g., Fe, Fe* *)
is minimized by alkaline extraction (step 5).
OTHER METHODS: This method combines and replaces P&CAM 169 [1], S317 [2] and P&CAM 319 [3]; the Cr(VI) criteria
document [4] contains a method similar to P&CAM 169. Method 7604 is also specific for hexavalent chromium, using ion
chromatography for measurement.

CHROMIUM, HEXAVALENT: METHOD 7600, Issue 2, dated 15 August 1994 - Page 2 of 4
1. Sulfuric acid, conc. (98% w/w). 1. Sampler: polyvinyl chloride (PVC) filter,
2. Sulfuric acid, 6 N. Add 167 mL conc. HZSO4 5.0-/ym pore size, 37-mm diameter in
to water in a 1-L flask; dilute to the mark. polystyrene cassette filter holder (FWSB [MSA]
3. Sulfuric acid, 0.5 N. Add 14.0 mL conc. or VM-1 [Gelman] or equivalent).
H2SO4 to water in a 1-L flask; dilute to the NOTE: Some PVC filters promote reduction
mark. of Cr(VI). Check each lot of filters for
4. Sodium carbonate, anhydrous. recovery of Cr(VI) standard.
5. Sodium hydroxide. 2. Personal sampling pump, 1 to 4 L/min, with
6. Potassium chromate. flexible connecting tubing.
7. Diphenylcarbazide solution. Dissolve 500 mg 3. Vials, scintillation, 20-mL glass, PTFE-lined
sym-diphenylcarbazide in 100 mL acetone and screw cap.**
100 mL water. 4. Forceps, plastic.
8. Cr(VI) standard, 1000 //g/mL Dissolve 5. Spectrophotometer, UV-visible (540 nm), with
3.735 g KgCrO,, in deionized water to make cuvettes, 5-cm path length.
1 L, or use commercially available solution.* 6. Filtration apparatus, vacuum.**
9. Calibration stock solution, 10 //g/mL Dilute 7. Beakers, borosilicate, 50-mL**
1000 fjg/mL Cr(VI) standard 1:100 with 8. Watchglass.**
deionized water. 9. Volumetric flasks, 25-, 100- and 1000-mL**
10. Filter extraction solution, 2% NaOH-3% 10. Hotplate, 120 to 400 °C.
Na2CO3. Dissolve 20 g NaOH and 30 g 11. Micropipettes, 10-//Lto 1-mL
Na2CO3 in deionized water to make 1 L of 12. Centrifuge tubes, 40-mL, graduated, with
solution. plastic stoppers.**
11. Nitrogen, purified. 13. Buchner funnel.**
14. Pipettes, TD 5 mL**
Clean all glassware with 1:1 HNO3 and rinse
thoroughly before use.
SPECIAL PRECAUTIONS: Insoluble chromates are suspected human carcinogens [4]. All sample
preparation should be performed in a hood.
SAMPLING:
1. Calibrate the sampling pump with a representative sampler in line.

2. Sample at an accurately known flow rate in the range 1 to 4 L/min for a sample size of 8 to
3. Remove the filter from the cassette within 1 h of completion of sampling and place it in a vial to
be shipped to the laboratory. Handle the filter only with forceps. Discard the backup pad.
SAMPLE PREPARATION:
NOTE: There are two sample preparation techniques outlined below. For soluble chromates or
chromic acid, follow step 4; for insoluble chromate or Cr(VI) in the presence of Fe, Fe2+
or other reducing agents, follow step 5.
4. Sample preparation for soluble chromates and chromic acid.
a. Remove the blank and sample filters from the vials, then fold and place them into centrifuge
tubes.
b. Add 6 to 7 mL 0.5 N H2SO4 to each tube, cap, and shake to wash all surfaces of the filter.
Allow filter to remain in tube 5 to 10 min [6].
c. Remove the filter from the tube with plastic forceps, carefully washing all surfaces with an

additional 1 to 2 mL 0.5 N H2SO4. Discard the filters. Start reagent blanks at this point.
d. Filter the solution through a moistened PVC filter in a Buchner funnel to remove
interferences from suspended dust. Collect the filtrate in a clean centrifuge tube. Rinse the
bottle, which contained the filter, with 2 to 3 mL 0.5 fjJ H2SO4 and pour into the funnel.
Rinse the funnel and filter with 5 to 8 mL 0.5 N H2SO4.
e. Add 0.5 mL diphenylcarbazide solution to each centrifuge tube. Bring the total volume in
each centrifuge tube to 25 mL with 0.5 N H2SO4. Shake to mix and allow color to develop
(at least 2 min but no longer than 40 min. [6]). Transfer the solution to a clean 5-cm cuvette
and analyze within 40 min of mixing (steps 9 through 11).
5. Sample preparation for insoluble chromates and for Cr(VI) in the presence of iron or other
reducing agents:
NOTE: If significant amounts of Cr(lll) are expected to be present, degas the sample solution by
bubbling nitrogen through it for 5 min. before proceeding and purge the headspace
above the solution during step 5.a.
a. Remove the PVC filter from the bottle, place it in a 50-mL beaker, and add 5.0 mL filter
extraction solution, 2% NaOH/3% Na2CO3. Start reagent blanks at this point. Purge the
headspace above the solution with nitrogen throughout the extraction process to avoid
oxidation of any Cr(lll). Cover the beaker with a watchglass and heat it to near the boiling
point on a hotplate with occasional swirling for 30 to 45 min. Do not boil the solution or
heat longer than 45 min. Do not allow the solution to evaporate to dryness because
hexavalent chromium may be lost owing to reaction with the PVC filter. An indication that
hexavalent chromium has been lost in this manner is a brown-colored PVC filter.
b. Cool the solution and transfer it quantitatively with distilled water rinses to a 25-mL
volumetric flask, keeping the total volume about 20 mL
NOTE: If the solution is cloudy, filter it through a PVC filter in a vacuum filtration apparatus
using distilled water rinses.
c. Add 1 .90 mL 6 N sulfuric acid to the volumetric flask and swirl to mix.
CAUTION: CARBON DIOXIDE WILL BE EVOLVED CAUSING INCREASED PRESSURE IN
THE FLASK. LET THE SOLUTION STAND FOR SEVERAL MINUTES UNTIL
VIGOROUS GAS EVOLUTION CEASES.
d. Add 0.5 mL diphenylcarbazide solution, dilute to the mark with distilled water and invert
several times to mix thoroughly. Pour out about one-half of the contents of the flask,
stopper the flask and shake it vigorously several times, removing the stopper each time to
relieve pressure.
NOTE: This step releases bubbles of carbon dioxide which otherwise would cause high and
erratic readings.
e. Transfer an aliquot of the solution remaining in the flask to a 5-cm cuvette and analyze
(steps 9 through 11).
6. Calibrate daily with at least six working standards. Transfer 6 to 7 mL 0.5 N H2SO4 to each of a
series of 25-mL volumetric flasks. Pipet 0 to 0.7 mL of 10 //g/mL calibration stock solution into
the volumetric flasks. Add 0.5 mL diphenylcarbazide solution to each and sufficient 0.5 N H2SO4
to bring the volume to 25 mL These working standards contain 0 to 7 fjg Cr(VI).
7. Analyze the working standards together with blanks and samples (steps 9 through 11).
8. Prepare a calibration graph [absorbance vs. //g Cr(VI)].
MEASUREMENT:
9. Set wavelength on the spectrophotometer to 540 nm.

10. Set to zero using a 0.5 N H2SO4 reagent blank.
11. Transfer sample solution to a cuvette and record the absorbance.
NOTE 1 : A sample containing 1 .5 //g Cr(VI)/25 mL gives ca. 0.2 absorbance.

NOTE 2: If the absorbance values for the samples are higher than the standards, dilute using
0.5 N H2SO4, repeat this step, and multiply the resulting absorbance by the
appropriate dilution factor.
CALCULATIONS:
12. From the calibration graph, determine the mass of Cr(VI) in each sample, W (JJQ), and in the
average blank, B (JJQ).
13. Calculate the concentration, C (mg/m3), of Cr(VI) in the air volume sampled, V (L):
C = Wy B, mg/m3.
P&CAM 169 and S317 are essentially the same method and are suitable for soluble chromate and
chromic acid. Method S317 was validated with generated samples of chromic acid mist [2,6], and
P&CAM 169 was tested with field samples [1,7]. P&CAM 319 was developed because a method was
needed to analyze for insoluble chromates [3]. This method was tested with insoluble chromates in
matrices such as paints, primer and ceramic powders [3].
Precision, analytical range, recovery data, etc., for the three methods pooled are as follows:
Total SrT: 0.084

Measurement Sr [1-3]: 0.02 to 0.04
Range [3]: 0.5 to 10 //g/m3
Collection Efficiency [5]: 94.5%
Sampling Rate [1,3]: 1.5 to 2.5 L/min
Stability (two weeks) [1]: 96% recovery
Acceptable Filters [3]: FWSB (MSA); VM-1 (Gelman).
REFERENCES:
[2] Ibid, V. 3, S317, U.S. Department of Health, Education, and Welfare, Publ. (NIOSH) 77-157-C (1977).
[3] Ibid, V. 6, P&CAM 319, U.S. Department of Health and Human Services, Publ. (NIOSH) 80-125
(1980).
[4] NIOSH (1975) Criteria for a Recommended Standard: Occupational Exposure to Chromium (VI).
Cincinnati, OH: U.S. Department of Health, Education, and Welfare, National Institute for
Occupational Safety and Health, DHEW (NIOSH) Publication No. 76-129.
[5] NIOSH/OSHA Occupational Health Guidelines for Chemical Hazards. Occupational Health
Guidelines for Chromic Acid and Chromates. U.S. Department of Health and Human Services
(NIOSH) Publication No. 81-123 (1981).
Publ. (NIOSH) 77-185 (1977).
[7] Abell, M. T. and J. R. Carlberg. A Simple Reliable Method for the Determination of Airborne
Hexavalent Chromium, Am. Ind. Hyg. Assoc. J., 35, 229 (1974).
METHOD REVISED BY:
Martin T. Abell, NIOSH/DPSE; Method S317 validated under NIOSH Contract CDC-99-74-45.

CHROMIUM, HEXAVALENT 7604
Cr (VI) MW: 52.00 (Cr); 99.99 (CrO3) CAS: 18540-29-9 RTECS: GB6262000

OSHA : 0.1 mg/m3 (as CrO3) PROPERTIES: oxidizing agent

NIOSH: 0.001 mg/m3/10 h; carcinogen
ACGIH: 0.050 mg/m3 (as Cr, soluble); some insoluble
chromates are human carcinogens
SYNONYMS: vary according to the compound.
SAMPLER: FILTER TECHNIQUE: ION CHROMATOGRAPHY,

(5.0-fjm PVC membrane) CONDUCTIVITY DETECTION
FLOW RATE: 1 to 4 L/min ANALYTE: chromate ion
VOL-MIN: 100 L @ 0.1 mg/m3 EXTRACTION: 5 mL 2% NaOH/3% Na2C03

-MAX: 1000 L
INJECTION
SHIPMENT: routine VOLUME: 50 //L
SAMPLE ELUENT: 7.0 mM Na2CO3/0.5 mM

STABILITY: at least 2 weeks at 25 °C NaOH, 2.0 mL/min
BLANKS: 2 to 10 field blanks per set COLUMN: Dionex HPIC-AG5 guard, HPIC-AS5
separator, and anion suppressor, or
equivalent
DETECTOR: 1 //S full scale

ACCURACY
CALIBRATION: standard solutions of Cr(VI) in 0.4%
RANGE STUDIED: 0.05 to 0.15 //g/m3 NaOH/0.6% Na2CO3
(400-L samples)
RANGE: 10 to 250 //g per sample [1]
BIAS: + 0.08%
OVERALL PRECISION (S^): 0.066 [1] ESTIMATED LOD: 3.5 //g per sample [1]
ACCURACY: ± 13.0%
PRECISION (Sr): 0.043 @ 22 to 62 //g per sample [1]
APPLICABILITY: The working range is 0.01 to 4 mg/m3 for a 500-L air sample. This method is less sensitive than method 7600
(colorimetric), but it contains fewer sample preparation steps and was found free from interferences when used for samples of
five chromate-containing paints. This method may be used for the determination of insoluble or soluble Cr(Vl).
INTERFERENCES: Interferences from reducing agents (e.g., Fe, Fe ' ' ) are eliminated by alkaline extraction. Cations of metals,
interfering with the colorimetric method, do not interfere with this method. Inadequately-cleaned glassware may create a
negative bias.
OTHER METHODS: This method is an alternative to NIOSH Method 7600 (colorimetric).

1. Sodium carbonate, anhydrous. 1. Sampler: polyvinyl chloride (PVC) filter,

2. Sodium hydroxide, reagent grade. 5.0-//m pore size, 37-mm diameter (FWSB
3. Extraction solution, 2% NaOH/3% Na2CO3. [MSA] or VM-1 [Gelman], or equivalent) with
Dissolve 20 g NaOH and 30 g Na2CO3 in backup pad in polystyrene cassette filter
deionized water to make 1 L of solution. holder.
4. Eluent, 7.0 mM Na2CO3-0.5 mM NaOH. NOTE: Some PVC filters promote reduction
Dissolve 2.97 g Na2CO3 in 4 L deionized water. of Cr(VI). Check each lot of filters for
Add 20 mL of 0.1 M NaOH (8 g/L). recovery of Cr(VI) standard.
5. Suppressor regenerant, 0.025 N H2SO4. Dilute 2. Personal sampling pump, 1 to 4 L/min, with
2.8 mL of conc. H2SO4 in deionized water to 4 flexible connecting tubing.
L 3. Ion chromatograph, with conductivity detector,
6. Cr(VI) standard, 1000//g/mL columns, suppressor (p. 7604-1).
7. Calibration stock solution, 100 //g/mL Dilute 4. Vials, scintillation 20-mL glass, PTFE-lined
1000 //g/mL Cr(VI) standard 1:100 with screw cap.
distilled or deionized water. 5. Forceps, plastic.
8. Nitrogen, purified. 6. Syringe, 10-mL, with in-line membrane filter
9. Water, distilled or deionized. 0.45-//m pore size.
7. Beakers, borosilicate, 50-mL
* See SPECIAL PRECAUTIONS. 8. Watchglasses.
9. Volumetric, flasks, 25-, 100-, and 1000-mL
10. Hotplate, 120 to 400 °C.
11. Micropipette, 20-//L, and other sizes.
12. Centrifuge tubes, 40-mL, graduated, with
plastic, screw caps.
SPECIAL PRECAUTIONS: Insoluble chromates are suspected human carcinogens [2]. All sample
preparation should be performed in a hood.
SAMPLING:

2. Sample at an accurately known flow rate in the range 1 to 4 L/min for a sample size of 100 to
1000 L Do not exceed 2 mg of particulate loading on the filter.
3. Remove the filter from the cassette within 1 hour of completion of sampling, and place it in a vial
to be shipped to the laboratory. Handle the filters only with forceps. Discard the backup pad.
SAMPLE PREPARATION:
4. Place the filter face down in a 50-mL beaker, and add 5.0 mL extraction solution. Start reagent
blanks at this point.
NOTE 1 : If significant amounts of Cr(lll) are expected to be present, degas the extraction
solution by bubbling a slow stream of nitrogen through it for 5 min before proceeding
and purge the headspace above the solution with nitrogen during this step.
NOTE 2: If only soluble chromates are of interest use distilled water in place of extraction
solution.
5. Cover the beaker with a watchglass and place on a hotplate preheated to 135 °C. Heat the
samples for 45 min with occasional swirling.
NOTE 1: Do not allow the solution to boil or evaporate to dryness. Hexavalent chromium may
be lost by reaction with the PVC filter, as indicated by a brown coloring in the filter.
NOTE 2: Longer heating times, up to 90 min. may be necessary for some samples (e.g., paint
spray [1]).

6. Cool the solution and transfer it quantitatively with distilled water rinses to a graduated centrifuge
tube. Adjust the final volume to 25 mL with distilled water.
7. Calibrate daily with at least six working standards over the range of 0 to 250 fjg Cr (VI) per
sample.
a. Pipet 0 to 2.5 mL calibration stock solution into each of a series of 25-mL volumetric flasks.
Add 5 mL extraction solution to each flask and dilute to the mark with deionized water.
b. Analyze the working standards (steps 8 through 10).
c. Prepare a calibration graph [peak height vs. //g Cr(VI) per sample].
MEASUREMENT:
8. Set ion chromatograph according to manufacturer's recommendations and to conditions on

page 7604-1 . Set regenerant flow to 3 mL/min.
9. Inject 50 fjL sample aliquot manually or with autosampler.
NOTE: All samples and standards must be filtered before injection to avoid plugging columns
and lines.
10. Measure peak height. (Retention time for Cr(VI) peak is approximately 12 min under these
conditions.)
CALCULATIONS:
11. From the calibration graph, determine the mass of Cr(VI) in each sample, W (//g), and in the
average blank, B (^g).
12. Calculate the concentration, C (mg/m3), of Cr(VI) in the air volume sampled, V (L):
C = W^B, mg/m 3.
This method was evaluated with three sets of 16 filter samples which were collected from a
chromate-containing paint aerosol [2]. The average amount of Cr(VI) on the filter ranged from 24 to 62
micrograms. Half of the samples were analyzed by this method while the other half were analyzed by
Method 7300 (ICP). The results were not significantly different at the 95% confidence level. To examine
sample stability, selected members of a fourth set of filters were analyzed and the remainder were stored
for two weeks under cover in a constant temperature and constant humidity environment. Comparison
of the results of analysis before and after storage indicated that the amount of Cr(VI) did not change
during this period.
REFERENCES:
[1] Molina, D. and M. T. Abell. An Ion Chromatographic Method for Insoluble Chromium in Paint
Aerosol. Am. Ind. Hyq. Assoc. J. 48:830-835 (1987).
[2] NIOSH Testimony on the OSHA Proposal Rules on Air Contaminants, Docket #H-020,
August 1, 1988.
METHOD REVISED BY:
Martin T. Abell, NIOSH/DPSE.

CHROMIUM, Hexavalent, in Settled Dust Samples 9101
Cr(VI) MW: 52.00 CAS: 18540-29-9 RTECS: GB6262000
METHOD: 91 01 , Issue 1 EVALUATION: PARTIAL Issue 1 : 1 5 May 1 996
PURPOSE: Estimation of soluble hexavalent chromium content of settled dust.
LIMIT OF
DETECTION: 1 ug Cr(VI) per sample
FIELD
EQUIPMENT: 1. Chromate (Diphenylcarbazide reagent) test kit (Chemetrics Chromate Kit, or
equivalent)
2. Sulfuric acid, 20% w/v (included in test kit)
3. Extraction solution, 2% NaOH/3% Na2CO3 in deionized water
4. Deionized water
5. Centrifuge tubes, 15-mL, graduated, clear plastic with screw-caps, disposable
6. Spatula, ~0.1 cm3 capacity
7. pH paper
PROCEDURE: 1 . Place 1 spatula full of dust (approximately 0.1 cm3; the size of a small pea) to be tested
in a 15-mL clear plastic centrifuge tube. Add extraction solution up to the 2-mL mark.
Cap the tube and shake vigorously.
2. Allow the tube to stand for 10 minutes, or longer, with occasional shaking.
NOTE: Gently heating the tube in hot water will increase the sensitivity of the test.
3. Uncap the centrifuge tube and add deionized water to the 7-mL mark. Mix and allow the
residue to settle.
4. Decant or pipet approximately 3 mL of the supernatant liquid into a second tube.

NOTE: The sample may be filtered, if excessively turbid.
5. Add 9 drops of 20% sulfuric acid (3 drops /mL of decanted liquid), cap the tube, and
invert to mix the contents.
6. Check the pH of the liquid with pH paper. If necessary, add 20% sulfuric acid dropwise
to bring to pH <1.
7. Follow the instructions for color development.
NOTE: For more accurate determination of total hexavalent chromium in the dust, send a
sample to the laboratory for analysis by Method 7600 or 7604.
METHOD WRITTEN BY: Mark B. Millson, MRSB/DPSE, and Peter M. Eller, Ph.D., QASA/DPSE

COBALT and compounds, as Co 7027
Co MW: 58.93 (Co) CAS: 7440-48-4 (Co) RTECS: GF8750000

OSHA : 0.01 mg/m3 PROPERTIES: magnetic, hard metal; valence +2, +3;
NIOSH: 0.05 mg/m3 MP 1495 °C; VP not significant
ACGIH: 0.05 mg/m3 (fume, dust)

(0.8-pm cellulose ester membrane)
ANALYTE: cobalt
ASHING: aqua regia, 3 mL, 140 °C;
VOL-MIN: 30 [email protected] mg/m3 conc. HNO3, 6mL, 140 °C;
-MAX: 1500 L room temperature, 30 min;
140 °C to near dryness
SHIPMENT: routine
FINAL SOLUTION: 5% HNO3, 10 mL
SAMPLE
STABILITY: stable FLAME: air-acetylene, oxidizing
FIELD BLANKS: 2 to 10 field blanks per set WAVELENGTH: 240.7 nm
BACKGROUND CORRECTION: D2 or H2 lamp
CALIBRATION: Co2* in 5% HNO3

ACCURACY
(270-L samples) ESTIMATED LOD: 0.6 //g per sample [3]
BIAS: 5.59%
PRECISION (§r): 0.03 [1]; 0.02 [3]
ACCURACY: ± 18.05%
APPLICABILITY: The working range is 0.01 to 0.3 mg/m3 for a 300-L sample. This is an elemental analysis, not compound
specifie. Verify that the types of compounds in the samples are soluble with this ashing procedure. Aliquots of the samples
can be analyzed separately for approximately four additional metals.
INTERFERENCES: The use of D2 or H2 continuum background correction is required to control molecular or flame absorption.
There are no known spectral line interferences.
OTHER METHODS: This method combines and replaces P&CAM 173 [4] and S203 [2] for cobalt. Method 7300 (Elements by
ICP-AES) is an alternate analytical technique.

COBALT and compounds, as Co: METHOD 7027, Issue 2, dated 15 August 1994 - Page 2 of 3

2. Hydrochloric acid, conc. 0.8-fjm pore size, 37-mm diameter; in cassette
3. Aqua regia: mix 3 volumes conc. HCI with 1 filter holder.
volume conc. HNO3. 2. Personal sampling pump, 1 to 3 L/min, with
4. Nitric acid, 5% (w/v). Add 50 mL conc. HNO3 flexible connecting tubing.
to water; dilute to 1 L 3. Atomic absorption spectrophotometer with an
5. Calibration stock solution, 1000 //g/mL Co. air-acetylene burner head and cobalt hollow
Commercially available or dissolve 1 .000 g Co cathode lamp.
metal in minimum volume of aqua regia. 4. Regulators, two-stage, for air and acetylene.
Dilute to 1 L with 5% HNO3. 5. Beakers, Phillips, 125-mL, or Griffin, 50-mL,
6. Distilled or deionized water. with watchglass covers.*
7. Air, filtered. 6. Volumetric flasks, 10- and 100-mL*
8. Acetylene. 7. Micropipets, 5 to 60 //L*
8. Hotplate, surface temperature 140 °C.
* Clean with conc. HNO3 and rinse

before use.
SAMPLING:

1500 L Do not exceed a filter loading of approximately 2 mg total dust.
SAMPLE PREPARATION:
NOTE: The following sample preparation gave quantitative recovery (see EVALUATION OF METHOD).
Steps 4 through 9 of Method 7300 or other quantitative ashing techniques may be necessary for
some samples, especially if several metals are to be determined on a single filter.
4. Add 3 mL aqua regia, cover with a watchglass, let stand at room temperature 30 min. Start
reagent blanks at this point.
5. Heat on hotplate (140 °C) until most of the acid has evaporated (ca. 0.5 mL remains).
6. Repeat 2 more times using 3 mL conc. HNO3 each time. Leave about 1 mL solution after the
last digestion.
7. Cool each beaker, remove watchglass, and rinse into the beaker with 5% HN03.
8. Dissolve the residues in 2 to 3 mL 5% HNO3.
10. Dilute to volume with 5% HNO3.
11. Calibrate daily with at least six working standards. Add known amounts, covering the expected
range of samples (0 to 60 //g Co per sample), of calibration stock solution to 10-mL volumetric
flasks and dilute to volume with 5% HNO3.

COBALT and compounds, as Co: METHOD 7027, Issue 2, dated 15 August 1994 - Page 3 of 3
13. Prepare a calibration graph of absorbance vs. solution concentration (mg/mL).
MEASUREMENT:
17. Set spectrophotometer according to the manufacturer's recommendations and to the conditions
on page 7027-1.
dilute the solutions with 5% HNO3, reanalyze, and apply the appropriate dilution factor in
the calculations.
CALCULATIONS:
19. Using the measured absorbances, calculate the corresponding concentrations (jjg/mL) of cobalt
in the sample, Cs, and average media blank, Cb, from the calibration graph.
concentration, C (mg/m3), of cobalt in the volume of air sampled, V (L):
c . (C-V-C^'
Method S203 [2] was issued on February 18, 1977, and validated over the range 0.03 to 0.22 mg/m3 Co
fume and 0.04 to 0.26 mg/m3 Co dust using spiked filters and generated atmospheres of cobalt dust
and fume (Co2O3) [1]. Precision and accuracy data are given on page 7027-1. A separate check on this
method showed 98% recovery from filters spiked with 12 or 96 //g soluble Co [3].
REFERENCES:
Publ. (NIOSH) 77-185 (1977).
[2] NIOSH Manual of Analytical Methods, 2nd ed., V. 4, Method S203, U.S. Department of Health,
[3] User check, UBTL, NIOSH Seq. #3990-N (unpublished, November 29, 1983).
METHOD REVISED BY:
Mark Millson, NIOSH/DPSE and R. DeLon Hull, Ph.D., NIOSH/DBBS; S203 originally validated under
NIOSH Contract CDC-99-74-45.

COPPER (dust and fume) 7029
Cu MW: 63.54 CAS: 7440-50-8 (Cu) RTECS: GL5325000

OSHA : 0.1 mg/m3 (fume); 1 mg/m3 (dust) PROPERTIES: soft metal; valence +1, +2 in salts
NIOSH: 0.1 mg/m3 (fume); 1 mg/m3 (dust) MP 1083 °C
ACGIH: 0.2 mg/m3 (fume);
1 mg/m3 (dust, mist)
SYNONYMS: vary depending upon the compound; CAS #1317-39-1 (Cu2O), CAS #1317-38-0 (CuO)

ANALYTE: copper
ASHING: conc. HNO3, 6 mL, 140 °C;
VOL-MIN: 50 L @ 0.1 mg/m3 conc. HCI, 6 mL, 400 °C
-MAX: 1500 L
FINAL SOLUTION: 0.5 N HCI; 25 mL
SHIPMENT: routine
FLAME: air-acetylene, oxidizing
SAMPLE
BLANKS: 2 to 10 field blanks per set BACKGROUND CORRECTION: not required
CALIBRATION: standard solutions of

Cu2* in 0.5 N HCI
ACCURACY RANGE: 5 to 125 //g per sample [4]
RANGE STUDIED: 0.05 to 0.59 mg/m3 (fume) [1,2] ESTIMATED LOD: 0.05 //g per sample [5]
0.47 to 1.8 mg/m3 (dust) [3]
PRECISION (Sr): 0.03 [1,3,5]
BIAS: - 0.44%
OVERALL PRECISION (SrT): 0.044 (fume) [1,2]
0.051 (dust) [3]
ACCURACY: ± 11.0%
APPLICABILITY: The working range is 0.05 to 1.3 mg/m3 for a 100-L air sample. This is an elemental analysis, applicable to
either dust or fume, with an additional separation step to quantitate soluble copper dust (e.g., CuSOj in the presence of copper
fume. Aliquots of the samples can be analyzed separately for many additional metals.
INTERFERENCES: Background correction is not required. Interferences to the fume/soluble dust separation step include
insoluble copper compounds and copper compounds such as copper acetate which form insoluble hydroxides when dissolved
in water.
OTHER METHODS: This method combines and replaces P&CAM 173 [5], S354 [4], and S186 [6]. Method 7300, plasma
emission (ICP-AES), is an alternate analytical method.

COPPER (dust and fume): METHOD 7029, Issue 2, dated 15 August 1994 - Page 2 of 4

2. Hydrochloric acid, conc. 0.8-fjm pore size, 37 mm-diameter; in cassette
3. Hydrochloric acid, 0.5 N. Add 41.5 mL conc. filter holder.
HCI to water, dilute to 1 L 2. Personal sampling pump, 1 to 3 L/min, with
4. Calibration stock solution, 1000^g/mL flexible connecting tubing.
Commercially available, or dissolve 1 .000 g Cu 3. Atomic absorption spectrophotometer with an
metal in minimum volume of (1:1) HNO3. air-acetylene burner head and copper hollow
Dilute to 1 L with 0.5 N HCI. cathode lamp and two-stage regulators for air
5. Distilled-deionized water. and acetylene.
6. Air, filtered. 4. Beakers, Phillips, 125-mL, or Griffin, 50-mL,
7. Acetylene. with watchglass covers.*
6. Assorted volumetric pipets, as needed.*
7. Hotplate, surface temperature 140 °C and
* See SPECIAL PRECAUTIONS. 400 °C.
8. Equipment for fume/dust separation step:
a. cellulose ester membrane filters, 47-mm,
0.3-//m pore size (Millipore PHWP or
equivalent);
b. cellulose ester membrane filter, 47-mm,
5-fjm pore size (Millipore SMWP or
equivalent);
c. filtration apparatus (Gelman No. 1107 or
equivalent).
* CIean all glassware with conc, nitric acid

and rinse thoroughly with distilled or
deionized water before use.
SAMPLING:

1500 L Do not exceed a total filter loading of ca. 2 mg total dust.
SAMPLE PREPARATION:
METHOD). Other quantitative ashing techniques (e.g., HNO3-HCIO4 [Method 7300]) may
be useful alternatives, especially if several metals are to be determined on a single filter.
3. Proceed to step 4 if fume/dust separation is not desired. For fume/dust separation:
a. Using forceps, prewet a 47-mm, 0.3-//m pore size cellulose ester membrane filter by placing
it on the surface of distilled water. Remove the filter, tap off excess water, and mount it on
the filtration unit.
b. Transfer the sample filter from the cassette filter holder to the filtration unit, placing it
concentrically on top of the 47-mm filter with the fume deposit up.

c. Apply and release the vacuum so that the 37-mm filter is gently wetted from the moisture
retained on the 47-mm filter. This also insures the removal of any air bubbles between the
filters.
d. When the fume sample is visually clear of air bubbles and wet throughout, apply a vacuum
of 10 to 15 PSIG (69 to 103 kPa). Release the vacuum.
e. Place a 47-mm, 5-fjm cellulose ester membrane filter on the surface of water to wet it,
remove excess water by blotting with tissue, and place it concentrically on top of the 37-mm
filter. Press the surface of the top filter with a clean tissue to insure that no air bubbles
remain between any of the filters.
f. Mount the upper part of the filtration unit, add 5 mL of distilled water, and allow vacuum to
draw water through the filters. Repeat with 5 mL more water. Combine the filtrates which
contain soluble copper compounds in a clean beaker. Start reagent blanks at this point.
g. Transfer all filters to a clean beaker. Proceed to step 5.
NOTE: Each sample blank is a combination of three filters.
5. Add 6 mL conc. HNO3. Cover with a watchglass and heat on hotplate (140 °C) until the volume
is reduced to approximately 0.5 mL Repeat two more times using 2 mL conc. HNO3 each time.
NOTE: Start reagent blanks at this point if step 3 was omitted.
6. Add 2 mL conc. HCI, cover with a watchglass, heat on hotplate (400 °C) until the volume is
reduced to approximately 0.5 mL. Repeat two more times using 2 mL conc. HCI. Do not allow
the solution to go to dryness at any point.
7. Cool solution and add 10 mL distilled water.
8. Transfer the solution quantitatively to a 25-mL volumetric flask. Dilute to volume with distilled
water.
9. Calibrate daily with at least six working standards. Add known amounts, covering the range 0 to
125 fjQ Cu per sample, of calibration stock solution to 25-mL volumetric flasks and dilute to
volume with 0.5 N HCI.
11. Prepare a calibration graph by plotting absorbance versus solution concentration
MEASUREMENT:
15. Set spectrophotometer as specified by the manufacturer and to conditions on page 7029-1.
16. Aspirate standards, samples, and blanks. Record absorbance readings.
dilute the sample solutions with 0.5 N HCI, reanalyze, and apply the appropriate dilution
factor in the calculations.
CALCULATIONS:
17. Using the measured absorbances, calculate the corresponding concentrations (/ug/mL) of
copper in the sample, Cs, and average media blank, Cb, from the calibration graph.
concentration of copper in the air volume sampled, V (L):

C .
Method S186 was validated on August 29, 1975, with overall sampling and analytical precision, S\T =
0.051, over the range 0.47 to 1.8 mg/m3 for a 90-L sample of CuO dust [3,6] and^Method S354 was
validated on September 30, 1977, with overall sampling and analytical precision, SrT = 0.058, over the
range 0.05 to 0.37 mg/m3 for a 480-L sample of Cu fume [1 ,4]. Copper fume atmospheres were
generated by thermal decomposition and subsequent oxidation of cupric acetate aerosol. The size of
the copper fume was 0.04 to 0.14 fjm by electron microscopy and the collection efficiency of the
sampler for this fume was 1.00 [1,4,9].
The dust-fume separation step was evaluated with samples laden with copper fume generated from
copper welding; the samples were then placed into a dust generation system and overlaid with a known
deposition of copper sulfate dust. With a dust loading of about 600 fjg CuSO4 and fume concentrations
of 0.13 to 0.59 mg/m3, an average of 96.5% of the dust was removed. The analysis of the copper fume
had a pooled Sr of 4.4% with an average bias of 5.3% [2].
Efficiencies of removal of Cu dust and fume were determined from samples containing only dust or only
fume. Measured efficiencies were: (1) from filters containing 213 to 265 fjg CuSO4, an average of 97.8%
was removed using 1 0 to 50 mL water; (2) filters laden with ca. 200 fjg Cu/filter lost 1 1 .5% Cu after
washing with 10 mL H2O. Because the non-equilibrium nature of the washing process does not lend
itself to accurate prediction of the amount of copper fume removed by the wash water, no correction
factor for the amount of fume removed was determined or employed. The elemental analysis used in
the evaluation did not distinguish between copper from the fume and from the dust [2].
REFERENCES:
[1] Backup Data Report for Copper Fume, S354, prepared under NIOSH Contract No. 210-76-0123,
available as "Ten NIOSH Analytical Methods, Set 5," Order No. PB 287-499 from NTIS, Springfield,
VA 22101.
[2] Carsey, T. Development of a Sampling and Analytical Method for Copper Fume, final report, NIOSH
(DPSE) (unpublished, September, 1982).
Publ. (NIOSH) 77-185 (1977).
[4] Ibid, V. 4, Method S354, U.S. Department of Health, Education, and Welfare, Publ. (NIOSH) 78-175
(1978).
[6] Ibid, V. 3, Method S186, U.S. Department of Health, Education, and Welfare, Publ. (NIOSH) 77-157-C
(1977).
[7] Winefordner, J. D., Ed. Spectrochemical Methods of Analysis. John Wiley & Sons (1971).
[8] Analytical Methods for Atomic Absorption Spectrophotometry, Perkin-Elmer (1976).
(1980).
METHOD REVISED BY:
Mark Millson, NIOSH/DPSE, and R. DeLon Hull, Ph.D., NIOSH/DBBS; originally validated under NIOSH
Contracts CDC-94-74-45 and 210-76-0123.

CRESOL (all isomers) and PHENOL 2546
CH3C6H4OH MW: 108.14 CAS: 1319-77-3 RTECS: GO5950000

C6H5OH 94.11 108-95-2 SJ3325000

NIOSH:
ACGIH:
SYNONYMS: o-cresol: 2-methylphenol; CAS #95-48-7; m-cresol: 3-methylphenol; CAS #108-39-4; g-cresol: 4-methylphenol;
CAS #106-44-5.
phenol: carbolic acid; hydroxybenzene
SAMPLER: SOLID SORBENT TUBE TECHNIQUE: GAS CHROMATOGRAPHY , FID

(XAD-7, 100 mg/50 mg)
ANALYTE: cresol isomers/phenol
DESORPTION: 2 mL methanol; sonicate
VOLUME: 1//L (split 20:1)
SHIPMENT: routine
STABILITY: at least 1 week @ 25 °C [1] -COLUMN: 160 - 225 ° C (3 °C/min)
BLANKS: 2 to 10 field blanks per set CARRIER GAS: He, 1 mL/min
COLUMN: Stabilwax DA fused silica capillary, 30 m,

0.32-mm ID, 0.25-mm film or equivalent
ACCURACY CALIBRATION: standard solutions of analytes in

methanol
RANGE: 20 to 800 /.g per sample
ESTIMATED LOD : 1 to 3 //g per sample
OVERALL PRECISION (§rT): not determined
ACCURACY: not determined PRECISION (Sr): 0.028 [1]
APPLICABILITY: The working range is 0.25 to 15 ppm (1 to 60 mg/m3) for cresols and phenol in a 20-L air sample.
INTERFERENCES: None identified. A DB-wax fused silica capillary column is an alternate column.
OTHER METHODS: This method uses a sampler similar to that of OSHA 32 [1] and replaces methods 2001 (Cresols) [2] and
3502 (Phenol) [3]. Analysis of the sample extracts can also be done by HPLC/UV [1,4].

CRESOL (all isomers) and PHENOL: METHOD 2546, Issue 1, dated 15 August 1994 - Page 2 of 4
1. Methanol, chromatographic quality. 1. Sampler: glass tube, 11 cm long, 6-mm OD,

2. n-Hexane. 4- mm ID;two sections of 20/40 mesh XAD-7
3. Cresol (all isomers).* Dissolve 2 g o-cresol separated by a 2-mm portion of silanized glass
(solid), 3 g p.-cresol (solid) in 4 g (4.13 mL) of wool (front = 100 mg, back = 50 mg).
m-cresol and mix. 2. Personal sampling pump, 0.01 to 0.1 L/min,
4. Calibration stock solution, 10.4 mg/mL Dilute with flexible connecting tubing.
104 mg cresol isomer mixture (1.0 mL at 20 3. Gas chromatograph, FID, integrator and
°C) to 10 mL with n-hexane. column (page 2001-1).
5. Hydrogen, prepurified. 4. Vials, glass, 2-mL, PTFE-lined crimp caps.
6. Nitrogen, purified. 5. Syringe, 10-//L, readable to 0.1 fjL.
7. Air, filtered. 6. Pipet, 1.0-mL, with pipet bulb.
* See SPECIAL PRECAUTIONS. 8. Ultrasonic bath.
SPECIAL PRECAUTIONS: Cresol and phenol cause severe burns [5]. They are toxic if absorbed
through skin, inhaled or ingested. All work with them should be performed in a hood.
SAMPLING:

to 24 L
SAMPLE PREPARATION:
5. Place the front sorbent section (together with the front glass wool plug) and back sorbent
sections of the sampler tube in separate vials. Discard the other plugs.
6. Add 2.0 mL methanol to each vial. Attach crimp cap to each vial.
7. Ultrasonicate 30 min.
8. Calibrate daily with at least six working standards over the range 1 to 800 ;/g cresol and phenol
per sample.
a. Add known amounts of calibration stock solution to methanol in 10-mL volumetric flasks and
dilute to the mark.
c. Prepare calibration graph (total peak area vs. //g analyte).
9. Determine desorption efficiency (DE) at least once per year for each lot of sorbent used for
sampling in the calibration range. Prepare three tubes at each of five concentrations plus three
media blanks.
microliter syringe.
e. Prepare a graph of DE vs. JJQ analyte recovered.

MEASUREMENT:
on page 2000-1. Inject 1-//L sample aliquot manually using solvent flush technique or with
autosampler.
NOTE: If peak area is above the linear range of the working standards, dilute with methanol,
12. Measure total peak area of the two analyte peaks.
CALCULATIONS:
13. Determine the mass, //g (corrected for DE) of cresols and phenol found in the sample front (Wf)
and back (Wb) sorbent sections, and in the average media blank front (B() and back (Bb) sorbent
sections.
14. Calculate concentration, C, of cresols in the air volume sampled, V (L):
. W,»Wb-B,-B
This is a modification of OSHA Method 32 (Phenol and Cresol) which uses the same sampling
procedure [1]. Phenol and all cresol isomers were easily resolved by capillary GC using a split injection
ratio of 20:1. The desorption efficiency (DE) results for all analytes were > 0.90. Analytes were stable
for 30 days when refrigerated.
REFERENCES:
[1] Phenol and Cresol, Occupational Safety and Health Administration, OSHA Method 32, OSHA
Analytical Laboratory, 1981.
[2] NIOSH Manual of Analytical Methods, 3rd ed., Vol. 2, Method 3502, U.S. Dept. of Health, Education,
and Welfare, Publication #84-100 (NIOSH), 1984.
[3] Ibid, Method 2001.
[4] DataChem Laboratories Report, Seq. #7478-L (NIOSH, unpublished, May 8, 1992).
[5] NIOSH/OSHA, Occupational Health Guidelines for Chemical Hazards, USDHHS (NIOSH), Publ. 81-
123 (1981).
[6] Pendergrass, S.M., An Improved Method for the Sampling and Analysis of Phenol and Q-, m-, and p_-
Cresol by Capillary GC/FID, Amer. Ind. Hyg. Assoc. J. (accepted for publication, 1994).
[7] Gessner, H., Ed., Condensed Chemical Dictionary, 10th ed., Van Nostrand Reinhold, 1981.
METHOD REVISED BY:
Stephanie M. Pendergrass, NIOSH/DPSE.

TABLE 1. PHYSICAL PROPERTIES [6].
Vapor Presssure 25 °C
Compound BP (°C) MP (°C) Density @ 20 °C (Pa) (mm Hg) NIOSH REL*
o-cresol 190.95 30.9 1.047g/mL 33 0.25 2.3 ppm

m-cresol 202.2 12.0 1.034 20 0.15 2.3 ppm
g-cresol 201.9 35.3 1.034 15 0.11 2.3 ppm
phenol 182.0 41.0 1.071 (25 °C) 47 0.35 5 ppm;
C 15.6 ppm/15 min
(skin)
* OSHA PEL and ACGIH TLV are 5 ppm (skin) for all the above compounds.
1 ppm = 4.42 mg/m3 @ NTP for the cresols; 1 ppm = 3.85 mg/m3 @ NTP for phenol.

CROTONALDEHYDE 3516
CH,CH = CHCHO MW: 70.09 CAS: 4170-30-3 RTECS: GP9499000
OSHA : 2 ppm PROPERTIES: liquid; pungent odor; BP 104 °C;

NIOSH: 2 ppm d 0.85 g/mL @ 20 °C; VP 2.7 kPa
ACGIH: 2 ppm; suspect carcinogen (20 mm Hg, 2.6% v/v) @ 20 °C; explosive
(1 ppm = 2.87 mg/m3 @ NTP) range 2.1 to 15.5% v/v in air
SYNONYMS: crotonic aldehyde; trans-2-butenal, crotonal
SAMPLER: MIDGET BUBBLER TECHNIQUE: DIFFERENTIAL PULSE POLAROGRAPHY

(hydroxylamine/formate buffer solution)
ANALYTE: crotonaldehyde oxime
DROP TIME: 1 s
-MAX: 49 L SCAN RATE: 5 mV/s
SHIPMENT: refrigerate bubblers at 8 °C during shipment if SCAN RANGE: - 0.6 to - 1 .2 V (vs. SCE)
samples cannot be analyzed within 4 h
CALIBRATION: standard solutions of crotonaldehyde in
SAMPLE hydroxylamine/formate buffer solution
STABILITY: 4 h maximum @ 25 °C, 7 days minimum at
8 °C RANGE: 35 to 139 //g per sample
BLANKS: 2 to 10 field blanks per set ESTIMATED LOD: not determined
PRECISION (§,): 0.024 [1]
ACCURACY

(12-L samples)
BIAS: -2.8%
OVERALL PRECISION (S,T): 0.061 (2.9 to 11.6 mg/m3) [1]
ACCURACY: ±14.8%
APPLICABILITY: The working range is 1 to 10 ppm (2.9 to 29 mg/m3) for a 12-L air sample. The upper limit of the method
is dependent on the concentration of hydroxylamine, which should be maintained at 50-fold molar excess over total amount of
crotonaldehyde sampled. Collection efficiency outside the method range has not been evaluated.
INTERFERENCES: Other volatile aldehydes (e.g., acrolein, formaldehyde, benzaldehyde).
OTHER METHODS: This is Method P&CAM 285 [2] in a revised format. An aldehyde screening method [3] and a method for
priority pollutants [4], both of which include crotonaldehyde, have been described.

CROTONALDEHYDE: METHOD 3516, Issue 1, dated 15 August 1994 - Page 2 of 4
1. Hydroxylamine hydrochloride, reagent grade. 1. Glass midget bubblers.

2. Sodium hydroxide, 0.1 M, reagent grade. 2. Personal sampling pump, 0.1 to 0.2 L/min,
3. Formic acid, reagent grade. and trap with flexible tubing. Trap is a midget
4. Sodium formate, reagent grade. bubbler or impinger with stem broke off.
5. Hydroxylamine collection solution. Dissolve 3. Volumetric flasks, 1 -L, 500-mL, and convenient
0.68 g of hydroxylamine hydrochloride in 1 L sizes for preparing stock standard solutions.
deionized water. Adjust to pH 5 with 0.1 M 4. Pipets, 10-mL, 5-mL, and other convenient
sodium hydroxide. sizes.
6. Formic acid/sodium formate buffer. Add 3.4 5. Syringes for preparing spiked standard
g sodium formate and 2 mL formic acid to samples.
500-mL volumetric flask. Bring to volume with 6. Potentiostat with differential pulse
deionized water. polarographic capability.
7. Crotonaldehyde,* 85%. 7. China marker.
8. Crotonaldehyde stock solution. Prepare 8. PTFE tubing 15 cm x 7-mm ID or PTFE plugs
solutions containing 17.19 and 1.179 mg/mL for sealing the inlet and outlet of the bubbler
of crotonaldehyde in deionized water. stem before shipment.
9. Nitrogen, prepurified.
NOTE: Wash all glassware with detergent, rinse
with deionized water and dry. Midget
* See SPECIAL PRECAUTIONS. bubblers should be heated in an oxidizing
atmosphere at about 580 °C to remove
organic contaminants.
SPECIAL PRECAUTIONS: Crotonaldehyde is highly toxic, flammable liquid [5]. Prevent contact with
skin, eyes, and clothing. Do not breathe vapors; crotonaldehyde vapors irritate the mucous membranes,
nose and respiratory tract. Vapors can severely irritate the eyes, causing lacrimation. Contact with eyes
can cause corneal burns. Contact with skin causes irritation and may cause burns. Wash thoroughly
after handling.
SAMPLING:
1. Calibrate each personal sampling pump with a representative sampler and trap in line.
2. Rinse bubblers with 10 mL hydroxylamine solution. Pipet 10 mL of hydroxylamine solution
buffered at pH 5 into each midget bubbler. Mark the liquid level on the bubbler with a china
marker. Ensure that bubbler frit is covered.
3. Attach outlet of midget bubbler to inlet of trap used to protect pump during sampling. Attach
trap to pump with metal holder. Connect outlet of trap to pump by flexible tubing.
to 49 L
NOTE: Sampled air should not pass through any tubing containing polyvinylchloride (PVC)
before entering the bubbler; PVC tubing is known to give interferences in the method.
5. Discard any material collected by the trap. If more than 1 mL of material is collected in the trap,
the sample should be considered invalid.
6. Seal the inlet and outlet of the bubbler stem by connecting a piece of PTFE tubing between
them or by inserting PTFE plugs in the inlet and outlet. Pack securely for shipment. If samples
cannot be analyzed within four hours, they must be refrigerated at 8 °C during shipping and
until analysis time.
7. Collect a bulk sample (ca. 1 g) in a glass vial with a PTFE-lined cap and ship separately.

CROTONALDEHYDE: METHOD 3516, Issue 1. dated 15 August 1994 - Page 3 of 4
SAMPLE PREPARATION:
8. Remove bubbler stem and drain contents into bubbler flask. If necessary, bring to 10-mL mark
with distilled water. Add 5 ml_ formate buffer solution and swirl bubbler to mix contents well.
9. Prepare at least six working standards having concentrations to cover the range of 6 to 280 //g
per sample (corresponding to 0.1 to 4 times the OSHA standard).
a. Add appropriate aliquots (< 100 yL) of stock solution to 10 mL of hydroxylamine solution,
followed by addition of 5 mL of formate buffer solution.
b. Analyze with samples and blanks (step 11).
c. Prepare calibration graph of peak current vs. mass (/ug) of crotonaldehyde per 15 mL of
sample.
MEASUREMENT:
11. Transfer sample to electrochemical cell and purge with oxygen-free nitrogen for 3 min at 200
mL/min. Analyze by differential pulse polarography: 1 second drbp time, 5 mV/second scan
rate, and -0.6 V to -1.2 V scan range vs. a saturated calomel electrode (SCE). Analysis should
be conducted in a relatively stable temperature environment. Measure peak current due to
reduction of crotonaldehyde oxime. The half wave potential, E,/2, of crotonaldehyde oxime is
-1 .03 V vs. SCE. Rinse electrodes before analyzing next sample.
CALCULATIONS:
12. Determine the mass, //g, for each sample (W) and for the average media blank (B) from the
standard calibration graph.
13. Calculate concentration, C, of crotonaldehyde in the air volume sampled, V (L), applying a
correction for the collection efficiency, which was determined to be 96%:
C = (W-B) /ma
V • 0.96 a
The average concentrations obtained from analysis of samples collected from test atmospheres at 0.5X,
1X, 2X, and 4X the OSHA standard were 10.0% lower, 2.1% lower, 3.7% higher, and 3% higher,
respectively, than the "true" concentrations. The difference between the "found" and "true"
concentrations may not represent a bias in the sampling and analytical method, but rather a random
variation from the experimentally determined "true" concentration. Therefore, the method has no
uncorrected bias. Storage stability studies on samples collected in a test atmosphere at a concentration
of 5.80 mg/m3 indicated that collected samples are stable for at least 7 days at 8 °C. Collection
efficiency for the midget bubbler was determined to be 0.96 for an average of 24 samples and a
correction must be applied. Statistical information [6] and details of the test procedures [1] can be
found elsewhere.

CROTONALDEHYDE: METHOD 3516, Issue 1, dated 15 August 1994 - Page 4 of 4
REFERENCES:
[1] Backup Data Report for Crotonaldehyde, prepared under NIOSH Contract No. 210-76-0123.
[2] NIOSH Manual of Analytical Methods, 2nd ed., V. 5, P&CAM 285, U.S. Dept of Health, Education,
[3] Aldehydes Screening Method #2539, NIOSH Manual of Analytical Methods, 3rd Ed., Third
Supplement, May 15, 1989.
[4] Spingham, A. L GC/MS Analytical Method for Priority Pollutants Including Crotonaldehyde, J.
Chromatoar. Sci., 20(6). 286-288 (1982).
Human Services Publ. (NIOSH) 81-123 (1981), available as GPO Stock #17-033-00337-8 from
[6] Documentation of the NIOSH Validation Test, National Institute for Occupational Safety and Health,
Cincinnati, Ohio (DHEW-NIOSH-Publication #77-185), 1977. Available from Superintendent of
Documents, U.S. Government Printing Office, Washington, D.C., Order No. 017-033-00231-2.
METHOD REVISED BY:
M. Eileen Birch, Ph.D., NIOSH/DPSE; data obtained under NIOSH Contract 210-76-0123.

CUMENE
See HYDROCARBONS, AROMATIC (Method 1501) for procedure

CYANIDES, aerosol and gas 7904
HCN and salts MW: 27.03 (HCN); CAS: 74-90-8 (HCN); RTECS: MW6825000 (HCN);
65.11 (KCN) 151-50-8 (KCN) TS8750000 (KCN)

OSHA : 1 1 mg/m3; skin (HCN) PROPERTIES: HCN: gas, BP 26 °C; VP 620 mm Hg 20 °C;
5 mg/m3; skin (cyanides, as CNT) vapor density 0.94 (air = 1); KCN: solid,
NIOSH: C5 mg/m3/10 min (as CNT) d 1.52g/mL, MP 634 °C
ACGIH: C 11 mg/m3; skin (HCN);
5 mg/m3; skin (cyanides, as CN)
SYNONYMS: HCN: hydrocyanic acid, prussic acid, formonitrile, cyanides.
SAMPLER: FILTER + BUBBLER TECHNIQUE: ION-SPECIFIC ELECTRODE

(0.8-^m PVC membrane
+ 15mL0.1 NKOH) [1] ANALYTE: cyanide ion (CN~)
FLOW RATE: 0.5 to 1 L/min EXTRACT FILTER: 25 mL0.1 N KOH; 30 min
VOL-MIN: 10 L@ 0.5 mg/m3 (as CN~) RINSE

-MAX: 180 L@ 11 mg/m3 (as CN") BUBBLER: 2mL0.1 N KOH; dilute to 25 mL
with 0.1 N KOH
SHIPMENT: routine
MEASURE: mV reading of cyanide ion electrode
SAMPLE STABILITY: analyze within 5 days; vs. reference electrode
particulate on filter may
liberate HCN gas [2] CALIBRATION: solutions of KCN in 0.1 N KOH
BLANKS: 2 to 10 field blanks per set RANGE: 0.05 to 2 mg CN-
ESTIMATED LOO- 2.5 //g CN~ [2]
ACCURACY PRECISION (Sr): 0.043 (HCN) [3];

0.038 (KCN) [2]
RANGE STUDIED: 5 to 21 mg/m3 (HCN) [3];
2.6 to 10 mg/m3 (KCN) [2]
BIAS: - 7.6%
OVERALL PRECISION (SrT): 0.062 (HCN) [3];
0.103 (KCN) [2]
ACCURACY: ± 20.0%
APPLICABILITY: The working range (as CN") is 0.5 to 15 mg/m3 for a90-Lair sample or 5 to 20 mg/m3 for a 10-Lair sample.
INTERFERENCES: Sulfide, chloride, iodide, bromide, cadmium, zinc, silver, nickel, cuprous iron and mercury interfere. In
humid atmospheres, some particulate cyanide collected on the filter will liberate hydrogen cyanide which will be trapped in the
bubbler [2]. The method cannot distinguish between HCN formed in this manner and HCN originally present in air.
OTHER METHODS: This method combines and replaces Methods S288 [4], S250 [5], and P&CAM 116 [6]. Method 6010
(Hydrogen Cyanide) uses a soda lime tube as sampler, with colorimetric measurement.

CYANIDES, aerosol and gas: METHOD 7904, Issue 2, dated 15 August 1994 - Page 2 of 4
1. Deionized water. 1. Sampler: polyvinyl chloride membrane filter,

2. Potassium cyanide.* 37-mm diameter, 0.8-//m pore size in 2-piece
3. Calibration stock solution, 1000 fjg/mL CN~. filter cassette holder, followed by a glass
Dissolve 0.250 g KCN in 0.1 N KOH to make midget bubbler containing 15 mL 0.1 N KOH.
100 ml solution. Stable for at least 1 week in 2. Personal sampling pump, 0.5 to 1 L/min, with
polyethylene bottle. splashover protection and flexible connecting
4. Potassium hydroxide (KOH), 0.1 N. Dissolve tubing.
5.6 g KOH in deionized water; dilute to 1000 3. Vials, polyethylene, with screw caps, 20-mL,
ml_. and plastic tape for sealing.
5. Lead acetate paper. 4. Cyanide ion electrode, (Orion 94-06 or
6. Cadmium carbonate (if sulfide present). equivalent).
7. Hydrogen peroxide, 30% (if sulfide present). 5. Reference electrode.
8. Sodium sulfite, 1 M (if sulfide present). 6. pH meter, readable to 0.1 mV.
7. Magnetic stirrer and stirring bars.
8. Jars, ointment, 60-mL, squat-form with
See SPECIAL PRECAUTIONS. aluminum-lined screw caps.
9. Pipets, 0.05- to 2 and 25-mL, with pipet bulb.
11. Beakers, 50-mL
12. Analytical balance, readable to 0.1 mg.
SPECIAL PRECAUTIONS: Hydrogen cyanide gas and the cyanide participates may be fatal if
swallowed, inhaled or absorbed through the skin. Work in a hood.
Amyl nitrite is the antidote for cyanide poisoning [7].
SAMPLING:

2. Sample at 0.5 to 1 L/min for a total sample size of 10 to 180 L
NOTE: Maintain bubblers in a vertical position during sampling. Do not allow the solution level
to fall below 10 mL
3. Remove the bubbler stem and tap it gently against the inside wall of the bubbler. Rinse the
bubbler stem with 1 to 2 mL of unused 0.1 N KOH. Add the rinse to the bubbler.
4. Quantitatively transfer the contents of the bubbler to a 20-mL vial. CIose cap tightly and wrap
with plastic tape to avoid sample loss during transit. Label each vial.
SAMPLE PREPARATION:
5. Transfer the filter from the cassette filter holder to a 60-mL ointment jar.
6. Pipet 25.0 mL 0.1 N KOH into the jar. Cap and allow to stand for at least 30 min with
occasional shaking to complete extraction. Analyze within 2 h after extraction.
7. Empty the contents of the vial into a 25-mL volumetric flask using 0.1 N KOH to rinse the vial.
Add rinse to the volumetric flask. Dilute to the mark with 0.1 N KOH.
NOTE: Sulfide ion irreversibly poisons the cyanide ion specific electrode and must be removed
if present. Check for the presence of sulfide ion by touching a drop of sample to a
piece of lead acetate paper; the paper will discolor in the presence of sulfide ion. If this
test is positive, remove sulfide by one of the following methods:
a. Add 1 mL 1 M H2O2 and 1 mL 1 M Na2SO3 to sample solutions prior to diluting to volume.

b. Add a small amount (spatula tip) of powdered cadmium carbonate to the sample. Swirl to
disperse the solid and recheck the liquid with lead acetate paper. If sulfide ion has not been
removed completely, add more cadmium carbonate. Avoid a large excess of cadmium
carbonate and long contact time with the solution. When a drop of liquid no longer
discolors a strip of lead acetate paper, filter the sample through a small plug of glass wool in
a Pasteur pipette and proceed with the analysis.
8. Prepare at least six working standards fresh daily to cover the range 50 to 2000 //g CN" per
sample by diluting aliquots of 1000 /yg/mL calibration stock solution with 0.1 N KOH (e.g., 0.05
to 2.0 mL calibration stock solution diluted to 25 mL).
9. Analyze the working standards according to steps 11 and 12 together with the samples and
blanks.
10. Prepare a calibration graph on semilog paper by plotting cyanide ion concentration on the
logarithmic axis and mV on the linear axis.
MEASUREMENT:
11. Transfer the solution to be measured to a 50-mL beaker. Immerse the cyanide ion electrode
and reference electrode in the sample and start the magnetic stirrer.
12. With the magnetic stirrer on, allow the potential reading to stabilize. Record the mV reading.
NOTE 1: Potential readings are a function of temperature. Measure samples and working
standards at the same temperature (± 2 °C).
NOTE 2: The cyanide electrode will malfunction if chloride, iodide and bromide ions, which form
insoluble silver salts, are present in sufficient quantity. Several metal ions are also
known to complex with cyanide such as cadmium, zinc, silver, nickel, cuprous iron and
mercury. Consult the electrode instruction manual for the procedure to use when such
ions are present.
CALCULATIONS:
13. Read the mass, //g, of cyanide ion present in the sample filter (Wf), sample bubbler (Wb),
average media blank filter (Bf) and media blank bubblers (Bb) from the calibration graph.
14. Calculate the concentration (mg/m3) of particulate cyanide, Cp, and hydrogen cyanide, CHCN, in
the air volume sampled, V (L):
Cp . "LI*. mg/m3 CHCN . (".-V"*
where 1 .04 is the stoichiometric conversion factor from CN" to HCN.

NOTE: Particulate cyanides will be collected on the filter. In humid atmospheres, however, it
has been observed that during the collection of particulate cyanide, HCN is gradually
liberated [2]; therefore, particulate cyanide interference is not completely removed.
HCN: Method S288 was issued on September 2, 1977 [4]. Test atmospheres of HCN were generated
by calibrated flow from a compressed mixture of HCN in nitrogen [3,8]. The range of HCN
concentrations in air was 5 to 21 mg/m3 for 12-L air samples. Eighteen HCN samples collected at 0.2
L/min for 60 min indicated overall precision of 6.2%, with a 96.7% recovery. An eight-day storage

stability study involving six samples at the OSHA standard concentration level indicated a 92.4% average
recovery for the one-day old samples and a 92.6% for eight-day old samples. A collection efficiency
study at twice the OSHA standard level, which included backup bubblers, indicated that an average of
99.8% of HCN was collected in the first bubbler. The HCN air generated concentrations were
independently confirmed by a titration method [3].
KCN: Method S250 was issued on January 30, 1976 [5]. A set of six weighed KCN samples in the
range of 1.8 to 2.5 mg KCN per filter indicated a 97% recovery and a 3.8% measurement precision [2].
Spiking with aqueous or basic solutions of KCN proved unsuccessful (low recovery) because of the
cyanide instability in the presence of water and CO2. Test atmospheres of KCN were generated by
atomization of an aqueous solution (162 g/L) of KCN into a dry airstream. Eighteen KCN samples
collected in 0.1 N NaOH at 1.5 L/min for 60 min indicated overall precision, SrT, of 0.103. Collection was
accomplished with cellulose ester membrane filters followed with backup bubblers. The collection
efficiency at twice the OSHA level was 100.0% on the filters. Cyanide salts are known to decompose in
moist air with liberation of HCN. This instability was determined with two sets of six samples at the one
and two times the OSHA level. Each of the samples which were twice the OSHA level were connected
with two backup bubblers. Both sets indicated a loss of 16.5%.
REFERENCES:
[1] Perkins, J.B., D.G. Tharr, J. Palassis, D.B. Fannin, and P.M. Eller, Case Studies: Reduction of Blank
Values in the Determination of Particulate Cyanides. Appl. Occup. Environ. Hyg. 5:836-837 (1990).
[3] Backup Data Report for Hydrogen Cyanide, S288, available as "Ten NIOSH Analytical Methods, Set
5," Order No. BP 287-499 from NTIS, Springfield, VA 22161.
[5] Ibid, V. 3, S250, U.S. Department of Health, Education, and Welfare, Publ. (NIOSH) 77-1 57-C (1977).
[6] Ibid, V. 1, P&CAM 116, U.S. Department of Health, Education, and Welfare, Publ. (NIOSH) 77-1 57-A
(1977).
[7] Criteria for a Recommended Standard. ..Occupational Exposure to Hydrogen Cyanide and Cyanide
Salts, 5-9, U.S. Department of Health, Education, and Welfare, Publ. (NIOSH) 77-108 (1976).
(1980).
METHOD REVISED BY:
J. Palassis, NIOSH/DTMD; S250 and S288 originally validated under NIOSH Contracts CDC-99-74-45
and 210-76-0123, respectively.

CYANURIC ACID 5030
C3N3(OH3) MW: 129.08 CAS: 108-80-5 RTECS: X21 800000

OSHA : no standard PROPERTIES: solid; d 2.50 g/mL @ 20 °C;

NIOSH: no recommended exposure limit MP >330 °C; (decomposes to cyanic
ACGIH: no TLV acid); VP not significant
SYNONYMS: 2,4,6-trihydroxy-1,3,5-triazine; isocyanuric acid; 1,3,5-triazine-2,4,6(1H,3H,5H)trione.
SAMPLER: Filter TECHNIQUE: HPLC, UV DETECTION

(5-fjm PVC membrane)
ANALYTE: cyanuric acid
EXTRACTION: 3 mL 0.005 M Na2HPO4, 5:95 (v:v)
VOL-MIN: 10 L @ 0.1 mg/m3 methanol:water (pH = 7.0), 10 min
-MAX: 1000 L ultrasonic
SHIPMENT: routine INJECTION VOLUME: 15 fjL
SAMPLE MOBILE PHASE: 0.005 M Na2HP04, 5:95 (v:v)

STABILITY: > 69 days at 25 °C [1] methanol:water (pH = 7.0)
FIELD BLANKS: 2 to 10 field blanks per set COLUMN: //-Bondapak C18, I0-//m particle, size;
Radial PAK cartridge, 11 cm x 8-mm ID
ACCURACY CALIBRATION: standard solutions of cyanuric acid in

mobile phase
PRECISION (Sr): 0.020 @ 12 to 412//g per sample [1]
INTERFERENCES: Trichloroisocyanuric acid interferes because it reacts with water (which is present in the eluent used for
recovery) to form cyanuric acid.
OTHER METHODS: None identified for air analysis. HPLC method for measurement in solution is a variation of the method
of Briggle et a]. [2].

CYANURIC ACID: METHOD 5030, Issue 2, dated 15 August 1994 - Page 2 of 4
1. Cyanuric acid, >98% pure.* 1. Sampler: 37-mm, 5-//m polyvinyl chloride

2. Water, distilled. (PVC) membrane filter in 2-piece cassette filter
3. Methanol, chromatographic quality.* holder.
4. Na2HPO4-7H2O, reagent grade. 2. Personal sampling pump, 1 to 3 L/min, with
5. HCI, 1 M (aqueous). flexible connecting tubing.
6. Eluent and mobile phase: 0.005 M 3. High performance liquid chromatograph
Na2HPO4, 5:95 (v:v) methanol :water (HPLC), UV absorption detector, 225 nm,
at pH = 7.0. Dissolve 5.36 g of recorder, intergrator and column (page
Na2HPO4 • 7H2O in 2000 ml_ water. Add 5030-1).
200 mL methanol. Add water until total 4. Vials, 4-mL, with PTFE-lined caps.
volume is 3990 mL. Add 1 M HCI until 5. Volumetric flasks, 25-mL
pH is 7.0. 6. Carboy, 4-L
7. Calibration stock solution, 1 mg/mL Dissolve 7. Graduated cylinders, 1-L, readable to 10-mL,
25 mg cyanuric acid in eluent to make 25 mL 250-mL, readable to 2 mL
solution. Prepare fresh monthly. 8. Syringes, 500-//L, readable to 10 fjL; 100-//L,
NOTE: Ultrasonic bath will facilitate readable to 1 juL; 10-jyL, readable to 0.1 //L
dissolution of cyanuric acid. 9. Beakers, 50-mL, internal diameter >37 mm.
8. Recovery stock solution, 1 .7 fJQ/fJ\_. Dissolve 10. Ultrasonic water bath.
42.5 mg cyanuric acid in water to make 25 mL 1 1 . Film, plastic, flexible, water-resistant.
solution. 12. Filter units, 25-mm PTFE membrane, 0.45-^m
NOTE: Ultrasonic bath will facilitate pore size, in polypropylene housing.
dissolution of cyanuric acid. 13. Vacuum oven.
14. Tweezers.
15. pH meter.
* See SPECIAL PRECAUTIONS. 16 Adhesive tape.
SPECIAL PRECAUTIONS: Cyanuric acid is a possible tumorigenic agent and a slight eye irritant [3,4].
Methanol is toxic. Ingestion of methanol may cause blindness or death. Methanol is a fire hazard (flash
point 12 °C).
SAMPLING:

2. Attach sampler to personal sampling pump with flexible tubing.
1000 L Limit the maximum loading of particulate matter on the filter to about 1 mg.
4. Seal the ends of the sampler with plugs. Pack securely for shipment.
SAMPLE PREPARATION:
5. Place the PVC filter face down into a 50-mL beaker (the filter should lie flat on the bottom of the
beaker). Retain the cassette filter holder (step 9).
6. Add 3 mL eluent to the beaker. Seal the mouth of the beaker with plastic film.
NOTE: The volume of 3 mL is sufficient when the quantity of cyanuric acid on the filter is 1 mg
or less. The limit of solubility of cyanuric acid in eluent is about 2 mg/mL at room
temperature.
7. Place the beaker into an ultrasonic bath for 10 min.

8. Filter the solution.

9. If cyanuric acid is found on the PVC filter (steps 13 and 14), prepare additional sample solution
by treatment of the interior surface of the front piece of the cassette filter holder with eluent.
NOTE: The quantity of cyanuric acid collected on the interior surface of the front piece of the
cassette filter holder may be significant (see EVALUATION OF METHOD).
a. Use adhesive tape to secure in place the plug in the inlet of the front piece of the cassette
filter holder.
b. Add eluent (ca. 6 mL) to the front piece until about 95% of the interior surface is in contact
with eluent.
c. Place the front piece into an ultrasonic bath for 5 min.
d. Transfer the solution from the front piece to a beaker, seal the mouth of the beaker with
plastic film, and place the beaker into an ultrasonic water bath for 10 min.
NOTE: Solid particles may be present in the solution after the first 5 min of ultrasonic
agitation. Transfer of the solution to a beaker helps protect the solution from
contamination.
10. Calibrate daily with at least six working standards over the range 0.1 to 250 mg cyanuric acid
per mL of solution.
a. Prepare a series of working standards in vials from calibration stock solution and eluent by
serial dilution.
NOTE: Working standards may be stored at -3 °C for at least 18 days without deterioration.
c. Prepare calibration graph (peak area or height vs. //g of cyanuric acid).
11. Determine recovery (R) at least once for each lot of PVC membrane filters used for sampling in
the calibration range (step 10). Prepare three filters at each of five levels plus three media
blanks.
a. Place an aliquot of recovery stock solution onto a PVC filter which is situated in the back
piece of a cassette filter holder. If the volume of the aliquot is greater than 15 fjL, transfer
the aliquot to the filter in portions which are about 15 //L in size.
NOTE: Portions of stock solution will appear as beads on the filter. A maximum of about
sixteen 15-//L portions of solution can be distributed on the filter. Thus, a maximum of
about 400 mg of cyanuric acid can be applied to the filter with the recovery stock
solution. A recovery stock solution which has a much higher concentration of cyanuric
acid in water at room temperature can not be prepared because the limit of solubility of
cyanuric acid in water at room temperature is about 2.5 mg/mL If higher loadings are
needed, allow the first portions to dry and repeat the process.
b. Join the front piece of the cassette filter holder with the back piece. Remove the plug from
the inlet.
c. Carefully transfer the filter holder to a vacuum oven.
d. Dry the filter at about 65 °C and 40 kPa (300 mm Hg). Filter will be dry in ca. 0.3 to 4.5 h.
e. Prepare sample (steps 5 through 8) and analyze with working standards (steps 13 and 14).
f. Prepare a graph of R vs. //g cyanuric acid recovered.
MEASUREMENT:
13. Set liquid chromatograph to manufacturer's recommendations and to conditions given on page
5030-1. Inject sample aliquot manually or with autosampler.
NOTE: If peak area is above the range of the working standards, dilute with eluent, reanalyze,
and apply the appropriate dilution factor in calculations.

CALCULATIONS:
15. Determine the mass, //g (corrected for R), of cyanuric acid found on the filter (W() and on the
average media blank (Bf).
16. Determine the mass, //g, of cyanuric acid found on the interior surface of the cassette filter
holder (Wc) and on the interior surface of a blank cassette filter holder (Bc).
17. Calculate concentration, C, of cyanuric acid in the air volume sampled, V (L):
c - W»*.-*-M mg/m,
Average recoveries after fortification of 37-mm PVC membrane filters with 12-, 36-, and 412-//g
quantities of cyanuric acid were 0.98, 1.00, and 1.00, respectively; precision (Sr) was 0.020 (16 samples,
pooled). The average recovery of 36-fjg quantities of cyanuric acid from PVC filters after 22 days of
storage at room temperature was 1.08; Srwas 0.065 (5 samples). Recovery of 1.08 was not significantly
different from 1.00 at the 95% confidence level. Recoveries of 10-, 80-, 200-, and 400-//g quantities of
cyanuric acid were 0.88, 1 .04, 0.98 and 0.98, respectively, after storage of fortified PVC filters for 69 days
at room temperature (one sample at each level). This method was not evaluated with controlled
atmospheres in a laboratory. However, the method was employed for measurement of cyanuric acid in
air at a plant in which trichloroisocyanuric acid was manufactured from cyanuric acid [1,5]. Significant
quantities (ca. 40% of the totals) of cyanuric acid were found on interior surfaces of the front pieces of
cassette filter holders.
Working standards of cyanuric acid at concentrations near 1 fjg/mL in eluent deteriorated in about 3
weeks during storage at room temperature; standards were stable for at least 18 days during storage at
- 3 °C. Deterioration of a C18 analytical column took place and caused the LOD of cyanuric acid to
increase from 0.1 to 0.25 //g/mL during 6 weeks.
Trichloroisocyanuric acid is an interference because it reacts with water (present in the eluent) to form
cyanuric acid. Average yields of cyanuric acid after treatment of 8.4-, 64-, and 424-//g quantities of
trichloroisocyanuric acid with eluent in glass vials were 74%, 89%, and 93%, respectively.
REFERENCES:
[1] Tucker, S.P., and LM. Blade. Anal. Lett. 25 (12), 2265-2277 (1992).
[2] Briggle, T. V., L M. Allen, R. C. Duncan, and C. D. Pfaffenberger. J. Assoc. Off. Anal. Chem.. 64 (5),
1222-1226 (1981).
[3] Canelli, E. Amer. J. Pub. Health. 64 (2), 155-162 (1974).
[4] Hammond, B. G., S. J. Barbee, T. Inoue, N. Ishida, G. J. Levinskas, M. W. Stevens, A. G. Wheeler
and T. Cascieri. Environ. Health Perspect.. 69, 287-292 (1986).
[5] Tucker, S. Analytical Report for DPSE/MRSB Analytical Sequence #6426, NIOSH, Unpubl. (1989).
METHOD WRITTEN BY:
Samuel P. Tucker, Ph.D., NIOSH/DPSE.

CYCLOHEXANE
See HYDROCARBONS, BP 36 to 126 °C (Method 1500) for procedure

CYCLOHEXANOL

CYCLOHEXANONE

CYCLOHEXENE
See HYDROCARBONS, BP 36 to 126 °C (Method 1500) for procedure

1 ,3-CYCLOPENTADIENE 2523
C5H6 MW: 66.10 CAS: 542-92-7 RTECS: GY1 000000


NIOSH: 75 ppm BP42°C;MP -85 °C; dimerizesto solid
ACGIH: TWA 75 ppm (MP 32.5 °C); VP not available
(1 ppm = 2.70 mg/m3 @ NTP)
SYNONYMS: none

(maleic anhydride on Chromosorb 104,
100 mg/50 mg) ANALYTE: 1 ,3-cyclopentadiene-maleic anhydride
adduct (see REAGENTS, 1.)
DISSOLUTION: 10 mL ethyl acetate; stand 15 min
-MAX: 5 L INJECTION VOLUME: 5fA.

-DETECTOR: 250 °C
STABILITY: at least 1 week @ 25 °C [1]
COLUMN: 3 m x 3-mm OD stainless steel packed
with 5% 0V- 17 on 100/120 mesh
Chromosorb WHP
ACCURACY
CALIBRATION: analyte in ethyl acetate
RANGE STUDIED: 73 to 370 mg/m3 [1 ]
(3-L samples) RANGE: 0.2 to 1.2 mg 1,3-cyclopentadiene per
sample
BIAS: 3.6%
OVERALL PRECISION (SrT): 0.066 [2] ESTIMATED LOD: 0.01 mg per sample [1]
ACCURACY: ± 16.5%
PRECISION (Sr): 0.031 @ 0.3 to 1.2 mg per sample [1]
APPLICABILITY: The working range is 25 to 150 ppm (67 to 400 mg/m3) for a 3-L air sample, based on sampler capacity at
high relative humidity.
OTHER METHODS: This revises P&CAM 294 [2].

1,3-CYCLOPENTADIENE: METHOD 2523, Issue 2, dated 15 August 1994 - Page 2 of 4
1. Analyte: 5-norbornene-2,3-dicarboxylic 1. Sampler: glass tube, 8.5 cm long, 6-mm OD,

anhydride (Eastman Chemicals). 4-mm ID, with plastic caps, containing two
NOTE: This is the Diels-Alder adduct formed sections of coated sorbent (front = 100 mg;
by reaction of 1,3-cyclopentadiene back = 50 mg), held in place and separated
and maleic anhydride.* Both endo- with glass wool plugs. Prior to packing, rinse
and exo- forms are present. the empty tube with acetone and dry to
2. Calibration stock solution, 50 mg/mL eliminate static adhesion of sorbent onto the
Dissolve 500 mg analyte in ethyl acetate* to tube wall. Pressure drop across sampler <2.5
make 10 ml_ solution. kPa (25 cm water) at 0.05 L/min airflow.
3. Acetone.* NOTE: See APPENDIX for preparation of
4. Ethyl acetate.* coated sorbent. Use the coated
5. Maleic anhydride.* sorbent within 20 days of preparation.
6. Sorbent: acrylonitrile-divinyl benzene Tubes available by special order
copolymer, 60/80 mesh, with surface area (SKC, Inc.).
100 to 200 m2/g (Chromosorb 104, 2. Personal sampling pump, 0.01 to 0.05 L/min,
Johns-Manville). with flexible connecting tubing.
7. Nitrogen, purified. 3. Gas chromatograph with FID, integrator, and
8. Hydrogen, prepurified. column (page 2523-1).
9. Air, filtered. 4. Vials, 20-mL, with PTFE-lined caps.
5. Flask, round-bottom, 250-mL
* See SPECIAL PRECAUTIONS. 6. Rotary evaporator.
7. Vacuum oven.
8. Syringes, 10-//L, readable to 0.1 fjL.
9. Pipet, volumetric, 10-mL, with pipet bulb.
SPECIAL PRECAUTIONS: Maleic anhydride is a powerful irritant and can cause burns and pulmonary
edema. Avoid exposure to concentrated vapor. Avoid contact with skin, eyes and clothing.
Acetone and ethyl acetate are serious fire risks.
SAMPLING:

2. Uncap the ends of the sampler immediately before sampling. Attach sampler to personal
1 to 5 L
SAMPLE PREPARATION:
glass wool plugs.
6. Add 10.0 mL ethyl acetate to each vial. Attach cap to each vial.

1,3-CYCLOPENTADIENE: METHOD 2523, Issue 2, dated 15 August 1994 - Page 3 of 4
8. Calibrate daily with at least six working standards over the range 0.01 to 1 .2 mg
1,3-cyclopentadiene (0.03 to 3 mg analyte) per sample.
a. Add known amounts of calibration stock solution, or a dilution thereof, to ethyl acetate in
10-mL volumetric flasks and dilute to the mark.
c. Prepare calibration graph (peak area vs. mg analyte).
9. Determine recovery at least once for each lot of coated sorbent used for sampling in the
calibration range (step 8). Prepare three tubes at each of five levels plus three media blanks.
b. Inject a known amount (1 to 20 //L) of calibration stock solution, or a dilution thereof,
d. Prepare (steps 5 through 7) and analyze together with working standards (steps 11 and 12).
e. Prepare a graph of recovery vs. mg analyte recovered.
MEASUREMENT:
autosampler. tr = 6.5 min under these conditions.
NOTE: If peak area is above the linear range of the working standards, dilute with ethyl acetate,
CALCULATIONS:
13. Determine the mass, mg (corrected for recovery) of analyte found in the sample front (Wf) and
sections.
14. Calculate concentration, C, of 1,3-cyclopentadiene in the air volume sampled, V (L) applying the
factor 0.403 (MW of 1 ,3-cyclopentadiene/MW of analyte) for conversion of adduct to 1,3-
cyclopentadiene:
c . W-W.-B.-EU- Q.4Q3. 10- _ mg/m3
P&CAM 294 [2] was issued in 1978 and evaluated over the range 73.4 to 370 mg/m3 [1,3]. The average
recovery for 3-L air samples was 1 .036 which represents a non-significant bias. Test atmospheres were
generated using a syringe pump delivering 3a,4,7,7a-tetrahydro-4,7-methano-1H-indene
(dicyclopentadiene) to a glass pyrolysis tube which thermally decomposed (375 °C) the dimer to
monomer. The concentrations of 1,3-cyclopentadiene were confirmed by collecting samples from the
generator in bubblers containing 15 mL solution of 74 mg/mL maleic anhydride in ethyl acetate and
analysis by GC/FID. Samples were stored at room temperature for one week and found to be stable.
Recovery averaged 0.99 in the range 0.75 to 3 mg analyte (equivalent to 0.3 to 1.2 mg
1,3-cyclopentadiene) per sample. Breakthrough capacity exceeded 3.8 mg 1,3-cyclopentadiene when

1.3-CYCLOPENTADIENE: METHOD 2523, Issue 2, dated 15 August 1994 - Page 4 of 4
sampling with freshly prepared (four-day old) coated sorbent and was 1 .6 mg with the same batch of
coated sorbent 24 days after preparation under similar sampling conditions (360 mg/m3, 0.045 L/min,
>80% RH).
REFERENCES:
[1] Backup Data Report, P&CAM 294 (NIOSH, unpublished, October 13, 1978).
(1980).
[4] Failure Report, S83 (NIOSH, unpublished, April 14, 1978).
METHOD REVISED BY:
Ardith Grote, NIOSH/DPSE; P&CAM 294 originally developed under NIOSH Contract 210-76-0123.
APPENDIX:
PREPARATION OF COATED SORBENT

1 . Add 25 g of sorbent to a 250-mL round-bottom flask.
NOTE: This will make enough coated sorbent to pack about 150 tubes.
2. Add 100 mL acetone, swirl, and allow sorbent to settle. Decant the acetone. Repeat twice.
NOTE: This removes the fines and washes the sorbent.
3. Remove the remaining solvent in a rotary evaporator. Dry in a vacuum oven at 30 °C for 1 h.
4. Weigh the dry sorbent and place it in a 250-mL round-bottom flask.
5. Weigh an amount of maleic anhydride equivalent to 20% of the weight of the sorbent and dissolve it
in 50 mL acetone.
6. Add the maleic anhydride solution to the sorbent, swirl, and remove the solvent in a rotary
evaporator. Dry in a vacuum oven at 30 °C for 15 min. Use the coated sorbent within 20 days of
preparation.
NOTE: Refrigeration in a sealed container may prolong shelf life [1,4].

2,4-D 5001
MW: 221.04 CAS: 94-75-7 RTECS: AG6825000

OSHA: 10mg/m3 PROPERTIES: solid; MP 138 °C; VP not significant

NIOSH: 10 mg/m3
ACGIH: 10 mg/m3
SYNONYMS: 2,4-D: (2,4-dichlorophenoxy)acetic acid; hedonal; Trinoxol

(glass fiber, binderless)
ANALYTE: 2,4-D anion
DESORPTION: 15 mL CH3OH; stand 30 min
VOL-MIN: 15 L@ 10 mg/m3
VOLUME: 50 //L
SHIPMENT: routine
ELUENT: 0.001 M NaCI04-0.001 M Na2B407
SAMPLE
STABILITY: at least 1 week @ 25 °C FLOW RATE: 1 .7 mL/min
BLANKS: 2 to 10 field blanks per set DETECTOR: UV @ 284 nm
COLUMN: stainless steel, 50 cm x 2-mm ID, packed

with Zipax SAX (DuPont) ambient
temperature; 6900 kPa (1000 psi)
ACCURACY
CALIBRATION: solutions of analyte in methanol
RANGE STUDIED: 5 to 20 mg/m3 [1,2]
(100-L samples) RANGE: 0.15 to 2 mg per filter
BIAS: - 1.26%
ESTIMATED LOD: 0.015 mg per filter [1]
OVERALL PRECISION (SrT): 0.051 (2,4-D) [1]
ACCURACY: ± 10.21%
APPLICABILITY: This method determines 2,4-D, 2,4,5-T, and their salts, but not their esters. The working range is 1.5 to 20
mg/m3 of either compound for a 100-L air sample.
INTERFERENCES: High concentrations of esters of either compound do not interfere but require the use of a pre-column to
prevent degradation of the HPLC column.
OTHER METHODS: This method combines and replaces Methods S279 [3] and S303 [3] which are the same except for eluent
composition and UV detector wavelength.

2,4-D AND 2,4,5-T: METHOD 5001, Issue 2, dated 15 August 1994 - Page 2 of 4
1. 2,4-dichlorophenoxyacetic acid.* 1 . Sampler: filter, glass fiber, binderless, in a

2. 2,4,5-trichlorophenoxyacetic acid.* 37-mm polystyrene two-piece cassette filter
3. Methanol, HPLC grade. holder (Gelman type AE or equivalent).
4. LC eluent: 2. Personal sampling pump, 1 to 3 L/min, with
a. 2,4-D: 0.001 N NaCIO4 and 0.001 N flexible connecting tubing.
Na2B4O7- Add 0.1 22 g NaCIO4 and 0.381 3. High pressure liquid chromatograph, UV
g Na2B4O7»10H2O to a 1-L volumetric detector at 284 nm (2,4-D) and 289 nm
flask. Bring to volume with distilled (2,4,5-T), integrator and column (page
water. Mix, filter and de-gas the 5001-1).
solution. 4. Filter, PTFE, 5-//m, 13-mm diameter in
b. 2,4,5-T: 0.003 M NaCIO4 and 0.001 M Swinny stainless (13-mm) filter holder.
Na2B4O7»10H2O. Add 0.366 g NaCIO4 5. Tweezers.
and 0.381 g Na2B4O7»10H2O to a 1-L 6. Syringes, 20-mL luer-lock.*
volumetric flask. Bring to volume with 7. Vials, glass, 20-mL*
distilled water. Mix, filter and de-gas the 8. Volumetric flasks, convenient sizes for
solution. preparing standard solutions.*
5. Compressed, filtered air or nitrogen for
drying syringes. * Wash all glassware with detergent,
6. Ethanol, absolute. thoroughly rinse with tap water and
7. Acetone. distilled water.
8. Calibration stock solution, 400 //g/mL
Dissolve 0.400 g 2,4-D or 2,4,5-T in methanol
and dilute to 1 L with methanol.
9. Recovery stock solution:
a. Dissolve 0.248 g 2,4-D in ethanol. Dilute
to 10 mL with ethanol.
b. Dissolve 0.250 g 2,4,5-T, triethylamine
salt, in acetone (or 0.250 g 2,4,5-T in
methanol).
Dilute to 10 mL with acetone.
NOTE: Use the same form (e.g., acid or
salt) of 2,4,5-T as in the air
sample. Recovery may vary with
the chemical form.
SPECIAL PRECAUTIONS: 2,4-D and 2,4,5-T are suspected animal carcinogens [4]. 2,3,7,8-Tetra-
chlorodibenzo-1,4-dioxin has been identified as an impurity in 2,4,5-T. Avoid any contact with these
substances.
SAMPLING:

200 L Do not exceed a total dust loading of 2 mg on the filter.
3. Obtain information on the chemical form of the analyte (i.e., ester, salt or free acid) likely to be
present in the air sample.

2,4-D AND 2,4,5-T: METHOD 5001. Issue 2, dated 15 August 1994 - Page 3 of 4
SAMPLE PREPARATION:
4. Remove the filter from the cassette with clean tweezers and place it in a 20-mL vial.
5. Add 15 mL methanol and mix by swirling. Allow to stand at least 30 min.
6. Filter the sample.
a. Pour the sample solution into a 20-mL syringe which is fitted with a 5-//m PTFE filter.
b. Filter the sample into a clean vial.
c. Clean the PTFE filter by backflushing with methanol. Rinse the syringe and plunger with
methanol. Dry with air or nitrogen.
7. Calibrate daily with at least five working standards.

a. Dilute aliquots of calibration stock solution to 10 mL with methanol in volumetric flasks.
b. Analyze working standards (steps 9 and 10).
c. Prepare calibration graph (peak area vs. mg 2,4-D or mg 2,4,5-T).
8. Check recovery with at least four spiked media blanks at each of four levels.
a. Add aliquot of recovery stock solution to media blank.
b. Analyze using standards prepared from the recovery stock solution.
c. Calculate R (mg recovered/mg added).
MEASUREMENT:
9. Establish chromatographic conditions listed on page 5001-1 for either 2,4-D or 2,4,5-T.
10. Inject 50 //L of sample in duplicate. Rinse and dry the syringe between samples.
NOTE 1 : The analyte is the chlorinated phenoxyacetate, whether the air sample contained salts
or free acid forms of 2,4-D and 2,4,5-T.
NOTE 2: Esters of 2,4-D and 2,4,5-T will not elute from the HPLC column and may, if present in
large amounts, degrade the HPLC column. Protect the main column with a precolumn
of Zipax SAX if esters are known to be present. The sample preparation conditions are
sufficiently mild so as to preclude hydrolysis of the esters.
CALCULATIONS:
11. Read the mass of analyte, mg (corrected for recovery), in the sample (W) and average media
blank (B) from the calibration curve.
12. Calculate the concentration, C (mg/m3), of 2,4-D or 2,4,5-T in air volume, V (L), taken:
C - - mg/m3.
Methods S279 (2,4-D) and S303 (2,4,5-T) were issued on February 17, 1978, and March 17, 1978,
respectively [3], and validated using 100-L air samples [1,2,5]. Atmospheres were generated using 2,4-D
dimethylamine salt for S279 and Weedar Amine BK (Amchem; equal parts of 2,4-D dimethylamine salt
and 2,4,5-T triethylamine salt) for S303. Overall precision and recovery for 100-L samples were as
shown, representing non-significant bias in each method:

2,4-D AND 2,4,5-T: METHOD 5001, Issue 2, dated 15 August 1994 - Page 4 of 4
Overall
Precision Ranae Studied Recovery 7-Dav Storaae Stability.
Method ma/m3 ma per sample &> 0.5 ma % of Day 1
S279 0.051 5 to 20 0.5 to 2 0.97 99
S303 0.053 5 to 21 0.5 to 2 0.86 to 0.99 104
REFERENCES:
[1] Backup Data Report S279 for 2,4-D prepared under NIOSH Contract No. 210-76-0123 (unpublished,
1976), available as Ten NIOSH Analytical Methods, Set 6," Order No. PB 288-629 from NTIS,
[2] Backup Data Report S303 for 2,4,5-T prepared under NIOSH Contract No. 210-76-0123
(unpublished, 1976), available as 'Ten NIOSH Analytical Methods, Set 6," Order No. PB 288-629 from
[3] NIOSH Manual of Analytical Methods, 2nd ed., V. 5, U.S. Department of Health, Education, and
[4] Criteria for a Recommended Standard... Occupational Exposure During Manufactur and Formulation
of Pesticides, U.S. Department of Health, Education, and Welfare, Publ. (NIOSH) 78-174
(1978).Welfare, Publ. (NIOSH) 79-141 (1979).
(1980).
METHOD REVISED BY:
Robert W. Kurimo, NIOSH/DPSE; originally validated under NIOSH Contract No. 210-76-0123.

DEMETON 5514
(C2H5O)2P(=S)O(CH2)2SC2H5 (1) MW: 258.34 CAS: 8065-48-3 RTECS: TF31 50000

(C2H50)2P( = 0)S(CH2)2SC2H5 (2)

OSHA : 0.1 mg/m3 (skin) PROPERTIES: liquid; d 1.18 g/mL @ 20 °C;

NIOSH: 0.1 mg/m3; Group I Pesticide BP 134 °C @ 270 kPa; MP -25 °C;
ACGIH: 0.01 ppm (0.11 mg/m3) (skin) VP 0.1 kPa (0.001 mm Hg; 1 ppm)
(1 ppm = 10.56 mg/m3 @ NTP) @33 °C
SYNONYMS: phosphorothioic acid 0,0-diethyl O-[2-(ethylthio)ethyl]ester (Demeton 0)mixture with 0,O-diethyl

S-[2-(ethylthio)ethyl]phosphorothioate (Demeton S); Systox; Bayer 8169; Demox; mercaptophos
SAMPLER: FILTER + SORBENT TUBE TECHNIQUE: GAS CHROMATOGRAPHY,

(2-fjm mixed cellulose ester PHOSPHORUS FPD
+ XAD-2, 150 mg/75 mg)
ANALYTE: (1) Demeton O and (2) Demeton S
DESORPTION: 5 mL toluene, 15 min
VOL-MIN: 30 L
VOLUME: 5//L
SHIPMENT: transfer filter and front sorbent section to
same vial TEMPERATURE-INJECTION: 200 °C
-DETECTOR: 210 °C
COLUMN: glass, 1.2 m x 3-mm OD; 1.5%
OV-17/1.95% OV-210 on 100/120 mesh
ACCURACY Chromosorb WHP
RANGE STUDIED: 0.03 to 0.1 9 mg/m3 [1] CALIBRATION: solutions of Demeton in toluene
(480-L samples)
BIAS: 0.49%
OVERALL PRECISION (S,T): 0.03 [1] ESTIMATED LOD: 0.1 fjg per sample [1]
ACCURACY: ± 13.9%
APPLICABILITY: The working range is 0.015 to 10 mg/m3 for a 200-L air sample. The use of a capillary column, e.g., a DB-210,
may improve sensitivity and resolution.

DEMETON: METHOD 5514, Issue 2, dated 15 August 1994 - Page 2 of 4
1. Demeton O/Demeton S mixture of known 1 Sampler: cellulose ester membrane filter,

concentration, reagent grade.* 0.8-fjm pore size, 37-mm diameter, supported
2. Toluene, reagent grade. by a stainless steel screen in a polystyrene
3. Methanol, reagent grade. cassette filter holder followed by a tube, 7 cm
4. Methylene chloride, reagent grade. long, 8-mm OD, 6-mm ID, packed with two
5. Calibration stock solution, ca. 2.4 mg/mL sections (front = 150 mg; back = 75 mg) of
Demeton O and 8.3 mg/mL Demeton S. 20/50 mesh XAD-2. Two plastic plugs are
Dilute 100 fjL of commercially available required for capping the tube after sampling.
mixture to 10 mL with toluene. Tubes are commercially available. (SKC, Inc.
6. Hydrogen, prepurified. 226-30-05, or equivalent).
7. Nitrogen, purified. 2. Personal sampling pump, 0.2 to 1 L/min, with
8. Oxygen, purified. flexible connecting tubing.
9. Air, purified. 3. Vial, scintillation, with PTFE-lined cap,
graduated at 15 mL
* See SPECIAL PRECAUTIONS. 4. Gas chromatograph with phosphorus-sensitive
FPD, integrator, and column (page 5514-1).
5. Syringes, 5-, 10- and 25-//L, for making
standard solutions and GC injections.
7. Pipets, 5-mL
8. Tweezers.
SPECIAL PRECAUTIONS: Demeton is a cholinesterase inhibitor and readily absorbed through the skin;
baseline and routine red blood cell cholinesterase monitoring is recommended [3,4].
SAMPLING:

2. Break ends of tubes immediately before sampling. Attach filter cassette to inlet of XAD-2 tube
with short piece of tubing. Connect the outlet of sampler to pump.
to 500 L
4. Transfer the filter, the front glass wool plug, and the front sorbent section to the same vial. Cap
the tube containing the back sorbent section.
5. Pack the samples securely for shipment.
SAMPLE PREPARATION:
6. Place the back sorbent section of the XAD-2 tube in a separate vial. Discard the remaining glass
wool plugs.
7. Add 5.0 mL toluene to each vial. Cap each vial.
8. Allow to stand 15 min with occasional agitation. Analyze within one day.

9. Calibrate daily with at least six working standards over the range 0.1 to 100 //g Demeton per
sample for each isomer.
a. Add known amounts of calibration stock solution to toluene in 10-mL volumetric flasks and
dilute to the mark.
c. Prepare calibration graph (peak area vs. //g of each isomer).
10. Determine desorption efficiency (DE) at least once for each lot of XAD-2 used for sampling in the
calibration range (step 9). Prepare three tubes at each of five levels plus three media blanks.
b. Inject a known amount (1 to 20 //L) of calibration stock solution, or a serial dilution thereof,
e. Prepare a graph of DE vs. //g of each Demeton isomer recovered.
MEASUREMENT:
autosampler. tr = 4 min for Demeton O and 7.5 min for Demeton S under these conditions.
NOTE: If peak area is above the linear range of the working standards, dilute with toluene,
CALCULATIONS:
14. Determine the mass, //g (corrected for DE) of Demeton (sum of Demeton O and Demeton S)
found on the sample filter plus front sorbent section (W + Wf), back (Wb) sorbent section, and
on the average media blank filter (B) and front (Bf) and back (Bb) media blank sorbent sections.
15. Calculate concentration, C, of Demeton in the air volume sampled, V (L):
C . C*»W.)»".-B-B,-^ mg/m°.
Method S280 for Demeton was issued on August 3, 1979 [2], and validated in the range 0.03 to 0.19
mg/m3 for 480-L samples [1,5]. The substance used to generate test atmospheres at 25 °C and 760
mm Hg in dry air was a 0.075% solution of Demeton (21% Demeton O, 74.5% Demeton S) in toluene
[1,5]. The atmosphere was generated by the aspirator method. Collection efficiencies and recovery
were 1 .00 for the isomers in the range 5 to 270 mg per sample. Sample filters extracted in toluene
immediately and stored one week at ambient conditions gave recoveries of 100%. Overall precision for
sampling plus measurement, SrT, was 0.08. No significant bias was found for either substance. No
breakthrough was observed after 12 hours of sampling at 1 L/min in atmospheres containing 0.14
mg/m3 Demeton O and 0.17 mg/m3 Demeton S at 80% RH.

REFERENCES:
[1] Backup Data Report, S280 (NIOSH, unpublished, August 3, 1979).

[2] NIOSH Manual of Analytical Methods, 2nd ed., Vol. 6, S280, U.S. Department of Health and Human
[3] NIOSH Criteria for a Recommended Standard. ..Occupational Exposure During the Manufacture and
Formulation of Pesticides, U.S. Department of Health, Education, and Welfare, Publ. (NIOSH) 78-174
(1978).
(1980).
METHOD REVISED BY:
Gangadhar Choudhary, Ph.D., CDC/ATSDR; S280 originally validated under NIOSH Contract
210-76-0123.

DIACETONE ALCOHOL

DIAZOMETHANE 2515
MW: 42.04 CAS: 334-88-3 RTECS: PA7000000

OSHA : 0.2 ppm PROPERTIES: yellow gas; MP -145 °C; BP -23 °C;
NIOSH: 0.2 ppm pure material explodes above 150 °C;
ACGIH: 0.2 ppm; suspect carcinogen impure material explodes at lower temp.
(1 ppm = 1.719 mg/m3 @ NTP)
SYNONYMS: azimethylene; diazirine

(octanoic acid-coated XAD-2 resin,
100 mg/50 mg) ANALYTE: methyl octanoate
FLOW RATE: 0.2 L/min DESORPTION: 1 mL carbon disulfide; stand 30 min
VOL-MIN: 6L INJECTION VOLUME: 5 fjL

-MAX: 30 L
-COLUMN: 95 °C
SAMPLE
STABILITY: not determined CARRIER GAS: N2, 30 mL/min
BLANKS: 2 to 10 field blanks per set COLUMN: stainless steel, 3 m x 3-mm OD, 5%
SP-1000 on 100/120 mesh Chromosorb
WHP preceded by a 15 cm x 3-mm OD
stainless steel precolumn packed with
ACCURACY 10% Carbowax 20M and 1.2% NaOH on
80/100 mesh Gas Chrom Q
(10-L samples) CALIBRATION: methyl octanoate in carbon disulfide with
internal standard
BIAS: -30% at 0.17 mg/m3 [1];
RANGE: 2 to 8 JJQ diazomethane (8 to 32 fjg
-10% at 0.36 to 0.75 mg/m3 [1]
methyl octanoate) per sample
OVERALL PRECISION (SrT): 0.084 [1] ESTIMATED LOD: not determined

ACCURACY: 22.5% at 0.36 to 0.75 mg/m3
APPLICABILITY: The working range is 0.1 to 0.6 ppm (0.2 to 1 mg/m3) diazomethane for a 10-L air sample.
INTERFERENCES: None reported.
OTHER METHODS: This revises S137 [2].

DIAZOMETHANE: METHOD 2515, Issue 2, dated 15 August 1994 - Page 2 of 4
1. Eluent: Carbon disulfide,* chromatographic 1 . Sampler: glass tube, 7 cm long, 6-mm OD, 4-
quality, with internal standard, tridecane (ca. mm ID.with plastic caps; two sections of
20 //g/mL). 20/50 mesh 1% octanoic acid-coated XAD-2
2. Methyl octanoate, reagent grade. resin preceded, separated and followed by
3. Octanoic acid-coated resin. Pack 20/50 mesh silylated glass wool plugs (front = 100 mg;
XAD-2 resin (Rohm & Haas Co.) into a column back = 50 mg). Tubes are commercially
(length to diameter ratio ca. 10:1). Wash with available (SKC, Inc. 226-23 or equivalent).
three bed volumes of methanol and two bed 2. Personal sampling pump, 0.2 L/min, with
volumes of pentane. Check the washings by flexible connecting tubing.
GC for interfering peaks. Dry at room 3. Gas chromatograph, FID, integrator and
temperature. Weigh out ca. 10 g washed and column (page 2515-1).
dried XAD-2 into a round-bottomed flask. Add 4. Vials, glass, 2-mL, PTFE-lined caps.
25 mL acetone to form a slurry. Add octanoic 5. Syringe, 10-//L, readable to 0.1 fjL.
acid equivalent to 1% of the sorbent weight. 6. Pipet, 1 .0-mL, with pipet bulb.
Evaporate the solvent in a rotary evaporator. 7. Volumetric flasks, 1 0-mL
Dry the coated resin at room temperature.
4. Hydrogen, prepurified.
5. Nitrogen, purified.
6. Air, filtered.
SPECIAL PRECAUTIONS: Carbon disulfide is toxic and a serious fire and explosion hazard (flash point
= -30 °C); all work with it must be done in a hood away from ignition sources.
Diazomethane is an explosive, insidious poison and a strong irritant which may cause delayed
hypersensitivity and cancer [3]. Concentrated solutions may explode violently, especially if impurities
are present. Rough surfaces, such as ground glass, may also cause explosions [4].
SAMPLING:

3. Sample at an accurately known flow rate of 0.2 ±0.03 L/min for a total sample size of 6 to 30 L
SAMPLE PREPARATION:
5. Place front and back sorbent sections of the sampler tube in separate vials. Discard the glass
wool plugs.
8. Calibrate daily with at least six working standards over the range 1 to 32 fjg methyl octanoate
per sample.

a. Add known amounts of methyl octanoate to eluent in 10-mL volumetric flasks and dilute to
the mark.
c. Prepare calibration graph (ratio of peak area of methyl octanoate to that of the internal
standard vs. //g methyl octanoate).
9. Determine desorption efficiency (DE) at least once for each lot of coated XAD-2 resin used for
sampling in the calibration range (step 8). Prepare three tubes at each of five levels plus three
media blanks.
b. Inject a known amount of methyl octanoate directly onto front sorbent section with a
microliter syringe.
e. Prepare a graph of DE vs. /yg methyl octanoate recovered.
MEASUREMENT:
autosampler.
same chromatogram.
CALCULATIONS:
13. Determine the mass, JJQ (corrected for DE) of methyl octanoate found in the sample front (Wf)
and back (Wb) sorbent sections, and in the average media blank front (Bf) and back (Bb)
sorbent sections.
14. Convert fjg methyl octanoate to //g diazomethane by multiplying the corrected //g per sample by
the conversion factor 0.2657 (molecular weight ratio, 42.04/158.24), and calculate apparent
concentration, Ca (mg/m3), of diazomethane in the air volume sampled, V (L):
C. . (W,^Wt-B,-Bt).Q.2657i
15. Calculate the recovery (R) from the equation:
R = 0.971 - ™327_
NOTE: This recovery was experimentally determined over the apparent concentration range 0.12 to
0.7 mg/m3 and may not be valid outside that range [1].
16. Calculate corrected concentration, C (mg/m3):
C = -, mg/m3.

Method S137 was issued on June 6, 1975 [2]. The precision and bias were determined by analyzing
generated atmospheres of diazomethane containing 0.17, 0.36 and 0.8 mg/m3 at 26 °C and 765 mm Hg
using 10-L samples [1]. The recovery (concentration found in air divided by concentration determined
by an independent method involving collection in solutions of benzoic acid in xylene) was found to
decrease with concentration according to the equation in step 15. Recoveries were 0.68 to 0.93 for six
pairs of data in the apparent concentration range 0.12 to 7 mg/m3. Sample stability was not
determined. The method does not meet the 10% bias criterion for a valid NIOSH method.
Breakthrough of the front section of the coated XAD-2 tube was not observed after sampling 53 L of dry
test atmosphere containing 0.83 mg/m3 for 240 min at 0.22 L/min. Desorption efficiencies for samples
spiked with methyl octanoate were 1.01 to 1.05. The collection efficiency and reaction of diazomethane
with the octanoic acid-coated resin may be strongly dependent on sample flow rates; therefore, all
samples must be collected at a flow rate of 0.2 L/min only.
REFERENCES:
[4] Merck Index, 10th ed., Merck & Co., Inc., NJ (1983).
METHOD REVISED BY:
Julie R. Okenfuss, NIOSH/DPSE; S137 originally evaluated under NIOSH Contract CDC-99-74-45.

DIBORANE 6006
B,H
2" '6 MW: 27.67 CAS: 19287-45-7 RTECS: HQ9275000

OSHA: 0.1 ppm PROPERTIES: gas; vapor density (air = 1) 0.96;

NIOSH: 0.1 ppm BP -92.5 °C; MP -165.5 °C
ACGIH: 0.1 ppm explosive range 0.8 to 98% v/v in air
(1 ppm = 1.131 mg/m3 @ NTP)
SYNONYMS: boroethane, boron hydride
SAMPLER: FILTER + SOLID SORBENT TUBE TECHNIQUE: PLASMA EMISSION SPECTROMETRY

(PTFE filter + oxidizer-impregnated
charcoal, 100 mg/50 mg) ANALYTE: boron
FLOW RATE: 0.5 to 1 L/min DESORPTION: 10 mL 3% H2O2; stand 30 min;

ultrasonic bath 20 min
-MAX: 260 L WAVELENGTH: 249.8 nm
SHIPMENT: routine ENTRANCE SLITS: 50 x 300 mm
SAMPLE STABILITY: at least 7 days CALIBRATION: aliquots of 1% (v/v) diborane

@25 °C[1] adsorbed on impregnated charcoal
FIELD BLANKS: 2 to 10 field blanks per set RANGE: 7 to 30 //g diborane per sample [1]
ESTIMATED LOD: 1 //g diborane per sample [1]
ACCURACY PRECISION (Sr): 0.063 @ 7 to 27 fjg diborane

per sample [1]
(120-L samples) [1]
BIAS: - 4.8%
OVERALL PRECISION (SrT): 0 085 [1]
ACCURACY: ± 21.5%
APPLICABILITY: The working range is 0.05 to 0.22 ppm (0.06 to 0.25 mg/m3) for a 120-L air sample.
INTERFERENCES: The filter removes boron-containing particulates. Avoid borosilicate glassware during sample preparation
to prevent boron contamination of samples. Higher boranes (e.g., tetraborane) interfere but are not likely to be encountered
in most samples.
OTHER METHODS: This revises P&CAM 341 [2]. The measurement can also be done by inductively-coupled plasma atomic
emission spectrometry (e.g., Method 7300).

DIBORANE: METHOD 6006, Issue 2, dated 15 August 1994 - Page 2 of 4
1. Diborane, 1% (v/v), certified gas mixture.* 1. Sampler:

2. Hydrogen peroxide (H2O2), 3% w/v in a. PTFE membrane filter, 13-mm diameter,
deionized water. 1-//m pore size (e.g., Millipore FALP), in a
3. Calibration stock solution, 1000 //g B/mL, plastic cassette (Millipore SX00013 or
commercially available or dissolve 0.572 g equivalent).
boric acid (H3BO3) in deionized water to make b. Glass tube, 7 cm long, 6-mm OD, 4-mm
100 mL solution. Store in a polyethylene ID, flame-sealed ends with plastic caps,
bottle. containing two sections (100 mg and 50
4. Argon, for DC plasma excitation. mg) of oxidizer-impregnated charcoal;
separated and retained by silylated glass
* See SPECIAL PRECAUTIONS. wool plugs.
3. Plasma emission spectrometer with a DC
plasmaexcitation source.
4. Pipets, plastic, 10-mL, and 5- to 50-fjL.
5. Volumetric flasks, plastic, 10-mL
6. Bottles, screw-top, plastic, 60-mL
7. Syringe, plastic, 10-mL, fitted with 0.5-//m
PTFE filter.
8. Vials, plastic, 7-mL, screw-on septum caps.
9. Ultrasonic bath.
SPECIAL PRECAUTIONS: Diborane is very toxic and flammable, having an Immediately Dangerous to
Life or Health (IDLH) level of 40 ppm. It is a strong irritant with a repulsive, sweet odor [3].
SAMPLING:

2. Break the ends of the charcoal tubes immediately before sampling. Attach the filter cassette in
front of the charcoal tube with a short piece of tubing. Attach the outlet of the charcoal tube to
the personal sampling pump with flexible tubing.
to 260 L
4. Separate the filter and the charcoal tube. Cap the charcoal tube. Pack securely for shipment.
SAMPLE PREPARATION:
5. Pipet 10.0 mL 3% H2O2 into a series of plastic bottles. Quickly add the front and back charcoal
sections to separate bottles and screw on the caps. Discard the glass wool plugs.
6. Allow to stand 30 min and then place in an ultrasonic bath for 20 min.
7. Draw the sample through a 0.5-//m PTFE membrane filter with a syringe.

a. Add known amounts of calibration stock solution to 3% H2O2 in 10-mL volumetric flasks and
dilute to the mark. Use serial dilutions as needed to obtain boron concentrations in the
range 0.1 to 4 //g B/mL

_DIBORANE: METHOD 6006, Issue 2, dated 15 August 1994 - Page 3 of 4_

c. Prepare calibration graph (response vs. fjg boron).
9. Determine desorption efficiency (DE) at least once for each lot of impregnated charcoal in the
range of interest. Prepare three tubes at each of five levels plus three media blanks.
a. Place 100 mg impregnated charcoal (e.g., unused front sorbent section) in a vial and screw
on the septum cap.
b. Flush the gas-tight syringe with inert gas (e.g., N2). Inject a known amount (0.1 to 5 mL) of
diborane gas mixture with the syringe into the vial. Treat two parallel blanks in the same
manner except that no diborane is added.
c. Allow the vials to stand overnight.
e. Prepare a graph of DE vs. jug boron recovered.
MEASUREMENT:
11. Set spectrometer to conditions on page 6006-1 and as specified by the manufacturer.
12. Analyze standards and samples.
NOTE: If response is above the range of the standards, dilute the sample solution with 3%
H2O2, reanalyze, and apply the appropriate dilution factor in the calculations.
CALCULATIONS:
13. Determine the mass, //g (corrected for DE) of boron found in the sample front (Wf) and back
(Wb) sorbent sections, and in the average media blank front (Bf) and back (Bb) sorbent
sections.
14. Calculate concentration, C, of diborane in the air volume sampled, V (L):
C .
where: 1.28 = the stoichiometric conversion factor from boron to diborane.
The method was tested by analyzing 18 samples, prepared by spiking 100 mg of impregnated charcoal
with 6.7, 13.4 or 26.8 mg of diborane gas representing the equivalent of 120-L air samples at 0.05, 0.1
and 0.2 ppm [2]. Desorption efficiency was determined to be 0.889, 0.964, and 0.994 at these three
concentrations, respectively. After analysis, the precision at the three concentrations was 8.4, 4.0, and
3.8%, respectively. Test atmospheres at 0.05, 0.1, and 0.2 ppm were generated using diborane gas.
The samples were collected at 1 L/min for 2 hours in charcoal tubes containing 100 mg front/50mg
back of impregnated charcoal. Eighteen samples were collected, and were desorbed one day later.
The backup sections of the samples at 0.2 ppm were analyzed also. Six additional generated samples
at 0.1 ppm were stored and analyzed seven days later. The average recovery of the 18 samples was
95.2%, pooled Sr = 2.7%. No trace of diborane (boron) was found in the backup section.
The seven-day storage stability samples indicated an average recovery of 101.6 ± 2.1%.
Breakthrough tests were conducted with a generated test atmosphere at 1.9 ppm with four impregnated
charcoal tubes. The sample volume was 120 L The average collection efficiency in the front sections
was 99.8 ± 0.3%. Breakthrough occurred in only two samples indicating 0.6 and 0.2% breakthrough.
An additional breakthrough study was conducted with a generated test atmosphere containing 0.34 ppm
diborane at a relative humidity of 60 to 70%. Two impregnated charcoal tubes were collected after

DIBORANE: METHOD 6006, Issue 2, dated 15 August 1994 - Page 4 of 4
60 min, two after 120 min, and two after 235 min. No breakthrough was detected in any sample.
Therefore, the capacity of the charcoal tube is at least 80 fjg diborane.
A filter study was conducted with 12 samples collected simultaneously, six with a prefilter and six without
the prefilter, at 0.1 ppm. The results indicated that the use of the PTFE filters does not affect the
precision or accuracy of the method. Mixed cellulose ester membrane prefilters produced a loss of
7.5% in the collection efficiency and, therefore, are not recommended as prefilters.
REFERENCES:
[1] Arthur D. Little, Inc., Backup Data Report for Diborane, prepared under NIOSH Contract No.
210-80-0099 (June 1, 1981).
[2] NIOSH Manual of Analytical Methods, 2nd td., Vol. 7, P&CAM 341, U.S. Department of Health and
and Human Services, Publ. (NIOSH) 81-123 (1981), available as Stock #PB83-154609 from NTIS,
METHOD REVISED BY:
B.R. Belinky, NIOSH/DPSE and J. Palassis, NIOSH/DTMD.

DIBUTYL PHOSPHATE 5017
(C4H902)(OH)P = MW: 210.21 CAS: 107-66-4 RTECS: TB9605000

OSHA : 1 ppm PROPERTIES: liquid; d 1.06 g/mL;

NIOSH: 1 ppm; STEL 2 ppm decomposes @ 100 °C; VP
ACGIH: 1 ppm; STEL 2 ppm unknown
(1 ppm = 8.59 mg/m3 @ NTP)
SYNONYMS: phosphoric acid dibutyl ester
SAMPLER: FILTER TECHNIQUE: GAS CHROMATOGRAPHY,

(1.0-/OT1 PTFE) PHOSPHORUS FPD
FLOW RATE: 1 to 3 L/min ANALYTE: dibutyl -trimethylsilyl phosphate
VOL-MIN: 50 L @ 1 ppm DESORPTION: acetonitrile

-MAX: 250 L
DERIVATIZATION: N,O-bis(trimethylsilyl)tri
SHIPMENT: routine fluoroacetamide (BSTFA)
SAMPLE STABILITY: at least 7 days at room INJECTION VOLUME: 1 fjL

temperature [1]
CARRIER GAS: He, 30 mL/min
-DETECTOR: 210 °C
-COLUMN: 155 °C
ACCURACY COLUMN: glass; 1.2 m x 6-mm OD; 3% OV-101 on

100/120 mesh Chromosorb WHP
(180-L samples) CALIBRATION: dibutyl phosphate in CH3CN with internal
standard
APPLICABILITY: The working range is 0.2 to 1.2 ppm (2 to 10 mg/m3) for a 200-L air sample.
OTHER METHODS: This method revises P&CAM 297 [2].

DIBUTYL PHOSPHATE: METHOD 5017, Issue 2, dated 15 August 1994 - Page 2 of 3
1. Dibutyl phosphate,* purified 99%, according to 1. Sampler: PTFE membrane filter, 1-//m,
Ref. [3]. (Millipore FA or equivalent), 37-mm diameter in
2. Eluent: Acetonitrile, reagent grade, containing a two-piece polystyrene cassette filter holder.
0.1% (v/v) tributyl phosphate internal 2. Personal sampling pump, 1 to 3 L/min, with
standard. flexible connecting tubing.
3. Calibration stock solution, 45 mg/mL 3. Jars, squat-form, 60-mL, with PTFE film
Dissolve 0.45 g purified dibutyl phosphate in gaskets, and screw caps.
10 mL acetonitrile. 4. Vial, 2-mL, with PTFE-lined caps.
4. NJO_-bis(trimethylsilyl)trifluoroacetamide 5. Gas chromatograph with phosphorus FPD,
(BSTFA), reagent grade. integrator, and column (page 5017-1).
5. Helium, purified. 6. Syringes, 5-, 10-, and 25-//L, for making
6. Hydrogen, prepurified. standard solutions and GC injections.
7. Air, filtered, compressed. 7. Volumetric flasks, 10- and 100-mL
8. Pipets, 1- and 5-mL
* See SPECIAL PRECAUTIONS. 9. Tweezers.
SPECIAL PRECAUTIONS: Dibutyl phosphate is toxic if inhaled or comes in contact with the eyes or
skin [3]. Sample preparations should be conducted in a hood.
SAMPLING:

2. Attach sampler to personal sampling pump with flexible tubing. Sample at an accurately known
flow rate between 1 and 3 L/min for a total sample size of 50 to 250 L
SAMPLE PREPARATION:
3. Using tweezers, carefully transfer the filter to a 60-mL jar.

4. Pipet 5.0 mL eluent into each jar. Cap the jar.
6. Transfer 1.0 mL of the extract to a 2-mL vial. Add 100 //L BSTFA. Cap the vial, shake
thoroughly, and let stand 30 min.
7. Calibrate daily with at least six working standards over the range 0.1 to 2 mg dibutyl phosphate
per sample.
a. Add known amounts of calibration stock solution to eluent in 10-mL volumetric flasks and
dilute to the mark.
c. Prepare calibration graph (ratio of peak area of dibutyl phosphate to peak area of internal
standard vs. mg dibutyl phosphate).

DIBUTYL PHOSPHATE: METHOD 5017, Issue 2, dated 15 August 1994 - Page 3 of 3
MEASUREMENT:

autosampler.
NOTE 1 : Under these conditions, approximate retention times are 4 min for dibutyl phosphate
and 6 min for tributyl phosphate.
10. Measure peak area. Divide the peak area of dibutyl phosphate derivative by the peak area of
internal standard on the same chromatogram.
CALCULATIONS:
11. Determine the mass, mg of dibutyl phosphate found in the sample (W), and in the average
media blank (B).
12. Calculate concentration, C (mg/m3), of dibutyl phosphate in the air volume sampled, V (L):
C . - - mg/m3.
Method P&CAM 297 was issued on November 8, 1978 [2]. The substance used to generate test
atmospheres at 25 °C and 760 mm Hg in dry air was technical grade dibutyl phosphate containing ca.
55% dibutyl phosphate and 45% monobutyl phosphate [1,4]. The collection efficiencies and
measurement recoveries were 1 .00 in the range 0.5 to 5 mg per sample. Sample filters stored one week
at ambient conditions gave recovery of 106 ± 5%. Overall sampling and measurement precision, §rT,
was 0.057. No independent method was available to estimate bias.
REFERENCES:
[1] Backup Data for P&CAM 297, prepared under NIOSH Contract 210-76-0123 (unpublished,
Novembers, 1978).
Human Services, Publ. (NIOSH) 81-123, available as GPO Stock #017-033-00337-8 from
(1980).
METHOD REVISED BY:
Gangadhar Choudhary, Ph.D., ATSDR. P&CAM 297 prepared under NIOSH Contract 210-76-0123.

DIBUTYL PHTHALATE 5020
C6H4(COO(CH2)3CH3); MW: 278.35 CAS: 84-74-2 RTECS: TI0875000

OSHA : 5 mg/m3 PROPERTIES: oily liquid; d 1.047 g/mL

NIOSH: 5 mg/m3 @ 20 °C; MP -37 °C; BP 340 °C;
ACGIH: 5 mg/m3 VP < 1 Pa (<0.01 mm Hg) @ 20 °C
SYNONYMS: di-n-butyl phthalate; phthalic acid dibutyl ester; DBP

(0.8 ATTI cellulose ester membrane)
ANALYTE: dibutyl phthalate
DESORPTION: 2 mL CS2; 30 min in ultrasonic bath
-MAX: 200 L INJECTION VOLUME:

-DETECTOR: 300 °C
SAMPLE STABILITY: at least 6 days @ 25 °C [1] -COLUMN: 200 to 250 °C
COLUMN: 2 m x 3-mm OD stainless steel, 5%

OV-101 on 100/120 mesh Chromosorb
W-HP
ACCURACY CALIBRATION: solutions of analyte in CS, with internal

standard
(30-L samples) RANGE: 30 to 500 fjg per sample
BIAS: -8.1%
ESTIMATED LOD: 10//g per sample
PRECISION (5r): 0.05 @ 70 to 300 //g per sample [1]
ACCURACY: ±16.4%
APPLICABILITY: The working range is 1 to 20 mg/m3 for a 30-L air sample. Phthalates are widely used as plasticizers for many
resins and elastomers.
INTERFERENCES: None identified. An alternate GC column is 10 m x 0.25-mm ID, 0.25-//m DB-1, fused silica capillary.
OTHER METHODS: This method combines and replaces Methods S33 [3] and S40 [4].

DIBUTYL PHTHALATE and DI(2-ETHYLHEXYL)PHTHALATE: METHOD 5020, Issue 2, dated 15 August 1994 - Page 2 of 3
Eluent: Carbon bisulfide*, chromatographic 1. Sampler: mixed cellulose ester membrane

quality, containing 0.05% (w/v) heneicosane, filter, 0.8-mm pore size, 37-mm diameter, in
tetradecane, tricosane, di(2-ethylhexyl)adipate two-piece cassette filter holder with backup
or other suitable internal standard. pad.
Analytes: dibutyl phthalate and 2. Personal sampling pump, 1 to 3 L/min, with
di(2-ethylhexyl) phthalate. flexible connecting tubing.
3. Recovery stock solution, 10 mg/mL Dissolve 3. Gas chromatograph, FID, integrator, and
0.1 g of each analyte in CS2 to make 10 mL column (page 5020-1).
solution. 4. Vials, glass, 5-mL, PTFE-lined caps.
4. Helium, purified. 5. Syringes, 1- and 10-//L and other convenient
5. Hydrogen, prepurified. sizes for making standards.
6. Air, filtered, compressed. 6. Volumetric flasks, 10-mL
7. Pipet, volumetric, 2-mL, with pipet bulb.
* See SPECIAL PRECAUTIONS. 8. Ultrasonic bath.
9. Tweezers.
SPECIAL PRECAUTIONS: Carbon disulfide is toxic and a dangerous fire and explosion hazard (flash
point = -30 °C); work with it only in a hood.
SAMPLING:

2. Remove cassette plugs immediately before sampling. Attach sampler to personal sampling
200 L
4. Cap the samplers with the cassette plugs and pack securely for shipment.
SAMPLE PREPARATION:
5. Open the cassette and carefully transfer the filter with tweezers to a 5-mL vial. Discard the
backup pad.
6. Add 2.0 mL eluent to each vial and attach caps.
8. Calibrate daily with at least six working standards over the range 10 to 500 //g analyte per
sample.
a. Add known amounts of analyte (or standard solution of analyte in CS2) to eluent in 10-mL
//g analyte).
9. Determine recovery (R) at least once for each lot of filters used for sampling in the calibration
range. Prepare three filters at each of five concentrations plus three media blanks.
a. Deposit a known amount (1 to 50 //L) of recovery stock solution onto the filter. Allow filters
to air dry.

DIBUTYL PHTHALATE and DI(2-ETHYLHEXYL)PHTHALATE: METHOD 5020, Issue 2, dated 15 August 1994 - Page 3 of 3
b. Store samples overnight in cassettes.

c. Prepare for analysis (steps 5 through 7) and analyze together with working standards (steps
11 and 12).
d. Prepare a graph of R vs. JJQ analyte recovered.
MEASUREMENT:
11. Set gas chromatograph according to manufacturer's recommendations and to conditions on

page 5020-1 . Inject sample manually using solvent flush technique or with autosampler.
same chromatogram.
CALCULATIONS:
13. Determine the mass, //g (corrected for recovery) of analyte found on the .filter (W) and in the
average media blank (B).
14. Calculate concentration, C, of analyte in the air volume sampled, V(L):
c.
Methods S33 (dibutyl phthalate) [3] and S40 [di(2-ethylhexyl) phthalate] [4] were issued on January 17,
1975 and validated over the range 2 to 10 mg/m3 at 23° and 25 °C and 767 mm and 761 mm Hg,
respectively, using 30- and 32-L air samples [1,2]. Test atmospheres of the phthalates were generated
using a Royco generator/impinger system and calibrated using the GC assay procedure. Overall
precision, SrT, was 0.057 for both compounds with average recoveries for generated samples of 94 and
107%, respectively. Extraction efficiencies were 97 and 96% in the range 0.07 to 0.30 mg per sample.
Collection efficiency for aerosols (less than 5 //m) on this type filter was greater than 99.9%. Storage
stability for dibutyl phthalate was at least 6 days at 25 °C. The stability of di(ethylhexyl)phthalate was
not determined.
REFERENCES:
[1] Documentation of NIOSH Validation Tests, S33, U.S. Department of Health, Education, and Welfare,
Publ. (NIOSH) 77-185 (1977), available as GPO Stock #017-033-00231-2 from Superintendent of
Documents, Washington, DC 20402.
[2] Ibid., S40.
[4] Ibid., S40.
METHOD REVISED BY:
Ardith A. Grote, NIOSH/DPSE; S33 and S40 originally validated under NIOSH Contract CDC-99-74-55.

0-DICHLOROBENZENE

P-DICHLOROBENZENE

3,3'-DICHLOROBENZIDINE 5509
(See Method 5509, BENZIDINE, for procedure)
(C6H3CINH2)2 MW: 253.13 CAS: 91-94-1 RTECS: DD0525000

OSHA : carcinogen (29 CFR 1910.1010) PROPERTIES: solid; MP 132 °C

NIOSH: carcinogen (29 CFR 1910.1010)
ACGIH: carcinogen (skin)
SYNONYMS: 3,3'-dichloro[1,1'-biphenyl]-4,4'-diamine.

(13-mm glass fiber)
ANALYTE: 3,3'-dichlorobenzidine
FLOW RATE: 0.2 L/min
DESORPTION: 0.5 mL 0.17% (v/v) triethylamine in
VOL-MIN: 20L@ 10//g/m3 methanol; stand 60 min
-MAX: 100 L
INJECTION
SHIPMENT: ship benzidine samples in dry ice VOLUME: 15 //L
SAMPLE MOBILE PHASE: 70% acetonitrile/30% water

STABILITY: 12 days @ 23 °C [1]
FLOW RATE: 1.5 mL/min; ambient temperature
COLUMN: //Bondapak C18, 10-//m particles, 30 cm x
4-mm

ACCURACY
CALIBRATION: solutions of 3,3-dichlorobenzidine in
RANGE STUDIED: 20 to 130 fjg/m3 [1] eluent
BIAS: - 4.0% RANGE: 0.2 to 7 fjg per sample
OVERALL PRECISION (SrT): 0.07 [1] ESTIMATED LOD: 0.05 //g per sample [1]
ACCURACY: ± 15.2% PRECISION (Sr): <0.07 [1]
APPLICABILITY: The working range is 4 to 200 mg/m3 for a 50-L air sample. Benzidinium sulfate and 3,3'-dichlorobenzidine
dihydrochloride will be collected and converted to benzidine and 3,3'-dichlorobenzidine, respectively, during sample preparation.
INTERFERENCES: Aniline interferes in the determination of benzidine but may be resolved [2].
4,4'-Methylenebis(2-chloroaniline) interferes in the determination of 3,3'-dichlorobenzidine [1]. A number of compounds were
shown not to interfere [1,2] (see NOTE 2, step 12).
OTHER METHODS: This combines and replaces P&CAM 243 and P&CAM 246 [3].

DICHLORODIFLUOROMETHANE 1018
CCUF
2i 2 MW: 120.91 CAS: 75-71 -8 RTECS: PA8200000

OSHA : 1000 ppm PROPERTIES: gas; BP -29.8 °C; MP -158 °C:

NIOSH: 1000 ppm d 1.35 @ 21.1 °C; nonflammable
ACGIH: 1000 ppm
(1 ppm = 4.95 mg/m3 @ NTP)
SYNONYMS: difluorodichloromethane; Refrigerant 12

(two coconut shell charcoal tubes in series,
400/200 mg and 100/50 mg) ANALYTE: dichlorodifluoromethane


-DETECTOR: 260 °C
STABILITY: at least 7 days @ - 10 °C 15 °C/min to
75 °C, hold 6 min
COLUMN: DEM fused silica capillary, 30 m x

0.32-mm ID, 1-//m film thickness or
equivalent
ACCURACY
RANGE STUDIED: 2940 to 10,500 mg/m3 [1] methylene chloride
BIAS: - 1.8% RANGE: 5 to 30 mg per sample [1]
ACCURACY: ± 12.8% PRECISION (Sr): 0.035 @ 7.4-30 mg per sample [1]
APPLICABILITY: The working ranges are 1000 to 6000 ppm dichlorodifluoromethane (5000 to 30,000 mg/m3); 700 to 5700
ppm 1,2-dichlorotetrafluoromethane (5000 to 40,000 mg/m3); and 300 to 4000 ppm chlorodifluoromethane (1000 to 14,000
mg/m3) for a 1-L air sample. This method was first evaluated for dichlorodifluoromethane and 1 ,2-dichlorotetrafluoroethane
with packed column gas chromatography [1]. The method was recently evaluated specifically for chlorodifluoromethane
using capillary chromatography [3]. Capillary GC conditions for the separation of the three compounds were established.

DICHLORODIFLUOROMETHANE, 1.2-DICHLOROTETRAFLUOROMETHANE, CHLORODIFLUOROMETHANE: METHOD 1018, Issue 1, dated 15 August 1994, Page 2 of 4
1. Chlorodifluoromethane, 99% Sampler: two glass tubes (9 cm long, 8-mm

2. Dichlorodifluoromethane, 99% OD, 6-mm ID, followed by 7 cm long, 6-mm
3. 1,2-Dichlorotetrafluoroethane, 99% OD, 4-mm ID) connected in series with a
4. Methylene chloride", distilled in glass. short piece of tubing, flame-sealed ends with
5. Nitrogen, purified. plastic caps, containing two sections of
6. Hydrogen, prepurified activated (600 °C) coconut shell charcoal
7. Air, filtered, compressed. (1st 400 mg/200 mg; 2nd 100 mg/50 mg),
8. Helium, purified front and back sections separated by a
2-mm urethane foam plug. A silylated glass
wool plug precedes the front section and a
3-mm urethane foam plug follows the back
* See Special Precautions section. Pressure drop across the tube at 1
L/min airflow must be less than 25 mm/Hg.
Tubes are commercially available.
2. Personal sampling pump, 0.01 to 0.05
mL/min, with flexible connecting tubing.
3. Refrigerant, bagged (Blue Ice, or equivalent).
4. Gas chromatograph with a FID detector,
recorder, integrator and column (page
1018-1).
5. Bottles, 22-mL, PTFE-lined septum screw
caps.
6. Syringes, gas-tight, 10-mL and other sizes as
needed.
7. Pipet, TD, 20-mL, with pipet bulbs.
8. DE apparatus. Glass or plastic T equipped
with septum in one arm to allow introduction
of analyte to a flowing stream of nitrogen.
SPECIAL PRECAUTIONS: Methylene chloride is an irritant, can be absorbed through the skin, and is
a suspect carcinogen [4]. Prepare samples in a hood.
SAMPLING:

1 to 4 L
4. Separate and cap the tubes. Pack securely for shipment in an insulated container with
bagged refrigerant.
SAMPLE PREPARATION:
NOTE: Refrigerate samples at -10 °C if not analyzed immediately.

5. Pipet 20.0 mL methylene chloride into a series of bottles.
6. Place both sections of the front sampler tube into a bottle containing solvent, discarding the
glass wool and foam plugs. Immediately cap and gently shake the bottle. Analyze within 6 hrs.
7. Perform step 6 for the back sampler tube.

DICHLORODIFLUOROMETHANE, 1 ,2-DICHLOROTETRAFLUOROMETHANE, CHLORODIFLUOROMETHANE: METHOD 1018, Issue 1, dated 15 August 1994, Page 3 of 4
8. Calibrate daily with at least five working standards.

a. Pipet 20.0 mL methylene chloride into each of a series of bottles. Cap the bottles.
b. Using a gas-tight syringe, add known amounts of analyte, e.g., 0.01 to 6 mL (0.0354 to 21.2
mg @ NTP) chlorodifluoromethane, or 0.01 to 6 mL (0.0495 to 29.7 mg @ NTP)
dichlorodifluoromethane, or 0.01 to 6 mL (0.0699 to 41.9 mg @ NTP) 1,2-
dichlorotetrafluoroethane by bubbling the gas slowly through the methylene chloride. Gently
shake the bottles.
c. Analyze with samples and blanks (steps 11 and 12).
d. Prepare calibration graph (area vs. mg analyte).
9. Determine desorption efficiency (DE) at least once for each lot of sorbent used for sampling in
the range of interest (step 8). Prepare three tubes at each of five levels plus three media blanks.
a. Using a gas-tight syringe, inject a known amount of analyte (0.01 to 6 mL)
through the septum of the DE apparatus unto a stream of nitrogen (ca. 20
mL/min) which carries the analyte into a large (400/200 mg) sorbent tube.
Allow the nitrogen to flow an additional 30.
b. Cap the tube. Allow to stand overnight.
c. Desorb (steps 5 through 7) and analyze with working standards (steps 11 and 12)
d. Prepare a graph of DE vs. mg analyte recovered.
MEASUREMENT:
autosampler.
desorbed liquid with methylene chloride, reanalyze and apply the appropriate dilution
factor in calculations.
NOTE: The order of elution is chlorodifluoromethane, dichlorodifluoromethane, 1,2-
tetrafluoroethane. If analyzing for two or more of the compounds, a temperature rate of
5 °C/min is required.
CALCULATIONS:
13. Determine the mass, mg (corrected for DE), of analyte found in the sample front (W() and back
C . (W,.Wt-B,-B.).1»
Validation this method for dichlorodifluoromethane and 1,2-dichlorotetrafluoroethane was done using
packed column gas chromatographic techniques. The column was stainless steel 1.2 m x 6-mm OD,
packed with 80/100 mesh Chromosorb 102. Chlorodifluoromethane was evaluated using the capillary
chromatographic conditions listed on p. 101 8-1. The use of capillary gas chromatographic analysis was
determined to be appropriate for all three compounds.

DICHLORODIFLUOROMETHANE, 1 ,2-DICHLOROTETRAFLUOROMETHANE, CHLORODIFLUOROMETHANE: METHOD 1018, Issue 1, dated 15 August 1994, Page 4 of 4
Dichlorodifluoromethane: Method S111 was issued September 30, 1976 [2], and validated using test
atmospheres generated in air and monitored with a calibrated total hydrocarbon analyzer [1,5]. Average
recovery for 18 samples was 98.2%. In breakthrough tests at 12 and 94% relative humidity (RH), the
capacity of the sampler was 61 and 44 mg of dichlorodifluoromethane, respectively, when sampling at
ca. 0.045 L/min from atmospheres containing ca. 10,000 mg/m3. Desorption efficiency averaged 0.97 in
the range 7.4 to 30 mg per sample.
Dichlorotetrafluoroethane: Method S108 was issued October 29, 1976 [2], and validated using test
atmospheres generated in air and monitored with a calibrated total hydrocarbon analyzer [1,4]. The
average recovery for 18 samples was 99.8%. Breakthrough (effluent concentration = 5% of test
concentration) occurred after 158 min when sampling 14,600 mg/m3 at 90% RH at 0.046 L/min.
Desorption efficiency averaged 0.99 in the range 10.7 to 42.8 mg per sample.
Chlorodifluoromethane: The precision and accuracy of the method were determined using test gas bag
atmospheres generated and monitored with a halide meter. Average recovery for 18 samples over the
range of 1780 to 6970 mg/ m3 was 100 %. In breakthrough tests at- 80% relative humidity, the sampler
retained 15.4 mg of Chlorodifluoromethane when sampling at 0.025 L/min from atmospheres containing
7000 mg/m3. The desorption efficiency of Chlorodifluoromethane from activated charcoal averaged 0.96
in the range 0.53 to 10.4 mg per sample.
REFERENCES:
[1] Backup Data Reports S111 (Dichlorodifluoromethane) and S108 (Dichlorotetrafluoroethane),

prepared under NIOSH Contract 210-76-0123, available as "Ten NIOSH Analytical Methods, Set 1,"
Order No. PB 271-712, from NTIS, Springfield, VA 22161.
[2] NIOSH Manual of Analytical Methods, 2nd ed., Vol. 2, S111 and S108, U.S. Department of Health,
Education, and Welfare, Publ. (NIOSH) 77-157-B (1977).
[3] Seymour, M.J., M.F. Lucas. Evaluation of Sampling and Analytical Methods for the Determination of
Chlorodifluoromethane in Air, Am. Ind. Hvg. Assoc. J., 54, 253-259 (1993).
[4] NIOSH Current Intelligence Bulletin 46, U.S. Department of Health and Human Services, Publ.
(NIOSH) 86-1 14 (1986).
(1980).
METHOD REVISED BY:
M.J. Seymour, NIOSH/DPSE.

1,1-DICHLOROETHANE

1,1-DICHLOROETHANE

D1CHLOROETHYL ETHER 1004
(CICH2CH2)20 MW: 143.01 CAS: 111-44-4 RTECS: KN0875000

OSHA: C 15 ppm (skin) PROPERTIES: liquid; d 1.218 g/mL @ 20 °C;

NIOSH: 5 ppm; STEL 10 ppm (skin); carcinogen BP 178 °C; MP -52 °C;
ACGIH: 5 ppm; STEL 10 ppm (skin); carcinogen VP 50 Pa (0.4 mm Hg; 530 ppm) @ 20 °C
(1 ppm = 5.85 mg/m3 @ NTP)
SYNONYMS: bis(2-chloroethyl) ether; 1,1'-oxybis[2-chloroethane]; 2,2'-dichlorodiethyl ether; sym-dichloroethyl ether

ANALYTE: dichloroethyl ether
DESORPTION: 1 mL CS2; stand 30 min
VOL-MIN: 2 L@ 15 ppm
SHIPMENT: routine
TEMPERATURE-INJECTION: 200 - 225 °C
SAMPLE -DETECTOR: 250 - 275 °C
STABILITY: at least 7 days @ 25 °C [1] -COLUMN: 100- 135 °C
COLUMN: 3 m x 3-mm ID stainless steel; 10% FFAP

on 80/100 mesh DMCS Chromosorb
W-AW or equivalent
ACCURACY
CALIBRATION: dichloroethyl ether in CS2
(15-L samples) RANGE: 0.15 to 4 mg per sample [2]
BIAS: - 7.61%
ACCURACY: ± 15.7%
APPLICABILITY: The working range is 1.7 to 46 ppm (10 to 270 mg/m3) for a 15-L air sample. This method may be used for
simultaneous analysis of two or more analytes by changing the chromatographic conditions (e.g., temperature programming).
High humidity during sampling will greatly reduce breakthrough volume.
INTERFERENCES: None identified. Alternate columns, e.g., 10% SP-1000 on 80/100 mesh Supelcoport, SP-2100 with 0.1%
Carbowax 1500 or DB-1 fused silica capillary column may be used.

DICHLOROETHYL ETHER: METHOD 1004, Issue 2, dated 15 August 1994 - Page 2 of 3
1. Eluent: Carbon disulfide*, chromatographic 1 . Sampler: glass tube, 7 cm long, 6-mm OD, 4-
quality containing 0.1% (v/v) toluene or other mm ID, flame-sealed ends, containing two
suitable internal standard. sections of activated (600 °C) coconut shell
2. Dichloroethyl ether (DCEE). charcoal (front = 100 mg; back = 50 mg)
3. Hexane. separated by a 2-mm urethane foam plug. A
4. Calibration stock solution, 0.244 mg/^L silylated glass wool plug precedes the front
Dilute 2.44 g DCEE (2.0 ml_ at 20 °C) to 10 section and a 3-mm urethane foam plug
mL with hexane. Prepare in duplicate. follows the back section. Pressure drop
5. Nitrogen, purified. across the tube at 1 L/min airflow must be
6. Hydrogen, prepurified. less than 3.4 kPa. Tubes are commercially
7. Air, filtered. available.
* See SPECIAL PRECAUTIONS. flexible connecting tubing.
= -30 °C); work with it only in a hood.
SAMPLING:

to 15 L
SAMPLE PREPARATION:
8. Calibrate daily with at least six working standards over the range 0.01 to 4 mg DCEE per
sample.
dilute to the mark.
mg DCEE).
blanks.

DICHLOROETHYL ETHER: METHOD 1004, Issue 2, dated 15 August 1994 - Page 3 of 3
microliter syringe.
e. Prepare a graph of DE vs. mg DCEE recovered.
MEASUREMENT:
autosampler.
same chromatogram.
CALCULATIONS:
13. Determine the mass, mg (corrected for DE) of DCEE found in the sample front (Wf) and back
sections.
14. Calculate concentration, C, of DCEE in the air volume sampled, V (L):
C - W * Wt - B, - BJ .
Method S357 [2] was issued on May 21, 1976, and validated over the range 45 to 180 mg/m3 at 24 °C
and 762 mm Hg using a 15-L sample [1]. Overall precision, SrT, was 0.059 with average recovery
90.7%, representing a non-significant bias. The concentration of DCEE was independently verified by a
direct hydrocarbon analyzer. Desorption efficiency was 0.94 in the range 0.7 mg to 2.7 mg per sample.
Breakthrough (5% on back section) occurred at 115 min when sampling an atmosphere containing 161
mg/m3 at 0.9 L/min in dry air.
REFERENCES:
[1] Documentation of the NIOSH Validation Tests, NIOSH, S357, U.S. Department of Health, Education,
[3] User check, UBTL, NIOSH Sequence #412t-J (unpublished, November 21, 1983).
METHOD REVISED BY:
CDC-99-74-45.

DICHLOROFLUOROMETHANE 2516
CHCUF MW: 102.92 CAS: 75-43-4 RTECS: PA8400000

OSHA : 1000 ppm PROPERTIES: gas; BP 8.9 °C; d 1.405 g/mL @ 9 °C;
NIOSH: 10 ppm vapor density (air = 1) 3.82;
ACGIH: 10 ppm not combustible
(1 ppm = 4.21 mg/m3 @ NTP)
SYNONYMS: Freon 21; Halon 112; dichloromonofluoromethane

(2 coconut shell charcoal tubes,
400 mg and 200 mg) ANALYTE: dichlorofluoromethane
FLOW RATE: 0.01 to 0.05 L/min DESORPTION: 5 mL CS2; stand 30 min
VOL-MIN: 0.25 L @ 1000 ppm INJECTION VOLUME: 5 //L

-MAX: 3L
SHIPMENT: separate front and backup tubes -DETECTOR: 220 °C
to avoid migration -COLUMN: 55 °C
SAMPLE STABILITY: at least 7 days @ 25 °C CARRIER GAS: N2, 30 mL/min
BLANKS: 2 to 10 field blanks per set COLUMN: stainless steel, 6 m x 3-mm, 10% FFAP
on 100/120 mesh Chromosorb WHP
CALIBRATION: dichlorofluoromethane solutions in

ACCURACY CS2 with internal standard
RANGE STUDIED: 1730 to 7640 mg/m3 [1] RANGE: 1 to 35 mg per sample

(3-L samples)
BIAS: 3.0%
OVERALL PRECISION (SrT): 0.061 [1] PRECISION (5r): 0.024 @ 6 to 34 mg per sample [1]
ACCURACY: ± 13.3%
APPLICABILITY: The working range is 120 to 1500 ppm (500 to 6300 mg/m3) for a 2-L air sample.

DICHLOROFLUOROMETHANE: METHOD 2516, Issue 2, dated 15 August 1994 - Page 2 of 4
1. Eluent: carbon disulfide,* chromatographic 1. Sampler: two glass tubes connected in series
quality, containing 0.4% v/v pentane as with a short piece of plastic tubing; each tube
internal standard. 10 cm long, 8-mm OD, 6-mm ID, with plastic
2. Dichlorofluoromethane, 99%.* caps, containing 20/40 mesh activated (600
3. Nitrogen, purified. °C) coconut shell charcoal (front tube = 400
4. Hydrogen, prepurified. mg; back tube = 200 mg). A plug of silylated
5. Air, filtered, compressed. glass wool is placed at each end of each tube.
Pressure drop across sampler less than 3.4
* See SPECIAL PRECAUTIONS. kPa (2.5 cm Hg) at 1 L/min airflow. Tubes are
commercially available.
4. Vials, glass, serum, 10-mL, with PTFE-lined
septa and crimp caps.
5. Syringe, 10-^L
6. Syringes, gas-tight, 10-mL and 100-//L
7. Syringe needles, 22-gauge.
SPECIAL PRECAUTIONS: Carbon disulfide is toxic and an extreme fire and explosion hazard (flash
point = -30 °C); work with it only in a hood. Dichlorofluoromethane may cause irregular heartbeat if
inhaled [3].
SAMPLING:

0.25 to 3 L
4. Separate the front and back tubes immediately after sampling. Cap the tubes. Pack securely
for shipment.
SAMPLE PREPARATION:
5. Place the front and back sorbent sections of the sampler in separate vials. Discard the glass
wool plugs. Attach crimp cap to each vial. Insert a syringe needle vent through the septum to
serve as a vent.
6. Add 5.0 mL eluent to each vial with a syringe. Remove the syringe needle vent from the
septum.
NOTE: To avoid loss of analyte, do not add eluent to the charcoal before sealing the vial.
8. Calibrate daily with at least six working standards over the range 0.05 to 35 mg (0.01 to 8.2 mL
at 20 °C and 101 kPa) dichlorofluoromethane per sample.
a. Add 5.0 mL eluent to each of a series of vials. Attach crimp cap to each vial.

DICHLOROFLUOROMETHANE: METHOD 2516, Issue 2. dated 15 August 1994 - Page 3 of 4
b. Immediately before adding dichlorofluoromethane, withdraw from each vial an amount of air
equal to that of dichlorofluoromethane to be added.
c. Slowly bubble a measured amount of dichlorofluoromethane into the liquid in each vial using
a gas-tight syringe.
d. Analyze together with samples and blanks (steps 11 and 12).
e. Prepare calibration graph (ratio of peak area of analyte to peak area of internal standard vs.
mg dichlorofluoromethane).
a. Inject a known amount of dichlorofluoromethane slowly and directly into a medial blank front
sorbent section with a gas-tight syringe.
b. Cap the tube. Allow to stand overnight.
c. Desorb (steps 5 through 7) and analyze together with working standards (steps 11 and 12).
d. Prepare a graph of DE vs. mg dichlorofluoromethane recovered.
graph and DE graph are in control
MEASUREMENT:
autosampler. tr = 6 min under these conditions.
NOTE 1 : If an autosampler is used, transfer an aliquot of the sample solution to a sealed
empty vial using a syringe needle as a vent.
12. Measure peak area. Divide the peak area of analyte by the peak area of internal standard of the
same chromatogram.
CALCULATIONS:
1 3. Determine the mass, mg (corrected for DE) of dichlorofluoromethane found in the sample front
(W() and back (Wb) sorbent tubes, and in the average media blank front (B,) and back (Bb)
sorbent tubes.
14. Calculate concentration, C, of dichlorofluoromethane in the air volume sampled, V (L):
C . W ^ Wt - B, - BJ •
Method S109 was issued on September 30, 1976 [2], and validated over the range 2100 to 12,600
mg/m3 by analyzing 18 spiked samples and 18 samples collected from dynamically-generated
atmospheres of dichlorofluoromethane gas [1,4]. These recoveries were 100.9 and 102.9%, respectively.
A combined storage migration study determined that samples of 17 and 35 mg had a 100% recovery
after seven days if stored without backup sections. At the same levels, those front sections stored with
backup sections had 83.2% recovery. Breakthrough (5%) in an atmosphere of 9120 mg/m3 and 90%
RH, sampling at 0.187 L/min, occurred at 23 min. giving a breakthrough volume of 4.3 L and tube
capacity of 39 mg. In a dry atmosphere of 8850 mg/m3, breakthrough occurred after 64 min sampling
at 0.187 L/min, giving a breakthrough volume of 12.0 L and tube capacity of 102 mg. Desorption
efficiencies averaged 101% over the range 5.9 to 34 mg dichlorofluoromethane per sample.

DICHLOROFLUOROMETHANE: METHOD 2516, Issue 2, dated 15 August 1994 - Page 4 of 4
REFERENCES:
[1] Backup Data Report, S109, available as "Ten NIOSH Analytical Methods, Set 1," Order No. PB
271-712 from NTIS, Springfield, VA 22161.
Education, and Welfare, Publ. (NIOSH) 77-157-B (1977).
[3] NIOSH/OSHA Occupational Health Guidelines for Chemical Hazards, Dichlorofluoromethane,
U.S. Department of Health and Human Services, Publ. (NIOSH) 81-123 (1981), available as GPO
Stock #017-033-00337-8 from Superintendent of Documents, Washington, DC 20402.
80-133 (1980).
METHOD REVISED BY:
Y.T. Gagnon, NIOSH/DPSE; S109 originally validated under NIOSH Contract 210-76-0123.

1 ,1 -DICHLORO-1 -NITROETHANE 1601
H3CC(CI)2NO2 MW: 143.96 CAS: 594-72-9 RTECS: Kl 1050000

OSHA: ClOppm PROPERTIES: liquid; d 1.405 g/mL @ 20 °C;

NIOSH: 2 ppm BP 124 °C; VP 2 kPa (15 mm Hg;
ACGIH: 2 ppm 2% v/v) @ 20 °C
(1 ppm = 5.89 mg/m3 @ NTP)
SYNONYMS: dichloronitroethane

(petroleum charcoal, 100 mg/50 mg)
ANALYTE: 1 , 1 -dichloro-1 -nitroethane
DESORPTION: 1 mL CS2, stand 30 min
-DETECTOR: 250 °C
SHIPMENT: routine -COLUMN: 70 °C
SAMPLE CARRIER GAS: N2 or He, 30 mL/min

COLUMN: 3 m x 3-mm stainless steel, 5% SP-1000
BLANKS: 2 to 10 field blanks per set on 100/120 mesh Chromosorb WHP, or
equivalent
CALIBRATION: analyte solutions in CS2 with undecane as

internal standard
ACCURACY
(17-L samples) ESTIMATED LOD : 0.01 mg per sample
BIAS: - 0.12%
PRECISION (Sr): 0.038[1]
ACCURACY: ± 11.6%
APPLICABILITY: The working range is 1 to 30 ppm (6 to 180 mg/m3) for a 15-L air sample. The method is applicable to ceiling
determinations.
INTERFERENCES: None identified. Alternate chromatographic columns to circumvent interferences are SP-2100, SP-2100 with
0.1% Carbowax 1500 or DB-1 fused silica capillary column.

1.1-DICHLORO-1-NITROETHANE: METHOD 1601, Issue 2, dated 15 August 1994 - Page 2 of 3
1. Eluent: Carbon disulfide,* chromatographic Sampler: glass tube, 7 cm long, 6-mm OD, 4-
quality, containing 0.2% v/v undecane or other mm ID, flame-sealed ends, containing two
suitable internal standard. sections of 20/40 mesh activated
2. 1,1-Dichloro-1-nitroethane. petroleum-based charcoal (front = 100 mg;
3. Calibration stock solution, 0.211 mg///L back = 50 mg) separated by a 2-mm urethane
Dilute 2.1 1 g 1,1-dichloro-1-nitroethane (1 .5 mL foam plug. A silylated glass wool plug
@ 20 °C) to 10 mL with CS2. Prepare in precedes the front section and a 3-mm
duplicate. urethane foam plug follows the back section.
4. Nitrogen, purified. Pressure drop across the tube at 1 L/min
5. Hydrogen, prepurified. airflow must be less than 3.4 kPa. Tubes are
6. Air. commercially available.
3. Gas chromatograph, flame ionization
detector, integrator and column (page 1601-1).
* See SPECIAL PRECAUTIONS. 4. Vials, 2-mL, PTFE-lined caps.
= -30 °C); work with it only in a hood.
SAMPLING:

3. Sample at an accurately known flow rate between 0.01 and 1 L/min for a total sample size of 1.5
to 15 L
SAMPLE PREPARATION:
8. Calibrate daily with at least six working standards over the range 0.01 to 2.7 mg
1,1-dichloro-1-nitroethane per sample.
dilute to the mark.
mg 1,1-dichloro-1-nitroethane).
blanks.

1,1-DICHLORO-1-NITROETHANE: METHOD 1601, Issue 2, dated 15 August 1994 - Page 3 of 3

microliter syringe.
e. Prepare a graph of DE vs. mg 1,1-dichloro-1-nitroethane recovered.
MEASUREMENT:
on page 1601-1 . Inject sample aliquot manually using solvent flush technique or with
autosampler.
same chromatogram.
CALCULATIONS:
13. Determine the mass, mg (corrected for DE) of 1,1-dichloro-1-nitroethane found in the sample
front (Wf) and back (Wb) sorbent sections, and in the average media blank front (Bf) and back
(Bb) sorbent sections.
14. Calculate concentration, C, of 1,1-dichloro-1-nitroethane in the air volume sampled, V (L):
C . WW.-B.-BJ
Method S213 [2] was issued on November 21, 1975, and validated over the range 27 to 115 mg/m3 at
23 °C and 763 mm Hg using a 17-L sample [1]. Overall precision, SrT, was 0.055, with average
recovery 97.7%, representing a non-significant bias. SKC Lot 104 charcoal was the collecting medium.
The concentration of analyte was independently verified by calibrated syringe pump. Desorption
efficiency was 0.910 in the range 0.5 mg to 2.0 mg analyte per sample. Breakthrough (5% on back
section) occurred at 193 min when sampling an atmosphere containing 116 mg/m3
1,1-dichloro-1-nitroethane at 0.79 L/min in dry air.
REFERENCES:
[1] Documentation of the NIOSH Validation Tests, NIOSH, S213, U.S. Department of Health, Education,
METHOD REVISED BY:
CDC-99-74-45.

1 ,2-DICHLOROTETRAFLUOROETHANE
See DICHLORODIFLUOROMETHANE (METHOD 1018) for procedure
CCIF,CCIF, MW: 170.92 CAS: 76-14-2 RTECS: KI1101000

OSHA : 1000 ppm PROPERTIES: gas; BP 3.8 °C; MP -94 °C

NIOSH: 1000 ppm
ACGIH: 1000 ppm
(1 ppm = 6.99 mg/m3 @ NTP)
SYNONYMS: cryofluorane, Refrigerant 114

(two coconut shell charcoal tubes in series,
400/200 mg and 100/50 mg) ANALYTE: 1 ,2-dichlorotetrafluoroethane
VOL-MIN: 1 L@ 1000 ppm INJECTION


-DETECTOR: 260 °C
STABILITY: at least 7 days @ - 10 °C 15 °C/min to
75 °C, hold 6 min
COLUMN: DB-1 fused silica capillary, 30 m x

0.32-mm ID, 1-pm film thickness or
equivalent
ACCURACY
RANGE STUDIED: 1800 to 6970 mg/m3 [3] methylene chloride
BIAS: 0% RANGE: 5 to 40 mg per sample [1]
ACCURACY: ± 14.5% PRECISION (Sr): 0.038 @ 10-40 mg per sample [1]
APPLICABILITY: The working range is 700 to 5700 ppm 1,2-dichlorotetrafluoroethane (5000 to 40,000 mg/m3) for a 1-L air
sample. This method was first evaluated for dichlorodifluoromethane and 1,2-dichlorotetrafluoroethane with packed column
gas chromatography [1].

DIETHYLAMINE
See AMINES, ALIPHATIC (Method 2010) for procedure

DIETHYLENETRIAMINE
See ETHYLENEDIAMINE, Method 2540, for Procedure
H2N(CH2)2NH(CH2)2NH2 MW: 103.2 CAS: 111-40-0 RTECS: I E1 225000
METHOD: 2540, Issue 2 EVALUATION: UNRATED Issue 1: 15 May 1989

OSHA : no PEL PROPERTIES: liquid; d 0.96 g/mL @ 20 °C;

NIOSH: 1 ppm (skin) BP 206.7 °C; VP 0.5 kPa (0.37 mm Hg);
ACGIH: 1 ppm (skin) flash point 98 °C
(1 ppm = 4.21 mg/m3)
SYNONYMS: diethylenetriamine: DETA; aminoethylethandiamine; 3-azapentane-1,5-diamine; bis(2-aminoethyl)amine
SAMPLER: SOLID SORBENT TUBE TECHNIQUE: HPLC, UV DETECTION

(1 -naphthylisothiocyanate-
coated XAD-2, 80 mg/40 mg) ANALYTE: naphthylisothiourea derivative of analytes
FLOW RATE: 0.01 to 0.1 L/min [1] DESORPTION: 2 mL dimethylformamide (DMF),

ultrasonic 30 min
SHIPMENT: routine COLUMN: 10-//m radial cyano, 10 cm x 8-mm ID in

Waters RCM-100 radial compression
SAMPLE mode
STABILITY: > 30 days @ 20 °C [2]
MOBILE PHASE: 50/50 isoctane/isopropanol at
BLANKS: 2 to 10 field blanks per set 3 m L/min
CALIBRATION: standard solutions of derivatives in DMF
ACCURACY RANGE: 1 to 80 pg per sample
RANGE STUDIED: 0.016 to 8 mg/m3; ESTIMATED LOD: 0.16 //g per sample
(10-L samples)
PRECISION (Sr): 0.007
BIAS: -1.9%
ACCURACY: ±13.5%
APPLICABILITY: The working range for DETA is 0.05 to 150 mg/m3 for a 10-L air sample. This method is the result of evaluation
[2] of OSHA Method #60 for DETA, EDA, TETA [1]. The theoretical capacity of each front section is 1.5 mg of DETA.
INTERFERENCES: Other primary or secondary amines may react with the sampler coating reagent, and thereby reduce the
sampler capacity.
OTHER METHODS: This replaces NIOSH Method P&CAM 276 [3]. The method of Anderson, et al., for EDA [4] is an alternate
method using thiourea derivatization and HPLC analysis.

DI(2-ETHYLHEXYL) PHTHALATE
See DIBUTYL PHTHALATE (Method 5020) for Procedure
C6H4(COOCH2CH(C2H5)(CH2)3CH3)2 MW: 390.56 CAS: 117-81-7 RTECS: TI0350000

OSHA : 5 mg/m3; STEL 10 mg/m3 PROPERTIES: oily liquid; d 0.983 g/mL @ 20 °C;
NIOSH: 5 mg/m3; STEL 10 mg/m3 (carcinogen) MP -50 °C; BP 386 °C; VP < 1 Pa
ACGIH: 5 mg/m3; STEL 10 mg/m3 (suspect carcinogen) (0.01 mm Hg) @ 20 °C
SYNONYMS: bis(2-ethylhexyl) phthalate; dioctyl phthalate; OOP; DEHP (listed incorrectly as di-sec-octyl phthalate in 29 CFR
1910.23)

(0.8 fjm cellulose ester membrane)
ANALYTE: di(2-ethylhexyl)phthalate
DESORPTION: 2 mL CS2; 30 min in ultrasonic bath
-MAX: 200 L INJECTION VOLUME: 5//L

-DETECTOR: 300 °C
SAMPLE STABILITY: unknown -COLUMN: 200 to 250 °C
COLUMN: 2 m x 3-mm OD stainless steel, 5%

OV-101 on 100/120 mesh Chromosorb
W-HP
ACCURACY CALIBRATION: solutions of analytes in CS2 with internal

standard
RANGE STUDIED: 2 to 1 1 mg/m3 [2]
(32-L samples) RANGE: 30 to 500 fjg per sample
BIAS: 7.56%
ESTIMATED LOD: 10^ per sample
OVERALL PRECISION (SrT): 0.057 [1,2]
PRECISION (Sr): 0.05 @ 0.07 to 0.3 mg per sample [2]
ACCURACY: ± 19.2%
APPLICABILITY: The working range is 1 to 20 mg/m3 for a 30-L air sample. Phthalates are widely used as plasticizers for many
resins and elastomers.
INTERFERENCES: None identified. An alternate GC column is 10 m x 0.25-mm ID, 0.25-fjm DB-1, fused silica capillary.
OTHER METHODS: This revises method S40 [4].

DIFLUORODIBROMOMETHANE 1012
CBr2F
2'2 MW: 209.83 CAS: 75-61-6 RTECS: PA7525000

OSHA: 100ppm PROPERTIES: liquid; d 2.35 g/mL @ 0 °C;

NIOSH: 100 ppm BP24.5 °C; FP -141 °C;
ACGIH: 100 ppm VP 83 kPa (620 mm Hg; 82% v/v)
(1 ppm = 8.58 mg/m3 @ NTP) @ 20 °C; non-flammable
SYNONYMS: dibromodifluoromethane; Freon 12B2

(2 tubes in tandem, each with 150 mg
coconut shell charcoal) ANALYTE: difluorodibromomethane
FLOW RATE: 0.01 to 0.2 L/min DESORPTION: 1.0 mL 2-prbpanol; stand overnight
VOL-MIN: 2.5 L INJECTION

-MAX: 10 L VOLUME: 5//L

-DETECTOR: 300 °C
COLUMN: 3 m x 6 mm OD stainless steel, packed
with 10% FFAP on 100/120 Chromosorb
WHP or equivalent
ACCURACY
CALIBRATION: difluorodibromomethane in 2-propanol
(10-L samples) RANGE: 2 to 20 mg per sample
BIAS: 2.5%
ESTIMATED LOD : 0.4 mg per sample
ACCURACY: ± 18.8%
APPLICABILITY: The working range is 200 to 2000 mg/m3 (23 to 230 ppm) for a 10-L air sample. Difluorodibromomethane
is used in the synthesis of dyes, Pharmaceuticals, and quaternary ammonium compounds, and as a fire extinguishing agent.
INTERFERENCES: Carbon disulfide has about the same GC retention volume as difluorodibromomethane [1].
OTHER METHODS: This is Method S107 in a revised format [2].

DIFLUORODIBROMOMETHANE: METHOD 1012, Issue 2, dated 15 August 1994 - Page 2 of 4
1. 2-Propanol, chromatographic grade. 1 . Sampler: two glass tubes in series, each with
2. Difluorodibromomethane.* both ends flame sealed, 7 cm long, 6-mm OD,
3. Nitrogen, purified. 4-mm rD, each containing 150 mg of 20/40
4. Hydrogen, prepurified. mesh activated (600 °C) coconut shell
5. Air, filtered, compressed. charcoal; four plastic caps for sealing after
use. A silylated glass wool plug precedes the
charcoal beds and a 3-mm urethane foam
See SPECIAL PRECAUTIONS. plug follows the charcoal beds.
NOTE: A pair of two-section (100 mg/50 mg)
tubes may be used.
4. Vials, 2-mL, glass, with PTFE-lined septa and
crimp seals.
6. Volumetric flask, 10-mL
7. Pipets, 1.0-mL
8. Cold room or cold box for preparing
standards at 0 °C or lower.
9. Syringes, gas-tight, 10- and 100-//L
SPECIAL PRECAUTIONS: Difluorodibromomethane does not have adequate warning properties [3].
SAMPLING:

2. Break the ends of the front and back sorbent tubes immediately before sampling. Connect the
tubes with a short piece of plastic tubing and attach sampler to personal sampling pump with
flexible tubing.
2.5 to 10 L
4. Separate the two sorbent tubes. Cap the ends of each tube with plastic (not rubber) caps and
pack securely for shipment.
SAMPLE PREPARATION:
5. Place the charcoal from the front and back sorbent tubes in separate vials. Discard the glass
6. Add 1 .0 mL 2-propanol to each vial. Attach crimp cap to each vial.
7. Allow to stand overnight with occasional agitation.
8. Calibrate daily with at least five working standards over the range 0.4 to 20 mg
dibromodifluoromethane per sample.

NOTE: Prepare the working standards in a cold room or cold box.

a. Add known amounts of cold (<0 °C) difluorodibromomethane to 2-propanol in 10-mL
volumetric flasks and stopper.
b. Allow standards to come to room temperature, and dilute to the mark.
d. Prepare calibration graph (peak area vs. mg difluorodibromomethane).
the calibration range (step 8). Prepare three tubes at each of five concentrations plus three
media blanks.
b. inject a known amount of cold (<0 °C) difluorodibromomethane directly onto front sorbent
NOTE 1 : Perform this step in a cold room or cold box.
NOTE 2: For small quantities (0.4 to 4 mg), use 2 to 20 //L of a 200 mg/mL standard
solution of
difluorodibromomethane in pentane.
e. Prepare a graph of DE vs. mg dibromodifluoromethane recovered.
MEASUREMENT:
autosampler.
desorbed liquid with 2-propanol, reanalyze, and apply the appropriate dilution factor in
calculations.
CALCULATIONS:
13. Determine the mass, mg (corrected for DE) of difluorodibromomethane found in the sample front
sorbent sections.
14. Calculate concentration, C, of difluorodibromomethane in the air volume sampled, V (L):
C .
Method S107 was issued on April 11, 1975, and evaluated at 470, 932, and 1876 mg/m3 [1]. Spiking of
samples and standards preparation were done in a cold room (0 °C). Samples of
difluorodibromomethane in air were generated and collected on activated coconut charcoal (SKC Lot
105). The air concentration was independently determined by gas chromatographic analysis using a
5-mL sampling loop and comparison to gas bag samples. The mean desorption efficiency over the
range 4.4 to 18.5 mg difluorodibromomethane per sampler was 99.5%. The breakthrough volume for
100-mg charcoal beds was 15.6 L at 1875 mg/m3, low relative humidity, and a flow rate of 0.2 L/min.
No storage stability study was done.

REFERENCES:
METHOD REVISED BY:
Y. T. Gagnon, NIOSH/DPSE; S107 validated under NIOSH Contract CDC-99-74-45.

DIISOBUTYL KETONE

DIMETHYLACETAMIDE 2004
MW: 87.12 CAS: 127-19-5 RTECS: AB7700000

OSHA: 10 ppm (skin) PROPERTIES: liquid; BP 164.5 - 166 °C; MP -20 °C;
NIOSH: 10 ppm (skin) d 0.937 g/mL @ 25 ° C; VP 1 .5 mm Hg
ACGIH: 10 ppm (skin) @ 20 °C; flash point 70 °C, explosive
(1 ppm = 3.56 mg/m3 @ NTP) range 1.8 to 11.5%
SYNONYMS: N,N-dimethylacetamide; acetyldimethylamine; DMAC

ANALYTE: dimethylacetamide
DESORPTION: 1 mLmethanol; 1 h in ultrasonic bath
VOL-MIN: 15 L@ 30 mg/m3
-MAX: SOL INJECTION
VOLUME: 5 //L
SHIPMENT: routine
STABILITY: at least 5 days @ 25 °C [1] -COLUMN: 140 °C
COLUMNS: 1.5 m x 6-mm OD glass; 10% UCON

50-HB-5100, 2% KOH on 100/120 mesh
Chromosorb WHP
ACCURACY
CALIBRATION: analyte in methanol
RANGE STUDIED: 18 to 105 mg/m3 [1J;
(45-L samples) RANGE: 0.5 to 4 mg per sample [1,2]
BIAS: - 0.8%
ACCURACY: ± 11.7%
APPLICABILITY: The working range is 10 to 80 mg/m3 of dimethylacetamide or dimethyformamdide for a 50-L air sample.
The lower limit is determined by the desorption efficiency which must be determined over the range used. Silica gel has a high
affinity for water; high relative humidity may adversely affect the efficiency of analyte adsorption.
INTERFERENCES: None identified. Separation conditions (column, temperature, ete.) may be changed to circumvent
problems. Alternate columns include: 60/80 mesh Chromosorb P coated with 20% UCON LB550X and 2% KOH; 100/120 mesh
Chromosorb WHP with 10% Carbowax 20Mand 2% KOH; 100/120 mesh Chromosorb WHP with 10% SP-2250; and 30-m xO.32-
mm capillary column coated with 0.5 /urn DB Wax..
OTHER METHODS: This combines and replace Methods S254 and S255 [2].

DIMETHYLACETAMIDE and DIMETHYLFORMAMIDE: METHOD 2004, Issue 2, dated 15 August 1994 - Page 2 of 4
1. Methanol, reagent grade.* 1. Sampler: . glass tube, 7 cm long, 6-mm OD,

2. Analyte: dimethylacetamide, reagent grade, 4-mm ID, with plastic caps, containing two
or dimethylformamide, reagent grade.* sections of 20/40 mesh silica gel (front = 150
3. Acetone, reagent grade.* mg; back = 75 mg) separated by a 2-mm
4. Desorption efficiency (DE) stock solution, urethane foam plug. A silylated glass wool
0.05 mg/mL Prepare solutions of plug precedes the front section and a 3-mm
dimethylacetamide or dimethylformamide urethane foam plug follows the back section.
fresh daily in acetone. The pressure drop across the tube must be
5. Hydrogen, prepurified. less than 3.4 kPa (2.5 cm Hg) at an airflow of
6. Air, filtered, compressed. 1 L/min. Tubes are commercially available.
7. Nitrogen, purified. 2. Personal sampling pump, 0.01 to 1 L/min, with
* See SPECIAL PRECAUTIONS. 3. Gas chromatograph, FID, integrator, and
4. Vials, 2-mL, PTFE-lined crimp cap, or
automatic sampler vials.
5. Microliter syringes, 10-//L and other convenient
size for making standards.
6. Pipets, 1 .0 mL
8. Ultrasonic bath.
SPECIAL PRECAUTIONS: Acetone and methanol are flammable and a dangerous fire and explosion
risk. They are moderately toxic by ingestion and inhalation.
Dimethylacetamide and dimethylformamide are strong irritants to skin and tissue and moderate fire risks.
SAMPLING:

3. Sample at an accurately known flow rate between 0.01 to 1 L/min for a total sample size of 15
to 80 L
SAMPLE PREPARATION:
6. Add 1.0 mL methanol to each vial. Attach crimp cap to each vial.
8. Calibrate daily with at least six working standards over the ranges 0.05 to 4 mg
dimethylacetamide or dimethylformamide per sample.
a. Add known amounts of analyte (neat or diluted with methanol) to methanol in 10-mL


c. Prepare calibration graph (peak area vs. mg analyte).
9. Determine desorption efficiency (DE) at least once for each lot of silica gel used for sampling in
b. Inject a known amount (1 to 20 fjL) of pure analyte or DE stock solution directly onto front
sorbent section with a microliter syringe.
MEASUREMENT:
autosampler.
NOTE: If peak area is above the linear range of the working standards, dilute with methanol,
CALCULATIONS:
13. Determine mass, mg (corrected for DE), of analyte found in the sample front (Wf) and back (Wb)
C . ,
Method S254 for dimethylacetamide was evaluated over the range of 18 to 105 mg/m3 at an
atmospheric temperature and pressure of 24 °C and 760 mm Hg using a 45-L sample [1].
Breakthrough occurred when sampling a test atmosphere containing 105.6 mg/m3 of dimethylacetamide
at 0.876 L/min for 240 min. The front section of the silica gel tube was found to hold 22.2 mg
dimethylacetamide under these conditions. The collection efficiency test conducted at a concentration
of 105.6 mg/m3 was determined to be 1.00. Desorption efficiency at 0.943, 1.886, and 3.77 mg per silica
gel tube was 88.8, 93.8, and 94.9%, respectively. A storage study for five days at 1.866 mg per silica gel
tube gave a recovery of 93.6%. Overall sampling and measurement precision, §rT, was 0.067.
Method S255 for dimethylformamide was evaluated over the range of 1 1 to 61 mg/m3 at an atmospheric
temperature and pressure of 23 °C and 761 mm Hg using a 45-L sample [1]. Breakthrough occurred
when a test atmosphere containing 119.5 mg/m3 of dimethylformamide was sampled at 0.859 L/min for
146 min. The front section of the silica gel tube was found to hold 15 mg of dimethylformamide under
these conditions. The collection efficiency test conducted at a concentration of 61.1 mg/m3 was
determined to be 1.00. Desorption efficiency at 0.759, 1.518, and 3.04 mg per silica gel tube was 88.7,
90.4, and 92.2%, respectively. A storage study for five days at 1.5 mg dimethylformamide per silica gel

tube gave a recovery of 91.7%. Overall sampling and measurement precision, SrT> was 0.056.
REFERENCES:
[1] Documentation of the NIOSH Validation Tests, S254 (Dimethylacetamide) and S255
(Dimethylformamide), U.S. Department of Health, Education, and Welfare, Publ. (NIOSH) 77-185
(1977), available as GPO Stock #017-033-00231-2 from Superintendent of Documents,
Washington, DC 20402.
[2] NIOSH Manual of Analytical Methods, 2nd ed., Vol. 3, S254 and S255, U.S. Department of
Health, Education, and Welfare, Publ. (NIOSH) 77-1 57-C (1977).
METHOD REVISED BY:
C. Neumeister, NIOSH/DPSE; S254 and S255 originally validated under NIOSH Contract CDC-99-74-45.

DIMETHYLAMINE

DIMETHYLAMINE

DIMETHYLFORMAMIDE 2004
(See Method 2004, DIMETHYLACETAMIDE, for procedure)
= CHN(CH3) MW: 73.10 CAS: 68-12-2 RTECS: LQ2100000

OSHA : 10 ppm (skin) PROPERTIES: liquid; d 0.95 g/mL @ 25 °C; BP 153 °C;
NIOSH: 10 ppm (skin) MP -61 °C; VP 2.7 mm Hg @ 20 °C;
ACGIH: 10 ppm (skin) explosive range in air (v/v) 2.2 to 15.2%
1 ppm = 2.99 mg/m3 @ NTP
SYNONYMS: N-formyldimethylamine; DMF; N,N-dimethylformamide

ANALYTE: dimethylformamide
DESORPTION: 1 mLmethanol; 1 h in ultrasonic bath
VOL-MIN: 15 L@30 mg/m3
-MAX: SOL INJECTION
VOLUME: 5 fjL
SHIPMENT: routine
STABILITY: at least 5 days @ 25 °C [1] -COLUMN: 140 °C
COLUMNS: 1.5 m x 6-mm OD glass; 10% UCON

50-HB-5100, 2% KOH on 100/120 mesh
Chromosorb WHP
ACCURACY
CALIBRATION: analyte in methanol
RANGE STUDIED: 11 to 61 mg/m3 [1];
BIAS: - 1.1%
OVERALL PRECISION (§„): 0.056 [1]
PRECISION (§r): 0.037 [1]
ACCURACY: ± 11.7%
APPLICABILITY: The working range is 3.3 to 27 ppm (10 to 80 mg/m3) for a 50-L air sample. The lower limit is determined
by the desorption efficiency which must be determined over the range used. Silica gel has a high affinity for water; high relative
humidity may adversely affect the efficiency of analyte adsorption.
INTERFERENCES: None identified. Separation conditions (column, temperature, etc.) may be changed to circumvent
problems. Alternate columns include: 60/80 mesh Chromosorb P coated with 20% UCON LB 550Xand 2% KOH; 100/120 mesh
Chromosorb WHP with 10% Carbowax 20M and 2% KOH; 100/120 mesh Chromosorb WHP with 10% SP-2250; and 30-m x 0.32-
mm capillary coated with 0.5 //m DB Wax.
OTHER METHODS: This combines and replace Methods S254 and S255 [2].

1,1-DIMETHYLHYDRAZINE 3515
(CH3)2NNH2 MW: 60.10 CAS: 57-14-7 RTECS: MV2450000
OSHA : C 0.5 ppm (skin) PROPERTIES: liquid; MP - 58 °C; BP 63 °C; d 0.80 @

NIOSH: C 0.06 ppm/120 min; carcinogen 20 °C; VP 157 mm Hg @ 25 °C; vapor
ACGIH: C 0.5 ppm (skin); suspected human carcinogen density (air = 1) 2.07; flash point - 15 °C
(1 ppm = 2.46 mg/m3 @ NTP) (closed cup); flammable range 2 to 95%
v/v in air
SYNONYMS: dimazine; unsym-dimethvlhvdrazine: N,N-dimethylhydrazine.
SAMPLER: BUBBLER TECHNIQUE: VISIBLE SPECTROPHOTOMETRY

(0.1 M hydrochloric acid)
ANALYTE: complex of phosphomolybdic acid and
FLOW RATE: 0.2 to 1.0 L/min 1,1 -dimethyl hydrazine
VOL-MIN: 2 L @ 0.5 ppm PROCEDURE: add phosphomolybdic acid; heat sample

-MAX: 100 L solution at 95 "C for 60 min; cool
solution under tap water; transfer sample
SHIPMENT: remove bubbler stem and rinse with 0.1 M to 1-cm cell; read absorbance at 730 nm
hydrochloric acid; seal bubbles with non-
reactive stopper CALIBRATION: standard solutions of 1,1-
dimethylhydrazine in 0.1 M hydrochloric
SAMPLE acid
ACCURACY PRECISION (Sr): 0.072 [1]

(91 -L samples)
BIAS: - 1.9%
OVERALL PRECISION (SrT): 0.062(1]
ACCURACY: ± 14.0%
APPLICABILITY: The working range is 0.008 to 1 ppm (0.02 to 2.5 mg/m3) for a 100-L air sample. This method is also
applicable to ceiling measurements.
INTERFERENCES: Other hydrazines, as well as, stannous ion, ferrous ion, zinc, sulfur dioxide, and hydrogen sulfide, may give
a positive interference. Negative interferences in the method may occur by oxidation of the 1,1 -dimethyl hydrazine by halogens,
oxygen (especially in the presence of copper (I) ion) and hydrogen dioxide.
OTHER METHODS: This revises Method 81 43 [2]. Method P&CAM 248 [3] describes an acid-coated silica gel sorbent tube/gas
chromatographic method for the determination of hydrazine, monomethylhydrazine, 1,1 -dimethylhydrazine, and phenylhydrazine.
Sample stability problems have been noted with P&CAM 248 [4].

1,1-DIMETHYLHYDRAZINE: METHOD 3515, Issue 2, dated 15 August 1994 - Page 2 of 3
1. 1,1-Dimethylhydrazine,* ACS reagent grade. 1. Sampler: 25-mL bubbler with 10 mL 0.1 M

2. Hydrochloric acid, ACS reagent grade. hydrochloric acid.
3. Collection medium, 0.1 M hydrochloric acid. 2. Personal sampling pump, 0.2 to 1.0 L/min,
To 300 mL of distilled water in a 1000-mL with flexible polyethylene or PTFE tubing.
volumetric flask, add 8.6 ml_ of concentrated 3. Glass or non-reactive stopper for bubbler.
hydrochloric acid with caution. Mix and 4. Glass tube, 5 cm long by 6-mm I.D., loosely
bring to volume with distilled water. packed with glass wool.
4. Phosphomolybdic acid solution. Dissolve 5. Spectrophotometer, set at 730 nm.
15 g of phosphomolybdic acid in 500 mL 6. 1 -cm spectrophotometer cells.
distilled water, allow to stand one day, and 7. Test tube, large.
filter through a fluted paper filter. 8. Volumetric flasks, 50-mL, 100-mL, 500-mL,
5. Water, deionized and distilled. 1000-mL
6. Calibration stock solution, 1 mg/mL Weigh 9. Pipets, 10-, 15-, 25, and 50-fjL; 10- and 15-mL
500 mg of 1,1-dimethylhydrazine in a 100-mL glass, delivery, with pipet bulb.
volumetric flask and fill to the mark with 0.1 10. Graduated cylinders, glass, 10-mL, 25-mL
M hydrochloric acid. 11. Water bath at 95 °C.
12. Stopwatch.
13. Thermometer, ca. 0-120 °C.
SPECIAL PRECAUTIONS: 1,1-Dimethylhydrazine may be fatal if inhaled, swallowed or absorbed

through the skin [5]. Contact may cause burns to skin and eyes. Vapor may be irritating to the eyes,
skin, and mucous membranes. Handle with caution and use appropriate protective equipment.
SAMPLING:

2. Transfer 10 mL 0.1 M hydrochloric acid to a bubbler.
3. Connect outlet arm of bubbler to the glass-wool-packed tube (to prevent splashover into the
pump) and then to the sampling pump with the flexible tubing.
4. Sample at an accurately known rate of 0.2 to 1.0 L/min for total sample size of 2 to 100 L
5. Remove bubbler stem and rinse with 2 mL of 0.1 M hydrochloric acid into bubbler body. Seal
bubbler with an inert stopper for shipment in a suitable container in order to prevent damage
during transit.
SAMPLE PREPARATION:
6. Transfer the liquid from the bubbler, quantitatively, to a volumetric flask.

7. Add 10 mL of phosphomolybdic acid solution and bring volume to 50 mL with 0.1 M
hydrochloric acid.
8. Transfer an aliquot of this solution to a large test tube and heat to 95 °C for 60 min. Place test
tube under running tap water to cool before measurement.
9. Calibrate daily with at least six working standards to cover the range of 1 to 250 //g 1,1 -dimethyl
hydrazine per sample.

1,1-DIMETHYLHYDRAZINE: METHOD 3515, Issue 2, dated 15 August 1994 - Page 3 of 3
a. Add appropriate aliquots (10, 20, 30, 40 and 50 fjL) of calibration stock solution to 10 mL of
0.1 M hydrochloric acid in 50-mL volumetric flasks. Prepare a reagent blank using only 10
mL of 0.1 M hydrochloric acid.
b. Treat with (steps 7 and 8) phosphomolybdic acid solution.
c. Analyze working standards together with samples and reagent blanks (steps 10 through 12)
on a spectrophotometer at 730 nm, using a 1-cm cell. Correct standards for reagent blank
absorbance.
d. Prepare a calibration graph of absorbance vs. amount (JJQ) of 1,1-dimethylhydrazine per 50
mL of sample.
MEASUREMENT:
10. Set spectrophotometer according to manufacturer's recommendations to monitor 730 nm.

11. Fill 1-cm sample cell with sample or standard.
12. Measure absorbance.
CALCULATIONS:
13. Determine mass, fjg, of analyte found in sample (W) and average reagent blank (B).
14. Calculate concentration (C) of 1,1-dimethylhydrazine in the air volume sampled V (L):
C = —-^— , mg/m3.
This method was evaluated over the range 0.5 to 2.3 mg/m3 using 91 -L samples [1]. Sampling and
measurement precision, S,T was 0.062 for samples collected at the OSHA standard. Bias could not be
determined owing to instability of the 1,1-dimethylhydrazine in the generator. Collection efficiency of the
bubblers was determined to be 99.1% at 2.2 mg/m3. Sample stability during storage was evaluated at
100 //g 1,1-dimethylhydrazine per sample. Samples showed 101.3% recovery after five days of storage
at ambient conditions.
REFERENCES:
[1] Backup Data Report for 1,1-Dimethylhydrazine, prepared under NIOSH Contract 210-76-0123
(1977).
[2] NIOSH Manual of Analytical Methods, 2nd e.d., V. 3, S143, U.S. Department of Health,
[3] NIOSH Manual of Analytical Methods, 2nd e.d., V. 4, 248, U.S. Department of Health, Education,
[4] LR. Cook, R.E. Glenn and G.E. Poddak, Am. Ind. Hyg. Assoc. J.. 40, 69-74 (1979).
and Human Services, Publ. (NiOSH) 81-123 (1981), available as GPO Stock #17-033-00337-8
from Superintendent of Documents, Washington, D.C. 20402.
METHOD REVISED BY:
E.R. Kennedy, Ph.D., NIOSH/DPSE.

DIMETHYL SULFATE 2524
(CH30)2S02 MW: 126.13 CAS: 77-78-1 RTECS: WS8225000

OSHA : 0.1 ppm (skin) PROPERTIES: liquid; d 1.332 g/mL @ 20 °C;

NIOSH: 0.1 ppm/8 hours (skin); carcinogen BP 188 °C with decomposition;
ACGIH: 0.1 ppm (skin); suspect carcinogen MP -31.8 °C; VP 0.07 kPa (0.5 mm Hg; 700
(1 ppm = 5.16 mg/m3 @ NTP) ppm) @ 20 °C
SYNONYMS: methyl sulfate
SAMPLER: SOLID SORBENT TUBE TECHNIQUE: GAS CHROMATOGRAPHY,

(Poropak P, 100 mg/50 mg) ELECTROLYTIC CONDUCTIVITY
DETECTOR (SULFUR MODE)
ANALYTE: dimethyl sulfate
VOL-MIN: 0.25 L @ 1 ppm
-MAX: 12 L DESORPTION: 1 mL diethyl ether, 30 min
SAMPLE INJECTION VOLUME: 4 //L

STABILITY: at least 1 week @ 25 °C [1]
BLANKS: 2 to 10 field blanks per set -COLUMN: 2 min @ 50 °C; then
30°C/minto120°C;hold
CARRIER GAS: He, 20 m L/min
COLUMN: 1.8 m x 3.2-mm OD stainless steel,

packed with 5% DEGS on 80/100 mesh
ACCURACY Chromosorb WHP
RANGE STUDIED: 1.8 to 24.5 mg/m3 [1] CALIBRATION: dimethyl sulfate in diethyl ether
(1.2-L samples)
RANGE: 1 to 120 //g per sample
OVERALL PRECISION (SrT): 0.073 [1] ESTIMATED LOD: 0.25 //g per sample [1]
PRECISION (Sr): 0.06 @ 1.1 to 39 //g per sample [1]
OTHER METHODS : This revises P&CAM 301 [2].

DIMETHYL SULFATE: METHOD 2524, Issue 2, dated 15 August 1994 - Page 2 of 4
1. Dimethyl sulfate, 99%.* 1. Sampler: glass tube, 7 cm long, 6-mm OD,

2. Diethyl ether,* anhydrous, preserved with 4-mm ID, flame-sealed ends with plastic caps,
ethanol. containing two sections of 50/80 mesh
3. Calibration stock solution, 12 //g///L Add 120 Porapak P (front = 100 mg; back = 50 mg)
mg (90 //l_) dimethyl sulfate to a pre-weighed separated by a 2-mm urethane foam plug. A
1 0-mL volumetric flask. Re-weigh and dilute to silylated glass wool plug precedes the front
the mark with diethyl ether. section and a 3-mm urethane foam plug
4. Helium, purified. follows the back section. Pressure drop
across the tube at 0.2 L/min airflow must be
* See SPECIAL PRECAUTIONS. available.
NOTE: Some batches of Porapak P initially
gave poor recovery. Good recoveries
were obtained after the sorbent had
been heated at 180 °C in a vacuum
oven for 16 hrs.
3. Gas chromatograph, electrolytic conductivity
detector (sulfur mode), integrator, and column
(see page 2524-1).
NOTE: A new column must be primed before
attempting quantitative work by repeatedly
injecting aliquots of calibration stock solution
until the detector response to dimethyl sulfate
reaches a plateau.
4. Vials, 2-mL, PTFE-lined crimp caps.
5. Syringes, 1 0-//L and other convenient sizes for
preparing standards, readable to 0.1 -fjL.
7. Pipets, 1-mL
SPECIAL PRECAUTIONS: Dimethyl sulfate is a suspect carcinogen, and both the liquid and vapor are
extremely severe irritants to skin, eyes, and mucous membranes. It is an insidious hazard -- warning
properties are poor and symptoms are delayed up to 10 h or more [3,4]. All transfers involving dimethyl
sulfate should be performed in a fume hood. Personal protective equipment should be used to prevent
any bodily exposure even to the vapor.
Diethyl ether is an extreme fire (flash point = -45 DC) and explosion hazard (possible peroxide
formation); work with it only in a hood.
SAMPLING:

0.25to 12 L

SAMPLE PREPARATION:
separating plugs.
6. Add 1.0 mL diethyl ether to each vial. Attach crimp cap to each vial.
7. Allow 10 stand 30 min with occasional agitation.
8. Calibrate daily with at least five working standards over the range 0.25 to 120 fjg dimethyl sulfate
per sample (2.5 to 1200 //g/10 mL).
a. Add known amounts of calibration stock solution to 10-mL volumetric flasks and dilute to the
mark with diethyl ether.
c. Prepare calibration graph (peak area vs. //g dimethyl sulfate).
9. Determine desorption efficiency (DE) at least once for each lot of Porapak P used for sampling
blanks.
microliter syringe.
e. Prepare a graph of DE vs. //g dimethyl sulfate recovered.
MEASUREMENT:
on page 2524-1. Set electrolytic conductivity detector for operation in sulfur mode according to
manufacturer's recommendations. Inject sample aliquot manually using solvent flush technique
or with autosampler.
desorbed liquid with diethyl ether, reanalyze, and apply the appropriate dilution factor in
calculations.
CALCULATIONS:
13. Determine the mass, fjg (corrected for DE) of dimethyl sulfate found in the sample front (Wf) and
sections.
14. Calculate concentration, C, of dimethyl sulfate in the air volume sampled, V (L):
^ Wf + Wbb - Bff - Bbb

For the evaluation, a Tracor Model 310 Hall electrolytic conductivity detector was used [1]. It was
operated with a furnace temperature of 950 °C, oxygen at 20 mL/min as the reactant gas, and filtered,
deionized water at 1 mL/min as the conductivity solvent. The capacity of Porapak P for the collection of
dimethyl sulfate was estimated from a log retention volume vs. reciprocal absolute temperature plot of
data obtained by chromatographing 30-//g quantities of dimethyl sulfate on a 100-mg sorbent bed.
Based on these data, the estimated volumetric capacity decreases from 39 L at 25 °C to 16 L at 35 °C.
In a test of humidity and storage effects, six tubes were spiked with 0.6 //g dimethyl sulfate. After
passing 12 L of humid air (80% RH) through each, they were stored for seven days. Upon analysis,
these samples showed no significant loss of dimethyl sulfate.
This method was compared with an independent method based on collection of dimethyl sulfate on
Tenax-GC, derivatization of g-nitrophenol with the collected dimethyl sulfate, and HPLC (UV detection) of
the resulting p_-nitroanisole. For three sets of six dynamically-generated samples, the concentrations and
precisions (relative standard deviations) found using this method were 1.8 (0.061), 4.35 (0.074), and 24.5
(0.070) //g/L The corresponding results found by the independent method for simultaneously-generated
samples were 3.18 (0.153), 7.18 (0.090), and 20.4 (0.086) //g/L Because of the inconsistency of the
results and possible inaccuracy in the independent method, the accuracy of this method remains to be
determined.
REFERENCES:
[1] Lunsford, R. A., and P. M. Fey. Backup Data Report for P&CAM 301 (NIOSH, unpublished,
December 29, 1978).
[3] The Merck Index, 11th Ed., Merck & Co., Inc., Rahway, NJ (1989).
METHOD WRITTEN BY:
R. Alan Lunsford, Ph.D., NIOSH/DPSE.

N,N-DIMETHYL-a-TOLUIDINE
See AMINES, AROMATIC (Method 2002) for procedure

DIOXANE 1602
MW:88.11 CAS: 123-91-1 RTECS: JG8225000

OSHA : 100 ppm (skin) PROPERTIES: liquid; d 1.0337 g/mL @ 20 °C;

NIOSH: 1 ppm/30 min; carcinogen BP 101 °C; MP 12 °C
ACGIH: 25 ppm (skin); carcinogen VP 3.9 kPa (29 mm Hg; 3.8% v/v) @ 20 °C;
(1 ppm = 3.60 mg/m3 @ NTP) explosive range 2 to 22% v/v in air
SYNONYMS: dioxan; p-dioxane; 1.4-diethylene dioxide; diethylene ether

ANALYTE: dioxane
DESORPTION: 1 mL CS2, 30 min
-MAX: 15 L INJECTION VOLUME: 5 //L
SAMPLE TEMPERATURE-INJECTION: 225 "C

STABILITY: > 1 week @ 25 °C -DETECTOR: 250 °C
>6 weeks @ -10 °C -COLUMN: 75 °C
BLANKS: 2 to 10 field blanks per set CARRIER GAS: He, 30 mL/min (60 psig)
COLUMN: 6 m x 3-mm stainless steel packed with

10% FFAP on 80/100 mesh Chromosorb
W-HP Chromosorb W-HP
ACCURACY CALIBRATION: solutions of dioxane in CS2 with internal

standard
BIAS: + 9%
ACCURACY: ± 18.7
APPLICABILITY: The working range is 5.5 to 190 ppm (20 to 700 mg/m3) for a 10-L air sample.
INTERFERENCES: None known. An alternate GC column is 30 m x 0.32-mm ID fused silica capillary coaled with 1 fjm DB-5
[3].
OTHER METHODS: This method combines and replaces S360 [4] and P&CAM 127 [5] for dioxane. A similar method appears
in the dioxane criteria document [6].

DIOXANE: METHOD 1602, Issue 2, dated 15 August 1994 - Page 2 of 4
1. Eluent: carbon disulfide,* chromatographic Sampler: glass tube, 7 cm long, 4-mm ID,
quality, containing 0.1% (v/v) octane, decane, flame-sealed ends with plastic caps, containing
or other suitable internal standard. two sections of activated (600 °C) coconut
2. Dioxane, reagent grade.* shell charcoal (front =100 mg; back = 50 mg)
3. Desorption efficiency (DE) stock solution, 0.1 separated by a 2-mm urethane foam plug. A
mg///L Dilute 1 g dioxane to 10 mL with silylated glass wool plug precedes the front
pentane. section and a 3-mm urethane foam plug
4. Helium, purified. follows the back section. Pressure drop
5. Hydrogen, prepurified. across the tube at 1 L/min airflow must be
6. Air, compressed, filtered. less than 3.4 kPa. Tubes are commercially
available.
* See SPECIAL PRECAUTIONS. with flexible connecting tubing.
5. Syringes, 10-//L and other convenient sizes for
preparing standards, readable to 0.1 -fjL.
7. Pipet, 1-mL
SPECIAL PRECAUTIONS: Carbon disulfide is toxic and a serious fire and explosion hazard (flash point
= -30 °C).
Dioxane is toxic, causing central nervous system depression and necrosis of liver and kidneys, as well
as a skin irritant [6], and a suspect carcinogen [7]. Use personal protective equipment and work only
in a hood.
SAMPLING:

0.5 to 15 L
SAMPLE PREPARATION:
8. Calibrate daily with at least five working standards over the range 0.01 to 7 mg dioxane per
sample.

a. Add known amounts of dioxane to eluent in 10-mL volumetric flasks and dilute to the mark.
By serial dilution, prepare solutions containing 0.01 to 7 mg dioxane/mL
mg dioxane).
b. Inject a known amount (1 to 20 //L) of dioxane or DE stock solution directly onto front
sorbent section with a microliter syringe.
e. Prepare a graph of DE vs. mg dioxane recovered.
MEASUREMENT:
autosampler.
same chromatogram.
CALCULATIONS:
13. Determine the mass, mg (corrected for DE) of dioxane found in the sample front (Wf) and back
sections.
14. Calculate concentration, C, of dioxane in the air volume sampled, V (L):
C . * Wb - B, - BJ •
Method S360 [4] was issued on March 14, 1975, and validated over the range 155 to 651 mg/m3 using
atmospheres generated by calibrated syringe pump [1]. Desorption efficiency averaged 0.88 in the
range 1.8 to 7.3 mg dioxane per sample. Breakthrough was observed when a test atmosphere
containing 651 mg/m3 of dioxane in dry air was sampled at 0.19 L/min for 210 min (40-L air sample
volume). The front section held 26 mg of dioxane. Precision and accuracy are listed on page 1602-1.
A similar method, without internal standard, was collaboratively tested in the range 6 to 190 ppm
dioxane [2,8].
REFERENCES:
Welfare, Publ (NIOSH) 77-185 (1977), available as GPO Stock #017-033-00231-2 from

[2] Collaborative Testing of Activated Charcoal Sampling Tubes for Seven Organic Solvents, 4-22, 4-27,
U.S. Department of Health, Education, and Welfare, Publ. (NIOSH) 75-184 (1975).
[3] UBTL, Inc., NIOSH Sequence Report #4176-K (unpublished, December 19, 1983).
[5] Ibid., Vol. 1., P&CAM 127, U.S. Department of Health, Education, and Welfare, Publ. (NIOSH)
77-1 57-A (1977).
[6] Criteria for a Recommended Standard. ..Occupational Exposure to Dioxane, U.S. Department of
[8] Larkin, R. L, J. V. Crable, L R. Catlett, and M. J. Seymour. Collaborative Testing of a Gas
Chromatogrphic Charcoal Tube Method for Seven Organic Solvents, Am. Ind. Hvg. Assoc. J., 38,
543 (1977).
METHOD REVISED BY:
Robert W. Kurimo, NIOSH/DPSE; S360 originally validated under NIOSH Contract CDC-99-74-45.

DIPHENYL 2530
C6H5C6Hf MW: 154.21 CAS: 92-52-4 RTECS: DU8050000

OSHA : 0.2 ppm PROPERTIES: MP 69 °C; BP 255 °C

NIOSH: 0.2 ppm VP 8 Pa (0.06 mm Hg; 79 ppm)
ACGIH: 0.2 ppm @25 °C; flash point 113 °C
(1 ppm = 6.30 mg/m3 @ NTP)
SYNONYMS: biphenyl

(Tenax GC, 20 mg/10 mg))
ANALYTE: diphenyl
DESORPTION: 1 mL CCI4, stand 15 min
VOL-MIN: 15 [email protected] ppm
-MAX: SOL INJECTION VOLUME:

-DETECTOR: 250 °C
SAMPLE STABILITY: 95% recovery after 7 days -COLUMN: 135 °C
@ room temperature
COLUMN: 1.8 m x 4-mm ID glass packed with 5%
OV-17 on 80/100 mesh Chromosorb W
CALIBRATION: standard solutions of biphenyl in CCI4

ACCURACY
RANGE: 4 to 120 //g per sample
RANGE STUDIED: 0.64 to 2.4 mg/rrr [1]
(30-L samples) ESTIMATED LOD: 0.09 fjg per sample [1]
BIAS: - 6.4%
PRECISION (Sr): 0.019 [1] @ 19 to 76 pg per sample
ACCURACY: ± 15.33%
APPLICABILITY: The working range is 0.02 to 0.63 ppm (0.13 to 4 mg/m ) for a 30-L air sample. Measurement of
concentrations down to 0.01 mg/m may be possible if the desorption efficiency remains adequate.

DIPHENYL: METHOD 2530, Issue 2, dated 15 August 1994 - Page 2 of 4
1. Acetone, reagent grade.* 1. Sampler: glass tube, 6 cm long, 6-mm OD, 4-

2. Hexane, reagent grade.* mm ID, containing two sections of cleaned
3. Carbon tetrachloride (CCI4), reagent grade.* 35/60 mesh Tenax GC (front = 20 mg; back
4. Diphenyl, reagent grade. = 10 mg), separated by 2-mm urethane foam
5. Calibration stock solution, 1.2 mg/mL Dilute plug. A silylated glass wool plug is placed at
an accurately weighed 120-mg portion of both ends. Pressure drop across the tube at
diphenyl to 100 mL with carbon tetrachloride. 0.5 L/min must be less than 3.4 kPa. CIeaned
6. Desorption efficiency (DE) stock solution, 12 Tenax GC Tubes are commercially available.
mg/mL Dilute an accurately weighed 120-mg NOTE: CIean bulk Tenax GC by placing it in
portion of diphenyl to 10 mL with hexane. sintered glass filter fitted to large
7. Nitrogen, purified. vacuum flask. Add volume of acetone
equal to twice that of sorbent and
mix, then remove acetone by filtration.
* See SPECIAL PRECAUTIONS. Repeat washing six times. Dry sorbent
at 120 °C under vacuum for 4 h.
column (see page 2530-1).
7. Pipets, 1-mL, and other convenient sizes.
8. Balance, readable to 0.1 mg.
SPECIAL PRECAUTIONS: Hexane (flash point = -22 °C) and acetone (flash point = -18 °C) are
highly flammable and carbon tetrachloride is highly toxic. Prepare sorbent, samples, and standards in
well-ventilated hood.
SAMPLING:

2. Break the ends of the sampler tube immediately before sampling. Attach sampler to personal
15 to 30 L
SAMPLE PREPARATION:
6. Add 1.0 mL CCI4 to each vial. Cap each vial.
NOTE: Fine particles of Tenax tend to plug an autosampler syringe. For use with autosampler,
transfer supernatant solutions to autosampler vials.

DIPHENYL: METHOD 2530. Issue 2, dated 15 August 1994 - Page 3 of 4
8. Calibrate daily with at least six working standards over the range 0.1 to 120 //g diphenyl per
sample. Use serial dilutions for the smallest concentrations.
a. Add known amount of calibration stock solution to CCI4 in 10-mL volumetric flask and dilute
to the mark.
c. Prepare calibration graph (peak height or area vs. //g diphenyl per sample).
9. Determine desorption efficiency (DE) at least once for each lot of sorbent used for sampling in
b. Inject 2 to 10 fjL of DE stock solution (or of a serially diluted solution in hexane) directly
e. Prepare a graph of DE vs. //g diphenyl recovered.
MEASUREMENT:
autosampler.
NOTE 1 : If peak area is above the linear range of the working standards, dilute an aliquot of
the desorbed liquid with CCI4, reanalyze and apply the appropriate dilution factor in
calculations.
NOTE 2: Under these conditions, tr for diphenyl is approximately 6 min.
12. Measure peak height or area.
CALCULATIONS:
13. Determine the mass, fjg (corrected for DE) of diphenyl found in the sample front (Wf) and back
sections.
14. Calculate concentration, C, of diphenyl in the air volume sampled, V (L):
c. .... mg/m3.
Method S24 was issued on November 25, 1977 [2], and validated over the range 0.64 to 2.4 mg/m3
using 32-L samples collected on Tenax GC, Lot 04901 (Applied Science Laboratories) [1]. The diphenyl
concentration was independently determined by UV analysis of samples collected in methanol. Overall
precision, SrT, was 0.068 with an average recovery of 92.7%. Desorption efficiency averaged 0.987 in the
range 19 to 76 fjg per sample. For samples collected at 2.5 mg/m3, 25 °C, and >85% RH,
breakthrough to the backup section averaged 3.9% between 31.5 and 48.6 L, and 9.4% between 48.6
and 64.2 L Recovery from a set of samples stored one week under ambient conditions was 95.0%
relative to a set analyzed immediately. Previous work showed desorption efficiency to be poor (<0.7)
for diphenyl on SKC Lots 104 and 105 charcoals [1,3].

DIPHENYL: METHOD 2530, Issue 2, dated 15 August 1994 - Page 4 of 4
REFERENCES:
[1] Backup Data Report No. S24, Diphenyl, prepared under NIOSH Contract No. 210-76-0123
(November, 1977), available as "Ten NIOSH Analytical Methods, Set 4," Order No. PB281-038 from
[3] Failure Report S24, NIOSH Contract CDC-99-74-45 (unpublished, 1977).
METHOD REVISED BY:
R. Alan Lunsford, Ph.D., NIOSH/DPSE; S24 originally validated under NIOSH Contract No. 210-76-0123.

DYES, BENZIDINE-, O-TOLIDINE-, O-DIANISIDINE- 5013

OSHA : no PEL PROPERTIES: colored powders; water soluble;

NIOSH: lowest feasible; carcinogen VP not significant
ACGIH: carcinogen
SYNONYMS: Table 1.

ANALYTE: benzidine, o-tolidine, o-dianisidine
DESORPTION: 2 mL H2O; ultrasonic
VOL-MIN: 150 L @ 0.1 mg/m3
-MAX: 500 L REACTION: reductive cleavage of dye to free amine
with sodium hydrosulfite
SHIPMENT: keep samples dry and cool; protect from light
INJECTION
SAMPLE VOLUME: 10 //L
STABILITY: at least 7 days @ 25 °C in the dark
MOBILE PHASE: 60% methanol/40% phosphate buffer;
FIELD ambient temperature
COLUMN: 10 cm x 8-mm ID, Waters Radial Pak C,8,
BULK 10-//m particles, with Radial Compression
SAMPLE: include 1 bulk sample for each dye present on Module or equivalent
the filter
DETECTOR: UV detector @ 280 nm
ACCURACY
CALIBRATION: solutions of benzidine, o-tolidine and o-
RANGE STUDIED: not studied dianisidine in methanol
RANGE: ca. 15 to 250 //g per sample (Table 1)
ESTIMATED LOD: 3 //g benzidine per sample [1]
PRECISION (Sr): 0.04 to 0.08 [2,3]
APPLICABILITY: The working range is ca. 0.06 to 8 mg/m3 for a 250-L air sample. This method determines benzidine,
o-tolidine or o-dianisidine from dyes based on these amines, but will not distinguish different dyes based on the same amine.
The method will not distinguish benzidine obtained from reduction of the dyes and free benzidine in the dye formulation.
INTERFERENCES: Aniline, azobenzene, p_-aminophenol, g-phenylenediamine or p_-nitroaniline do not interfere in the

measurement when present in equimolar amounts.
OTHER METHODS: This revises P&CAM 325 [2,3]. P&CAM 234 [4,5], a general colorimetric method for diazonium salts and
azo dyes, has not been revised.

DYES, BENZIDINE-, o-TOLIDINE-, o-DIANISIDINE-: METHOD 5013, Issue 2, dated 15 August 1994 - Page 2 of 5
1. Water, deionized and distilled. 1. Sampler: PTFE filter, 5-//m, 37-mm (Millipore
2. Methanol, HPLC Grade. Mitex or equivalent), with backup pad in a
3. Benzidine.* three-piece plastic cassette filter holder.
4. o-Tolidine.* 2. Personal sampling pump, 1 to 3 L/min, with
5. o-Dianisidine.* flexible connecting tubing.
6. Calibration stock solutions. Dilute the 3. High pressure liquid chromatograph equipped
following amounts to 10 mL with methanol. with 280-nm UV detector, integrator and
Stable one month at 4 °C. column (page 501 3-1 ), Waters Model RCM 1 00
a. Benzidine, 15.6 mg Radial Compression Module with Waters
b. o-Tolidine, 15.3 mg Radial Pak C18 column or equivalent.
c. o-Dianisidine, 5.6 mg 4. Syringe or autosampler for HPLC injection.
7. Disodium hydrogen phosphate, Na2HPO4. 5. Syringes, volumetric, 10-, 25- and 50-fjL
8. Potassium dihydrogen phosphate, KH2PO4. 6. Flasks, volumetric, 10- and 100-mL, 1-L
9. Sodium hydrosulfite, Na2S2O4. 7. Vials, 4-mL, with screw caps.
10. HPLC mobile phase buffer. Dilute 3.39 g 8. Pipets, volumetric, 1-mL
KH2PO4 and 4.30 g Na2HPO4 to 1 L with water. 9. Tweezers.
Prepare daily. 10. Beakers, 50-mL
11. Reduction buffer. 1 1 . Ultrasonic water bath.
a. Solution A. Dilute 1.179 g KH2PO4 and
4.30 g Na2HPO4 to 1 L with water.
Prepare daily.
b. Solution B. Dilute 11.79 g KH2PO4 and
43.00 g Na2HPO4 to 1 L with water.
Prepare daily.
12. Reducing solution. Dilute 200 mg Na2S2O4 to
10 mL with the appropriate reduction buffer of
Solution A or B (see Table 1) immediately
before use.
SPECIAL PRECAUTIONS: NIOSH recommends that benzidine- and benzidine-congener-based dyes

be recognized and handled as human carcinogens because they can be reduced to the free aromatic
amine in living systems and eliminated by the usual metabolic pathways [4,6].
Benzidine is a recognized human carcinogen and regulated by the Occupational Safety and Health
Administration. o-Tolidine and o-dianisidine are currently suspect carcinogens and should be handled
accordingly [4,6]
SAMPLING:

2. Sample at an accurately known flow rate between 1 and 3 L/min for a total sample size of 150
to 500 L
SAMPLE PREPARATION:
3. Remove the filter from the cassette with clean tweezers and place it face up in a 50-mL beaker.
4. Add 1 .0 mL H2O to the beaker and swirl to wet the entire deposit.
5. Add another 1.0 mL H2O to the beaker and swirl.

DYES, BENZIDINE-, O-TOLIDINE-, o-DIANISIDINE-: METHOD 5013, Issue 2, dated 15 August 1994 - Page 3 of 5
6. Turn the filter sample side down and place the beaker in an ultrasonic bath for 15 min.
7. Pipet 1.0 mL desorbed sample solution to a 4-mL vial.
8. Add 1.0 mL freshly prepared reducing solution.
NOTE: Where the composition of the sample dye is unknown or different from the dyes listed in
Table 1, reduce a 1-mL aliquot of the desorbed dye solution with the reducing solution
made from buffer A. If precipitation of the dye from solution is observed at this point,
reduce the remaining 1-mL aliquot of the desorbed dye solution with the reducing
solution made with buffer B.
9. Cap the vial and allow to stand with occasional shaking for at least 1 h or until the change in
solution color is completed.
10. Calibrate daily.

a. Dilute aliquots of the calibration stock solutions for each of the amines (benzidine, o-tolidine,
o-dianisidine) to 10 mL with methanol in volumetric flasks. Prepare at least six working
standards to cover the ranges of interest (0.38 to 16 //g/mL benzidine; 0.77 to 15.3 //g/mL
o-tolidine; 0.56 to 11.7 //g/mL o-dianisidine).
b. Analyze the working standards together with samples and blanks (steps 12 through 14).
c. Prepare separate calibration graphs (peak area vs. //g per sample) for benzidine, o-tolidine.
and o-dianisidine. At the completion of step 9, the total effective volume of the solution
containing the entire sample is 4 mL
11. Determine recovery if the filter sample is known to contain only one dye.
a. Prepare a solution of a known concentration of the bulk sample of the dye in 10 mL H2O.
b. Add known volumes of this solution to PTFE filters using a microliter syringe and allow to
dry. Prepare three filters at each of five concentration levels.
c. Analyze the filters by steps 3 through 9 and 12 through 14.
d. On the day of analysis of the filters, add the same volume of dye solution which was spiked
onto the filters to 2.0 mL H2O. Reduce this solution (steps 7 through 9) and analyze
together with samples and standards (steps 12 through 14).
e. Calculate recovery (/jg benzidine, o-tolidine, or o-dianisidine recovered from the filter///g
from step 11.d).
f. Prepare graph of recovery vs. //g benzidine, o-tolidine or o-dianisidine recovered.
MEASUREMENT:
12. Set the HPLC to conditions given on page 5013-1 and in Table 1.
13. Inject 10 //L sample into the HPLC. Make duplicate injections of samples and standards.
14. Measure peak areas.
CALCULATIONS:
15. Read the mass, //g (corrected for recovery, if applicable) of the free amine corresponding to
each peak area for the sample (W) and average media blank (B) from the appropriate calibration
graph.
16. Calculate the concentration, C, of benzidine, o-tolidine or o-dianisidine in the air volume
sampled, V (L):
C - ( W " B ). mg/m3.

DYES, BENZIDINE-, o-TOLIDINE-, o-DIANISIDINE-: METHOD 5013, Issue .2, dated 15 August 1994 - Page 4 of 5
This method was laboratory evaluated over the ranges listed in Table 1 [2]. The concentration of dye
remaining after reduction varied from 0 to 6% as determined by visible spectrophotometry. The reduced
free amine was confirmed by GC/MS. The lower end of the measurement range was defined as the
level which gave at least 75% recovery with approximately 10% Sr. For C. I. Direct Red 28, the range
covered 27.3 to 273 jug dye per sample. The lower level of this range gave 94.4% recovery (Sr = 6.3%)
based on free benzidine for six replicate samples. For the other three dyes the results were as follows:
C. I. Direct Blue 6, 15.0 to 300.0 //g dye per sample, 100.3% recovery (Sr = 4.34%); C. I. Direct Brown
95, 24.3 to 243 //g dye per sample_, 78.5% recovery (Sr = 6.7%); C. I. Direct Black 38, 12.5 to 250.0 //g
dye per sample, 78.1% recovery (Sr = 12.8%). The pooled precisions (Sr) for samples at three
concentrations in the measurement range for each dye are as follows: Direct Red 28, 0.045; Direct Blue
6, 0.061; Direct Brown 95, 0.072; Direct Black 38, 0.078. Since the method does not distinguish between
various benzidine-based dyes, recovery correction factors cannot be applied unless a single known dye
is contained on the filter. Recovery studies must be performed on the bulks collected with the samples
because of variability in sample purity and variety of benzidine-based dyes. Recovery studies on spiked
samples stored at 75% relative humidity indicated no change due to humidity in the recoveries or sample
stability.
A user check of this method [1] gave estimated LODs for benzidine (3 jug per sample; 0.7 //g/mL) and
dianisidine (4.5 //g per sample; 1.1 //g/mL). The LODs could be lowered to 0.06 //g/mL for benzidine
and 0.07 //g/mL for dianisidine by using fluorescent detection with excitation at 285 nm and emission at
375 nm.
REFERENCES:
[1] User check, Wisconsin Occupational Health Laboratory (NIOSH, unpublished,

September 27, 1984).
[2] NIOSH Manual of Analytical Methods, 2nd ed., Vol. 6, P&CAM 325, U.S. Department of Health
[3] Kennedy, Eugene R. and Martha J. Seymour. Development of an Analytical Method for
Benzidine-Based Dyes, Chemical Hazards in the Workplace Measurement and Control, ACS
Symposium Series 149, American Chemical Society, Washington, DC, 21-35 (1981).
[4] Special Occupational Hazard Review for Benzidine-Based Dyes, U.S. Department of Health,
[6] Preventing Health Hazards from Exposure to Benzidine Congener Dyes, U.S. Department of
METHOD WRITTEN BY:
Eugene R. Kennedy, Ph.D., Martha J. Seymour and Charles E. Neumeister, NIOSH/DPSE.

UNIVERSITY OF MINNESOTA
3 1951 D01 338810 5
Delivering on the Nation's promise:

Safety and health at work
For all people
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U.S. DEPARTMENT OF HEALTH AND HUMAN SERVICES

NIOSH Manual of Analytical Methods (NMAM'™')

U.S. DEPOSITORY PROPERTY

May 15, 1996

NIOSH Manual of Analytical Methods

INSTRUCTIONS FOR INSERTING FIRST SUPPLEMENT INTO YOUR MANUAL

Using NMAM (Blue pages)

Indexes (Yellow pages - end of 3rd volume)

Ammonia by IC, 6016

Peter M. Eller, Ph.D., CIH

Mary Ellen Cassinelli

U.S. DEPARTMENT OF HEALTH AND HUMAN SERVICES

DHHS (NIOSH) Publication No. 94-113

Adherence to exposure control limits has been an important strategy

The methods presented in this improved Fourth Edition are intended to be

Linda Rosenstock, M.D., M.P.H.

5/15/96 vi NIOSH Manual of Analytical Methods

BARIUM, soluble compounds 7056

CADMIUM by FAAS 7048

5/1 5/96 vii NIOSH Manual of Analytical Methods

2,4-D and 2,4,5-T 5001

ELEMENTAL CARBON (DIESEL EXHAUST) 5040

ELEMENTS by ICP 7300

5/1 5/96 viii NIOSH Manual of Analytical Methods

FLUORIDE in urine 8308

GLUTARALDEHYDE by HPLC/UV 2532

5/15/96 ix NIOSH Manual of Analytical Methods

LEAD in air by chemical spot test 7700

MALEIC ANHYDRIDE 3512

5/15/96 x NIOSH Manual of Analytical Methods

5/1 5/96 xi NIOSH Manual of Analytical Methods

SILICA, AMORPHOUS 7501

5/15/96 xii NIOSH Manual of Analytical Methods

A. Unit Equivalents A-1

IV. Glossary of Abbreviations, Definitions and Symbols A-3

5/15/96 xiii NIOSH Manual of Analytical Methods

Meth. Eval Flow Rate Min. Max. Analytical

Acetaldehyde 2538 ACETALDEHYDE U 0.01-0.05 1 12 GC-FID XAD-2/HMP

Acetaldehyde 2539 ALDEHYDES, SCREENING P 0.01-0.05 5 5 GC-FID/MS XAD2/HMP

Acetaldehyde 3507 ACETALDEHYDE F 0.1-0.5 6 60 HPLC-UV BuB

Acetic acid 1603 ACETIC ACID F 0.01-0.1 20 300 GC-FID CCT

Acetic anhydride 3506 ACETIC ANHYDRIDE F 0.2-1.0 25 100 VIS BuB

Acetone 1300 KETONES 1 F 0.01-0.2 0.5 3 GC-FID CCT

Acetone 2549 VOLATILE ORGANIC CPDS (Screening) P 0.01-0.05 1 6 TD/GC-MS TD

Acetone cynnohydrin 2506 ACETONE CYANOHYDRIN P 0.2 0.3 12 GC-NPD PorQS

Acetonltrile 1606 ACETONITRILE P 0.01-0.2 3 25 GC-FID CCT

Acetylene dlchlorlde 1003 HYDROCARBONS, HALOGENATED P 0.01-0.2 0.2 5 GC-HD CCT

Acetylene tetrabromide 2003 1,1.2,2-TETRABROMOETHANE P 0.2-1.0 50 100 GC-FID SG

Acetylene tetrachloride 1019 1 .1 ,2,2-TETRACHLOROETHANE P 0.01-0.2 3.0 30 GC-FID PCT

Acids, inorganic 7903 ACIDS, INORGANIC F 0.2-0.5 3.0 100 IC SG (washed)

Acrolein 2501 ACROLEIN P 0.01-0.1 1.5 48 GC-NPD XAD-2/HMP

Acrolein 2539 ALDEHYDES, SCREENING P D.01-O.O5 5 5 GC-FID/MS XAD-2WMP

Acrylonitrilft 1604 ACRYLONITRILE F 0.01-0.2 3.5 20 GC-FID CCT

Aldehydes, screening 2539 ALDEHYDES, SCREENING P 0.01-0.05 5 5 GC-FID/MS XAD-2

Alkaline dusts 7401 ALKALINE DUSTS F 1 -4 70 1000 Titration PTFE

Allyl alcohol 1402 ALCOHOLS III P 0.01-0.2 1 10 GC-FID CCT

Allyl chloride 1000 ALLYL CHLORIDE F 0.01-1.0 16 100 GC-FID CCT

Allyl trichloride 1003 HYDROCARBONS, HALOGENATED P 0.01-0.2 2 60 GC-FID CCT