2000AKCX

United States Environmental Monitoring EPA/600/4-89/049 t/.
(_
Environmental Protection Systems Laboratory December 1989
Agency P.O. Box 93478
Las Vegas NV 89193-3478
Research and Development ? B qo.. '" ~ o~ {)
&EPA Evaluation of Sample Extract
Cleanup Using Solid-Phase
Extraction Cartridges
Project Report
EVALUATION OF SAMPLE EXTRACT CLEANUP
USING SOLID-PHASE EXTRACTION CARTRIDGES
by
--.._ Viorica Lopez-Avila, Janet Benedicto, and June Milanes

('. .,
Acurex Corporation
C."-
1 Environmental Systems Division
lj)
Mountain View, California 94039
'
I
Contract Number 68-03-3511
Project Officer
Werner F. Beckert
Quality Assurance Division
Environmental Monitoring Systems Laboratory
Las Vegas, Nevada 89193-3478
ENVIRONMENTAL MONITORING SYSTEMS LABORATORY

OFFICE OF RESEARCH AND DEVEWPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
LAS VEGAS, NEVADA 89193-3478
U.S. Environmental Protection Agency

Region 5. Library (PL·l2J)
17 WP.st Jackson Boulevard, 12th Fk8
Chicago, IL 60604-3590
NOTICE
The study presented in this document has been funded wholly or in part by the United
States Environmental Protection Agency under Contract Number 68-03-3511 to Acurex
Corporation. This report has been subjected to the Agency's peer and administrative review,
and it has been approved for publication as an EPA document. Mention of trade names or
commercial products does not constitute endorsement or recommendation for use.
ii
PREFACE
This is the final report for Work Assignment 0-11, EPA Contract No. 68-03-3511,
"Evaluation of Sample Extract Cleanup Using Solid-Phase Extraction Cartridges," conducted at
Acurex Corporation, Project No. 8110. The project was directed by Dr. Viorica Lopez-Avila.
The report was written by Dr. Viorica Lopez-Avila. Technical support for this project
was provided by Ms. Janet Benedicto and Mr. June Milanes.
iii
ABSTRACT
Fractionation and cleanup of sample extracts prior to instrumental analysis is used to

remove coextracted materials that interfere with the determination of target analytes. Such
fractionations and cleanups are usually accomplished by column chromatography, gel permeation
chromatography, or acid-base partitioning. The purpose of this project was to evaluate the
application of solid-phase extraction cartridges containing Florisil, alumina, silica, and dial to the
fractionation and cleanup of sample extracts containing organochlorine pesticides and
polychlorinated biphenyls listed in SW-846 Methods 8080/8081, phthalate esters listed in
Method 8061, and phenolic compounds listed in Method 8040. Cartridge loading and the effects
of matrix interferents such as those present in com oil and diesel hydrocarbons, and elemental
sulfur were investigated. Such interferents were selected because they mimic typical background
contamination in the presence of which the target compounds may need to be determined. In
addition to these synthetic matrices, several extracts of environmental samples were spiked with
the target analytes at known concentrations and were then fractionated using the solid-phase
extraction procedures. A draft protocol for the use of solid-phase extraction cartridges was
prepared and was tested with spiked synthetic matrices and spiked extracts of real samples.
The results of this study indicate that the use of solid-phase extraction cartridges for the
cleanup of sample extracts is feasible for a variety of matrices and target compounds. The use
of cartridges simplifies the cleanup procedure, especially when automated (robotic) systems are
used, reduces solvent and adsorbent usage and decreases labor cost in sample preparation. Also
included in this report as an appendix is a literature review covering the state-of-the-art
technology on the solid-phase extraction cartridges and their use in extract cleanup/fractionation.
iv
TABLE OF CONTENTS
Section
1 INTRODUCTION 1
2 CONCLUSIONS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
3 RECOMMENDATIONS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
4 EXPERIMENTAL . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
5 RESULTS AND DISCUSSION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
5.1 ORGANOCHLORINE PESTICIDES AND

POLYCHLORINA1ED BIPHENYLS . . . . . . . . . . . . . . ....... 13
5.2 PHTHALA1E ESIBRS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
5.3 PHENOLS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
5.4 EVALUATION OF THE ASPEC SYS1EM . . . . . . . . . . . . . . . . . 54
REFERENCES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
APPENDIX A -- EVALUATION OF SAMPLE EXTRACT CLEANUP

USING SPE CARTRIDGES -- LTIERATURE
REVIEW ................................... A-1
APPENDIX B - METHOD 3670 -- SAMPLE EXTRACT CLEANUP
USING SPE CARTRIDGES {DRAFT PROTOCOL) .. B-1
v
FIGURES
Number Pa&e
1 GC/ECD chromatograms of Method 8081 organochlorine pesticides

analyzed on a DB-608/DB-1701 column pair . . . . . . . . . . . . . . . . . . . . . . . . . 10
2 GC/ECD chromatograms of a phthalate esters standard analyzed on the
DB-608/DB-1701 column pair . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
3 GC/ECD chromatograms of the PFB derivatives of phenolic compounds

analyzed on the DB-1701/DB-5 column pair . . . . . . . . . . . . . . . . . . . . . . . . . 12
4 GC/ECD chromatograms of a Method 8081 organochlorine pesticide

standard containing elemental sulfur, passed through a silica cartridge . . . . . . 33
5 GC/ECD chromatograms of a Method 8081 organochlorine pesticide

standard containing elemental sulfur, passed through a diol cartridge. 34
6 GC/ECD chromatograms of a phthalate esters standard spiked with
organochlorine pesticides and elemental sulfur and eluted from the 1-g
Florisil cartridge with hexane with 10 percent acetone . . . . . . . . . . . . . . . . . . 40
7 GC/ECD chromatograms of a phthalate esters standard spiked with

organochlorine pesticides and elemental sulfur and eluted from the 1-g
alumina cartridge with hexane with 20 percent acetone . . . . . . . . . . . . . . . . . 41
vi
TABLES
Number
1 Retention times and relative retention times of organochlorine pesticides

analyzed on the DB-608/DB-1701 column pair . . . . . . . . . . . . . . . . . . . . . . . 5
2 Retention times and relative retention times of phthalate esters analyzed
on the DB-608/DB-1701 column pair . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3 Retention times and relative retention times of the PFB derivatives of

phenolic compounds analyzed on the DB-1701/DB-5 column pair . . . . . . . . . . 7
4 Samples used in method development . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
5 Elution patterns and percent recoveries of the organochlorine pesticides

from silica cartridges . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15

from Florisil cartridges . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
7 Percent recoveries of the Aroclors from Florisil and silica cartridges . . . . . . . 17

from Florisil cartridges . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18

from silica cartridges . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19

and Aroclor 1260 from silica cartridges . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
11 Percent recoveries and elution patterns of 17 organochlorine pesticides

from 0.5-g silica cartridges . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22

from 1-g silica cartridges . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23

14 Elution patterns and percent recoveries of 17 organochlorine pesticides

from 0.5-g diol cartridges . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25

from 1-g diol cartridges . . . . . . . . . . . . . . . . . . . • . . • . . . . . . . . . . . . . . . . . . 26

from 2-g diol cartridges . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
vii
TABLES (continued)
Number Page
17 Elution patterns and percent recoveries of 17 organochlorine pesticides and

Aroclor 1260 from 1-g diol cartridges . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29

from 1-g silica cartridges in the presence of com oil and diesel
hydrocarbons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31

from 1-g diol cartridges in the presence of com oil and diesel
hydrocarbons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
20 Elution patterns and percent recoveries of the phthalate esters from the
Florisil cartridges using hexane with 10 percent acetone . . . . . . . . . . . . . . . . . 35
alumina cartridges using hexane with 10 percent and 20 percent acetone . . . . 36
alumina cartridges of various sizes using hexane with 20 percent acetone . . . . 37
23 Percent recoveries of the phthalate esters from Florisil and alumina

cartridges when interferents were present . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
24 Elution patterns and percent recoveries of phthalate esters from Florisil

cartridges using hexane with 50 percent diethyl ether . . . . . . . . . . . . . . . . . . . 42
25 Results of the Florisil cartridge cleanup evaluation study (phthalate ester

standards only; elution with hexane/methylene chloride (4:1) and
hexane/acetone (9:1)) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
26 Experimental design for Florisil cartridge cleanup method development . . . . . 45
27 Recovery of phthalate esters from 1-g Florisil cartridges . . . . . . . . . . . . . . . . 48
28 Recovery of phthalate esters from 1-g Aorisil cartridges in the presence

of organochlorine pesticides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
29 Interferenc~ in ~~ determination of phthalate esters caused by

organochlorme pest1ades . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
30 Results of method blank analyses for the f1orisil cartridges . . . . . . . . . . . . . . 51
viii
TABLES (concluded)
Number Page
31 Percent recoveries of phthalate esters in extracts from various matrices

subjected to Florisil cartridge cleanup . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
32 Method detection limit study -- Florisil cartridges method blanks . . . . . . . . . . 53
33 Elution patterns and percent recoveries of the PFB derivatives of phenols

from 0.5-g silica cartridges . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55

36 Percent recoveries and elution patterns of phenols from 1-g silica cartridges
in the presence of com oil and diesel hydrocarbons . . . . . . . . . . . . . . . . . . . . 58
37 Percent recoveries and elution patterns of phenols from 1-g silica cartridges
in the presence of matrix interferents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
38 Method reproducibility using the ASPEC robotic system . . . . . . . . . . . . . . . . 60
41 Evaluation of matrix interferents using the ASPEC robotic system . . . . . . . . . 63
42 Percent recoveries of 17 organochlorine pesticides spiked into SS-2 soil

extract . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64

extract . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65

extract . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66

extract . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
ix
SECTION 1
INTRODUCTION
Fractionation or cleanup of sample extracts prior to instrumental analysis for organic

compounds (e.g., gas chromatography) is used to remove coextracted materials that interfere
with the determination of target analytes. Such fractionations are usually accomplished by
column chromatography (e.g., on Florisil, alumina, silica gel), gel permeation chromatography,
or acid-base partitioning. More elaborate fractionation schemes that involve a combination of
such cleanup procedures can be quite tedious, and experienced analysts are required for their
successful application.
Standardized cleanup procedures such as Methods 3610 and 3620, published in the
Office of Solid Waste Manual SW-846, revised recently (1), specify amounts of alumina and
Florisil in excess of 10 g and large volumes of eluting solvents. For example, a 10-g Florisil
column and 100 mL of 20 percent diethyl ether in hexane are recommended for cleanup of
sample extracts containing phthalate esters. Such large volumes of solvents increase the
likelihood of sample contamination by impurities present in solvents. Furthermore, the
adsorbent materials and the solvents are not recycled, and although such materials are not overly
expensive, the time required for the preparation of the adsorbent, for the packing of the
chromatographic columns, for the elution of the target analytes from the columns, and for the
evaporation of solvents contributes to the overall cost of analysis.
The purpose of this study was to evaluate the application of solid-phase extraction
cartridges containing Florisil, alumina, silica, and diol to the fractionation/cleanup of sample
extracts containing organochlorine pesticides and polychlorinated biphenyls listed in SW-846
Methods 8080/8081, phthalate esters listed in Method 8060, and phenolic compounds listed in
Method 8040. Cartridge loading and the effects of matrix interferents such as those present in
corn oil and diesel hydrocarbons, and elemental sulfur were investigated. Such interferents were
selected because they mimic typical background contamination in the presence of which the
target compounds may have to be determined. For example, corn oil is representative of the
fatty acid triglycerides, and diesel hydrocarbons are representative of petroleum hydrocarbons.
Elemental sulfur was chosen because this compound is extracted from soils or sediments along
with target analytes and interferes with their gas chromatographic determination, especially when
an electron capture detector is used for compound identification and quantification. In addition
to these synthetic matrices, we have also used extracts of real samples which were spiked with
the target analytes at known concentrations and were then fractionated using the solid-phase
extraction cartridge procedure.
Subsequent sections of this report present the conclusions and recommendations of this
study, details of the experimental procedures, and the results and discussion. Appendix A
contains the literature review summary, and the protocol for sample extract cleanup is included
as Appendix B.
1
SECTION 2
CONCLUSIONS
Currently, there are no EPA-approved sample extract cleanup procedures that specify
the use of solid-phase extraction (SPE) cartridges. The only methods specifying SPE cartridges
are Test Method No. SPE-500, Methods for Organochlorine Pesticides and Chlorophenoxy Acid
Herbicides in Drinking Water and Raw Source Water for Endrin, Lindane, Methoxychlor, and
Toxaphene, and Method 525, Determination of Organic Compounds in Drinking Water by
Liquid-Solid Extraction and Capillary Column Gas Chromatography/Mass Spectrometry. Both
methods use such cartridges for sample preconcentration and not for cleaning or fractionating
the sample extract. Work presented in this report involves the development of such simplified
extract cleanup procedures for use with methods presented in the EPA's SW-846 procedures
manual.
Use of SPE cartridges reduces solvent and adsorbent usage and labor cost in sample
preparation. Because cartridges are prepackaged and ready for use, there is no need for
adsorbent calibration, activation, or deactivation. Furthermore, when commercially available
automated systems are used, sets of 12 or 24 extracts, depending on the capacity of the vacuum
manifold, can be cleaned up simultaneously with no danger of sample crosscontamination; thus,
sample throughput can be increased significantly. In addition, errors resulting from operator and
material variables that may affect the quality of the results can be minimized.
2
SECTION 3
RECOMMENDATIONS
• The protocol for extract cleanup using SPE cartridges which is presented in this
report has been evaluated in a single laboratory only with a few relevant sample
extracts. To establish the applicability range of the cartridge method and to define
the interlaboratory method performance, the protocol should be evaluated by other
laboratories and with additional samples.
• Use of SPE cartridges helps increase sample throughput, and reduces solvent and
adsorbent usage and labor cost in sample preparation. To take full advantage of
these benefits, automation of the sample extract step should be explored. Several
robotics systems which are available commercially should be evaluated.
• Bonded-phase silicas and polymeric materials such as those available from

Interaction Chemicals of Mountain View, California, should be evaluated for
removal of matrix interferents present in extracts of soils, sediments, and other
environmental matrices, and for fractionation of analytes of environmental
significance.
3
SECTION 4
EXPERIMENTAL
Apparatus
a. Vacuum manifold -- VacElute manifold SPS24 (Analytichem International) or Visiprep

(Supelco Inc.) or equivalent, consisting of glass vacuum basin, collection rack and funnel,
collection vials, replaceable stainless steel delivery tips, built-in vacuum bleed valve and
gauge; the system was connected to· a vacuum pump or water aspirator through a vacuum
trap made from a 500-mL side arm flask fitted with a one-hole stopper and glass tubing.
b. ASPEC robotic system (Gilson Medical Electronics, Inc) consisting of a sample processor and
injector module and the Gilson fluid transfer unit (Model 401 Diluter).
c. Gas chromatographs -- Varian 6000 with constant current/pulsed frequency dual electron
capture detector (ECO) and interfaced to a Varian Vista 402 data system; Varian 6500 with
constant current/pulsed frequency dual ECO and interfaced to a Varian Vista 604 data
system.
d. Autosampler -- Varian, Model 8000
e. GC columns -- DB-608 and DB-1701, 30-m x 0.53-mm ID fused-silica open tubular columns
for Method 8060 phthalate ester analysis and Method 8080 organochlorine
pesticide/polychlorinated biphenyls analysis; DB-5 and DB-1701, 30-m x 0.53-mm ID fused-
silica open tubular columns for Method 8040 phenol analysis. The GC operating conditions
are given in Tables 1 through 3.
Materials
a. Cartridges -- Florisil, alumina, silica gei or diol (40-µm particles, 60-A pores) of 0.5 g, 1 g,
and 2 g in size. The cartridges consist of serological-grade polypropylene tubes, 3 mL or
6 mL in volume; the adsorbent material is held between two polyethylene frits (30-µm pores).
b. Standards -· Analytical reference standards of the test compounds were obtained from the
U.S. Environmental Protection Agency, Pesticides and Industrial Chemical Repository,
Aldrich Chemical, Ultra Scientific Inc., Chem Service, and Scientific Polymer Products.
Purities were stated to be greater than 98 percent. Stock solutions of each test compound
were prepared by serial dilutions of a composite stock solution prepared from the industrial
stock solutions.
c. Com oil -- Stock solution was prepared in hexane at 1.1 mg/mL.
4
TABLE 1. RETENTION TIMES AND RELATIVE RETENTION TIMES OF ORGANO-
CHLORINE PESTICIDES ANALYZED ON THE DB-608/DB-1701 COLUMN
PAIR8
DB-608 DB-1701
Compound
No. Compound name tr (min) RRT tr (min) RRT
1 alpha-BHC , 9.79 0.912 10.22 0.953

2 gamma-BHC 11.28 1.051 11.64 1.086
3 beta-BHC 11.59 1.080 14.18 1.323
4 Heptachlor 12.47 1.162 12.41 1.158
5 delta-BHC 12.97 1.209 15.02 1.401
6 Aldrin 13.69 1.276 13.37 1.247
7 Heptachlor epoxide 15.84 1.476 15.79 1.473
8 Endosulfan I 17.13 1.596 16.73 1.561
9 4,4'-DDE 18.06 1.683 17.41 1.624
10 Dieldrin 18.28 1.704 17.99 1.678
11 Endrin 19.63 1.829 18.72 1.746
12 4,4'-DDD 20.14 1.877 20.07 1.872
13 Endosulfan II 20.32 1.894 20.32 1.896
14 4,4'-DDT 21.22 1.978 20.68 1.929
15 Endrin aldehyde 21.54 2.007 21.71 2.025
16 Endosulfan sulfate 21.99 2.049 22.81 2.128
17 4,4 •-Methoxychlor 24.48 2.281 22.81 2.128
Pentachloronitrobenzene (IS)b 10.73 1.000 10.72 1.000
1
The GC operating conditions were as follows: 30-m x 0.53-mm ID DB-608 (0.83-µm film)
and 30-m x 0.53-mm ID DB-1701 (1.0-µm film) connected to an 8-in injection tee (Supelco,
Inc.). Temperature program: 150°C (0.5-min hold) to 275°C (15-min hold) at 5°C; injector
temperature 250°C; detector temperature 320°C; helium carrier gas 6 mL/min; nitrogen
makeup gas 20 mL/min.
blnternal standard.
s
TABLE 2. RETENTION TIMES AND RELATIVE RETENTION TIMES OF PHTHALATE
ESTERS ANALYZED ON THE DB-608/DB-1701 COLUMN PAIR•
DB-608 DB-1701
Compound
no. Compound name t. (min) RRT t. (min) RRT
1 Dimethyl phthalate (DMP) 6.72 0.554 6.73 0.585

2 Diethyl phthalate (DEP) 8.69 0.716 8.85 0.770
3 Diisobutyl phthalate (DIBP) 12.74 1.050 13.36 1.162
4 Di-n-butyl phthalate (DBP) 14.68 1.210 15.13 1.316
5 Bis(4-methyl-2-pentyl) phthalate (BMPP) 15.76 1.299 16.73 1.455
6 Bis(2-methoxyethyl) phthalate (BMEP) 17.24 1.421 16.96 1.475
7 Diamyl phthalate (OAP) 17.94 1.479 18.64 1.621
8 Bis(2-ethoxyethyl) phthalate (BEEP) 18.93 1.561 18.80 1.635
9 Dihexyl phthalate (DHP) 19.70 1.624 19.56 1.701
10 Hexyl 2-ethylhexyl phthalate (HEHP) 21.50 1.772 22.48 1.955
11 Butyl benzyl phthalate (BBP) 24.64 2.031 23.76 2.066
12 Bis(2-n-butoxyethyl) phthalate (BBEP) 25.71 2.120 25.96 2.257
13 Bis(2-ethylhexyl) phthalate (DEHP) 24.94 2.056 26.35 2.291
14 Dicyclohexyl phthalate (DCP) 28.33 2.336 27.06 2.353
15 Di-n-octyl phthalate (DOP) 29.14 2.402 30.57 2.658
16 Dinonyl phthalate (DNP) 32.97 2.718 34.71 3.018
Benzyl benzoate (ISt 12.13 1.000 11.50 1.000
• GC operating conditions were as follows: 30-m x 0.53-mm ID DB-608 (0.83-µm film) and 30-m x
0.53-m ID DB-1701 (1.0-µm film) connected to an 8-in injection tee (Supelco, Inc.). Temperature
program: 150"C (0.5-min hold) to 220°C at 5°C/min, then to 275°C (18-min hold) at 3°C/min;
injector temperature 2500C; detector temperature 320"C; helium carrier gas 6 mL/min; nitrogen
makeup gas 20 mL/min.
b Internal standard.
TABLE 3. RETENTION TIMES AND RELATIVE RETENTION TIMES OF THE PFB
DERIVATIVES OF PHENOLIC COMPOUNDS ANALYZED ON THE
DB-1701/DB-5 COLUMN PAIRa,b,c
DB-1701 DB-5
Compound
no. Compound name t, (min) RRT t, (min) RRT
1 Phenol 7.76 0.518 5.40 0.446

2 2-Methylphenol 9.03 0.603 6.73 0.556
3 3-Methylphenol 9.62 0.643 7.20 0.595
4 4-Methylphenol 9.76 0.652 7.38 0.610
5 2,4-Dimethylphenol 10.83 0.723 8.62 0.712
6 2-Chlorophenol 11.76 0.786 8.67 0.717
7 2,6-Dichlorophenol 13.70 0.915 10.98 0.907
8 4-Chloro-3-methylphenol 14.33 0.957 11.42 0.944
9 2,4-Dichlorophenol 15.56 1.039 12.22 1.010
10 2,4,6-Trichlorophenol 16.20 1.082 13.66 1.129
12 2-Nitrophenol 18.59 1.242 1_3.38 1.106
15 2,3,5,6-Tetrachlorophenol 19.98 1.335 17.23 1.424
19 Pentachlorophenol 23.64 1.579 20.76 1.716
20 2,4-Dinitrophenol 28.07 1.875 20.78 1.717
Pentachloronitrobenzene (IS)d 14.97 1.000 12.10 1.000
1
Not able to obtain a detector response from 4-nitrophenoL dinoseb, or 4,6-dinitro-o-cresol
PFB derivatives.
b GC operating conditions were as follows: 30-m x 0.53-mm ID DB-5 (0.83-µm film) and
30-m x 0.53-mm ID DB-1701 (1.0-µm film) connected to an 8-inch injection tee (Supelco,
Inc.). Temperature program: 150°C (5 min hold) to 275°C (15 min hold) at 5°C/min;
injector temperature 250°C; detector temperature 3200C; helium carrier gas 6 mL/min;
nitrogen makeup gas 20 mL/min.
c: Phenols were derivatized with pentafluorobenzyl bromide (PFBBr) following the procedure
by Lee et al. (2).
d Internal standard.
7
d. Diesel hydrocarbons -- Stock,solution was prepared in hexane at 1 mg/mL.
e. Elemental sulfur -- Stock solution was prepared in hexane at 0.28 mg/mL.
f. Samples -- Those used in the method development are identified in Table 4.
Cartridge Cleanup Procedure
Florisil cartridges were conditioned with 4 mL hexane prior to use. Diol cartridges were
conditioned with hexane with 10 percent acetone. Silica cartridges were conditioned with 4 mL
hexane. Aliquots of 2 mL of standards or sample extracts in hexane were loaded onto SPE
cartridges using a micropipette and were eluted with the solvents indicated in the tables
summarizing the data. A Supelclean Visiprep vacuum manifold (Supelco, Inc.) and a
VacElute SPS24 (Analytichem International) were used to simultaneously prepare as many as
12 samples (for the Visiprep system) or 24 samples (for the VacElute SPS24 system). When
using the Visiprep system, the vacuum for each cartridge was adjusted manually using chemically
inert screw-type valves. Additional details of the cartridge cleanup procedure can be found in
the protocol included in Appendix B of this report.
Gas Chromatographic Analysis
All fractions were analyzed by gas chromatography with ECD using the dual-column
approach. The retention times and the relative retention times of the target compounds are
presented in Tables 1 through 3. Figures 1 through 3 show GC/ECD chromatograms obtained
for each group of target compounds. Quantification of compounds was performed using internal
standard calibrations.
8
TABLE 4. SAMPLES USED IN METHOD DEVELOPMENT
Material Description
Sandy loam soil Mixture of 20 percent organic soil and 80 percent sand
Sediment of undefined origin Sediment sample contaminated with petroleum

hydrocarbons
SRM-1572 Citrus leaves from Lake Alfred area of central Florida.

The material was air-dried, ground to pass through a
425-µm screen, dried at 85°C, mixed in a feed blender,
and sterilized with cobalt-60 radiation.
SRM-1632a Coal obtained from the Humphrey No. 7 mine and coal
preparation plant of the Consolidation Coal Co., Osage,
West Virginia. Contains approximately 1.8 to
1.9 percent sulfur and was ground to pass through a
60-mesh sieve.
SRM-1633a Coal flyash, obtained from a coal-fired power plant that

uses Pennsylvania and West Virginia coals. The material
was sieved to pass through a 90-µm screen.
Sample 1 Soil sample taken from a greenhouse, identified as S-2A

greenhouse south; known to contain 4,4'-DDE at
460 µg/Kg
Sample 2 Soil sample known to contain ppm levels of polynuclear

aromatic hydrocarbons
Sample 3 Soil sample known to contain 4,4 '-DDE at 4000 µg/Kg

and 4,4 '-DDD at 34,000 µg/Kg
Samples SS-2, SS-5, SS-7 Soil samples taken from a farm in Northern California,
and SS-8 which was known to have used organochlorine pesticides,
diazinon, ethion, ziram, carbaryl, benomyl,
carbophenothion, and malathion.
9
2
, DB- 608
' 5 6
10
9
._
(.)
7 8
12 13
11 14
..,w 15
16
z
- 3
17
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l,i..-"' ._..
2 DB-1701
, ' 6
16
10
13 17
t;
..,w 3
15
z
-
I I I
0 10 30
TIME (min)
Figure 1. GC/ECD chromatograms of Method 8081 orpnochlorine pesticides analyzed on a

DB-608/DB-1701 column pair. 1be GC operating conclltlons are given In Table 1.
10
I/)
N
.
f""
<:1" -
CD
N
1 11 N
13 12 °'
N
16
15
10
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2
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([I
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5
14
0 f\I
Ct'.
w
r~
.0
9 °' Ill
J~1tL1!_ l1
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'='
r~
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~
.
-ti
DB-1701
~ N
(j 11
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.....
8
z" -ti I/)
-
:E:
1(1
6
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.
-ti
I'-
'If"
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CD
4
7 13 l"l
15 16
z 10
14
-~
E: If) N
' ..
E:
(.)
If)
l"l
0 9 'If" -ti
t9 0::
t9N
•W '°f'- N t'l
0
WN
Wt'l
tl.
. . .......z,
!I)
a:w
([
It-
0,<J:
Figure 2. GC/ECD chromatograms or a pbtbalate esten standard analyzed on the

DB-608/DB-1701 column pair. 1be GC operating conditions and peak assignments
are given in Table 2.
11
14
13 DB-1701
12 30 m x 0.53 mm ID
IS>~
ID ..-
co r-
v .....
NID
lf"l!'l ....
.,.. ID ISl16 CD If'
1.0 µm film
I":
"'~
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(p•.D
Cl) r-
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7 ....
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10 11
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"' 18 N
(\I"'
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19
-
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:c
4
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a:
LLJ
N r
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i
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rJ
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z
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ID t•
19
DB-5
30 m x 0.53 mm ID
I-
......
z
1 zr, 7"'89
1011131715
I 14 16
18
20 0.83 µm film
:c
I
z
-~
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u r. ,...
0
s a: C:•
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0
LI.IN
l
UJ r<'l
Q.
U'l
I- z
.. ....
a:: UJ
4: I-
:::c .....
u 4:'. h
Figure 3. GC/ECD chromatograms of the PFB derivatives of phenolic compounds analyzed on

the DB-1701/DB-5 column pair. 1be GC operating conditions and peak assignments
are given In Table 3.
12
SECTION 5
RESULTS AND DISCUSSION
5.1 ORGANOCHLORINE PESTICIDES AND POLYCHLORINATED BIPHENYLS
The current SW-846 Methods 8080/8081 for organochlorine pesticides and

polychlorinated biphenyls (PCBs) determination recommend use of either Florisil (Method 3620)
or silica gel for cleanup of sample extracts containing organochlorine pesticides and PCBs. In
Method 3620, Florisil (60/80 mesh) is activated for 16 hrs at 130°C. The charged Florisil column
( 10 g) is eluted with 200 mL of 6 percent diethyl ether in hexane (Fraction 1), 200 mL of
15 percent diethyl ether in hexane (Fraction 2), and 200 mL of 50 percent diethyl ether in
hexane (Fraction 3). Compounds recovered in Fraction 1 include aldrin, the four BHC isomers,
chlordane, 4,4 '-DOD, 4,4 '-DOE, 4,4 '-DDT, endosulfan I, heptachlor, heptachlor epoxide,
toxaphene, and the PCBs. Compounds recovered in Fraction 2 include dieldrin, endosulfan I,
endrin, and endrin aldehyde. Endosulfan Il, endosulfan sulfate, and some endrin aldehyde are
recovered in Fraction 3. We evaluated Method 3620 and reported that, although compound
recoveries were quantitative, the Florisil fractionation method is not suitable for samples that
contain both organochlorine pesticides and PCBs (3) since the PCBs are eluted in the same
fraction as the bulk of the organochlorine pesticides. We undertook the evaluation of the
Florisil cartridges specifically for samples that contain only the organochlorine pesticides. The
silica cartridges were considered since Method 8081 describes a procedure in which PCBs can
be separated from the bulk of the organochlorine pesticides using ·silica gel deactivated with
3 percent water. Finally, dial cartridges were evaluated since at the time our study was
conducted, EPA was considering the use of dial cartridges for incorporation into the Contract
Laboratory Program protocols. This section describes the results of the Florisil, silica, and diol
cartridge evaluation studies.
Two elution schemes were attempted initially. In Scheme A, the charged Florisil and
silica cartridges were eluted with 3 mL hexane (Fraction 1) followed by 5 mL hexane with
26 percent methylene chloride (Fraction 2) and 5 mL hexane with 10 percent acetone
(Fraction 3); in Scheme B, the charged Florisil and silica cartridges were eluted with 3 mL
hexane (Fraction 1), 5 mL hexane with 4 percent diethyl ether (Fraction 2), and 5 mL hexane
with 56 percent diethyl ether (Fraction 3). Hexane with 26 percent methylene chloride has
approximately the same solvent strength as hexane with 4 percent diethyl ether, and hexane with
10 percent acetone has approximately the same solvent strength as hexane with 56 percent
diethyl ether. Under the Scheme A conditions, silica gel proved superior to Florisil because it
allowed complete separation of the PCBs from all but four organochlorine pesticides,
quantitative recovery of all compounds, and almost complete separation of the Method 8081
organochlorine pesticides from the Method 8060 phthalate esters. The four organochlorine
pesticides that eluted with the 16 phthalate esters could be identified and quantified without any
difficulty because they were resolved from the phthalate esters on a 30-m x 0.25-mm ID DB-5
fused-silica capillary column.
13
The solvents used in Scheme B gave almost identical elution patterns for the Florisil and
silica gel procedure with quite a few organochlorine pesticides spread among the three fractions.
Because of this, no further work was undertaken using Scheme B.
The procedure given in Scheme A was tested at 2 organochlorine pesticide

concentrations in quadruplicate. The results presented in Tables 5 and 6 show elution patterns,
compound recoveries, and method precision for the 17-organochlorine pesticides listed in
Table 1 and gamma-chlordane. The silica gel cartridges seemed to perform better than the
Florisil cartridges (Table 5). Three organochlorine pesticides (heptachlor, aldrin, and 4,4 •-DDE)
were eluted only in Fraction 1. Nine organochlorine pesticides (the four BHC isomers,
heptachlor epoxide, gamma-chlordane, endosulfan I, dieldrin, and 4,4 •-DDD) were eluted only
in Fraction 2. Endosulfan TI was eluted in Fraction 3. Endrin aldehyde, 4,4 ·-DDT, endosulfan
sulfate and 4,4 •-methoxychlor were eluted in more than one fraction. Compound recoveries
were quantitative and method precision (%RSD) was better than 11 percent for 14 of the 18
target compounds. Since endosulfan sulfate was not resolved from 4,4 ·-DDT on the 30-m x
0.25-mm ID DB-5 column, it is difficult to specify in which fraction this compound was
recovered. Based on the other data presented in this section, it is expected that endosulfan
sulfate would elute in Fraction 3 from either the silica cartridge (Table 5) or the Florisil
cartridge (Table 6).
Table 6 presents the results for the Florisil SPE cartridge procedure. Eight pesticides
(alpha-BHC, gamma-BHC, heptachlor, aldrin, gamma-chlordane, 4,4 •-DDE, 4,4 '-DDD, and
4,4 '-DDT) were eluted in Fraction 1. All pesticides except heptachlor, aldrin, and 4,4 •-DDE
were also recovered in Fraction 2. Endosulfan II, endrin aldehyde, possibly endosulfan sulfate
and 4,4 •-methoxychlor were also eluted in Fraction 3.
Seven Aroclor mixtures were tested individually on the silica and the Florisil cartridges.
In each case, the cartridges were loaded with 10 µg of the corresponding Aroclor and were
eluted with 3 mL hexane. The recovery data given in Table 7 indicate that the Aroclors were
recovered quantitatively from either cartridge with 3 mL hexane. Larger cartridges may require
additional solvent to ensure complete removal of PCBs.
Other solvent mixtures used in eluting the organochlorine pesticides from 1-g Florisil
and silica cartridges included hexane, hexane with 6 percent diethyl ether, hexane with
15 percent diethyl ether, and hexane with 50 percent diethyl ether (Tables 8 and 9). The Florisil
cartridge is somewhat less polar than the silica cartridge, and more organochlorine pesticides
were eluted from the Florisil cartridge with hexane.
To reduce the number of fractions that have to be collected in order to recover all
18 organochlorine pesticides, we eluted the silica cartridges with two 3-mL hexane portions and
5 mL of hexane with 50 percent diethyl ether. At least 3 mL hexane need to be passed through
the silica cartridge to elute any PCBs that would interfere with the gas chromatographic analysis
of the organochlorine pesticides. The second 3-mL hexane portion was used to verify the
complete removal of PCBs from the cartridge (Table 10). Elution of silica cartridges with 5 mL
hexane with 50 percent diethyl ether resulted in quantitative recovery of all organochlorine
pesticides retained on the cartridge.
This elution scheme was further tested with silica cartridges of 0.5-g, 1-g, and 2-g size,
each charged with 17 organochlorine compounds at 0.2 pg, 1.0 pg, and 2.0 pg per cartridge.
Gamma-chlordane was not included among the target compounds because it was not available
in pure form at the time the study began. Two fractions were collected from the 0.5-g and 1-g
14
TABLE 6. ELUTION PATTERNS AND PERCENT RECOVERIES OF THE ORGANO-
CHLORINE PESTICIDES FROM FLORISIL CARTRIDGES•
Spiked at 11.5 µg per compound Spiked at 5.0 µg per compound
Fraction 2 Fraction 2
(5 mL hexane with Fraction J (5 mL hexane with Fraction 3
Frartion I 26 percent (5 mL hexane with Fraction I 26 percent (5 mL hexane with
(J mL hexane) methylene chloride) IO pel't'ent acetone) (3 mL hexane) methylene chloride) 10 percent acetone
Co•pound A•g. %RSI> Avg. %RSI> Avg. %RSI> Avg. %RSI> Avg. %RSI> Avg. %RSI>
alpha-BHC 82.(1 3.4 2<>.1 10.7 0 79.0 13.7 34.I 5.6 0

gamma-BHC 35.R 13.3 11.5 :u 0 32.0 20.9 82.R 3.R 0
beta-BHC 0 I02 2.3 0 0 104 3.6 0
Heptachlor 94.4 2.3 0 0 94.8 14.8 0 0
delta-BHC 0 99.6 1.4 0 0 103 2.3 0
Aldrin 93.1 2.0 0 0 94.6 14.2 0 0
Heptachlor epoxide 0 102 2.4 0 0 104 3.9 0
gamma-Chlordane 47.6 9.8 65.6 3.5 0 44.2 18.0 73.2 5.4 0
Endosulfan I 0 IOI 2.7 0 0 104 4.3 0
4,4'-DDE 94.5 1.7 II II 96.8 14.9 0 0
Dieldrin 0 IOI 2.9 0 0 105 4.4 0
.... Endrin 0 57.2 1.5 0 • • •
°' 4,4'-DDD
Endosulran II
38.5
0
12.3 <•R.K
5K.2
2.9
13.3
0
61.1 9.9
37.7
0
19.9 77.3
60.3
4.9
5.2
0
58.3 10.!I
Endrin aldehyde 0 36.3 7.2 78.7 2.6 0 47.5 2.7 72.7 6.7
4,4'-DDT 49.6 1.9 11.2 16.4 59.4 3.1 51.6 15.0 12.2 13.7 56.11 9.8
Endosulfan sulfate•
4,4 '-Methoxychlor 0 96.0 3.4 11.7 :rn 0 105 5.5 11.2 15.0
•t-g LC-Florisil cartridges (Supelco Inc.) were used. The amount of compound loaded to the cartridge is 0.5 pg or 5.0 µg per compound (or 2 mL of a
0.25-1&g/mL or 2.5-pg/mL solution in hexane). Fraction 1 was eluted with 3 mL hexane, fraction 2 with 5 mL hexane with 26 percent methylene chloride, and
Fraction 3 with S mL hexane with 10 percent acetone. Numher of replicates was 4.
•o.ta not available due to poor chromatography on the 30-m x 0.25-mm ID DB-5 fused-silica capillary column.
•These compounds coelute on the 30-m x 0.25 mm ID DB-5 fused-silica capillary column.
TABLES. ELUTION PATTERNS AND PERCENT RECOVERIES OF THE ORGANO-
CHLORINE PESTICIDES FROM SILICA CARTRIDGES•
Spiked at 0.5 µg per 01mpound Spiked at S.O µg per compound
(S mL hexane with Fraction 3 (S ml, hexane with Fraction 3
Fraction I 26 percent (5 mL hexane in l•ractlon I 26 percent (5mL hexane in
(3 mL hexane) methylene chloride) IO percent acetone) (3 mL hexane) methylene chloride) 10 percent acetone)
Compound Avg. %RSD Avg. %RSI> Avg. %RSD Avg. %RSI> Avg. %RSI> AvJ:. %RSI>
alpha-BHC 0 111 IU II II 111 2.4 fl

gamma-BHC 0 I IO 8.5 II II Ill 2.:l II
heta-BHC 0 1119 7.8 0 II 111 2.7 II
Heptachlor 98.4 111.8 0 0 1115 1.0 (I II
delta-BHC 0 106 9.3 0 0 110 3.5 (J
Aldrin 96.6 9.9 0 0 108 0.9 0 0
Heptachlor epoxide 0 1119 7.9 0 0 112 2.8 0
gamma-Chlordane 0 1115 3.5 0 0 108 6.5 0
Endosulfan I 0 111 6.2 0 0 114 2.6 0
4,4'-DDE 104 5.7 0 0 l()IJ I.I 0 0
-
VI
Dieldrin
Endrin•
4,4'-DDD
Endosulfan II
4,4'-DD"r
0
0
0
•
40.I 25.5
110
•
Ill
0
16.7
7.8
6.2
24.3
0
•
0
111
63.4
47.7
2.3
3.2
0
0
0
•
44.6 10.3
114
•
tl4
0
19.4
52.4
2.4
3.3
25.9
3.1
0
h
0
1111
63.3
41.9
3.0
4.1
9.9
Endrin aldehyde 0 48.9 14.0 12.4 0
Endosulfan sulfate•
4,4 •-Methoxychlor 0 84.5 22.2 33.6 29.0 0 94.3 10.4 26.1 111.2
•t-g LC-silica cartr~ (Supeloo Inc.) were used. The amount of compound loaded to the cartridge is 0.5 or 5.0 pg per compound (or 2 mL of a 0.25-µg/mL or
2.S-pg/mL solution m hexane). Fraction I was eluted with 3 mL hexane. Fraction 2 with 5 mL hexane with 26 percent methylene chloride, and Fraction 3 with
S mL hexane with to percent acetone. Number of replicates was 4.
•Data not available due to poor chromatography on the 30-m x 0.25-mm ID DB-5 fused-silica capillary column.
•These compounds coelute on the 30-m x 0.25-mm ID DB-5 fused-silica capillary column.
TABLE 7. PERCENT RECOVERIES OF THE AROCLORS
FROM FLORISIL AND SILICA CARTRIDGES
Percent recovery8
LC-Florisil LC-Silica
Com2ound c1 s> c1 s>
Aroclor 1016 105 124
Aroclor 1221 76.5 93.5
Aroclor 1232 90.1 118
Aroclor 1242 93.6 116
Aroclor 1248 97.2 114
Aroclor 1254 95.4 108
Aroclor 1260 89.7 112
1
1-g LC-Florisil or LC-silica solid-phase extraction
cartridges (Supelco Inc.) were used. The amount of
Aroclor loaded to each cartride is 10 µ.g (or 2 mL of
5-µ.g/mL solution in hexane). Hexane (3 mL) was
used as eluent.
17
TABLE 8. ELUTION PATTERNS AND PERCENT RECOVERIES OF THE ORGANOCHLORINE
PESTICIDES FROM FLORISIL CARTRIDGES•
Fraction 2 Fraction 3 Fraction 4

(S mL hexane (S mL hexane (5 mL hexane
Fraction 1 with 6 percent with 15 percent with 50 percent
Compound (3 mL hexane) diethyl ether) diethyl ether) diethyl ether)
alpha-BHC 88.7 24.4 0 0

gamma-BHC 60.0 66.1 0 0
beta-BHC 0 87.0 0 0
Heptachlor 88.8 3.6 0 0
delta-BHC 0 27.3 81.4 0
Aldrin 90.7 4.2 0 0
Heptachlor epoxide 0 94.5 0 0
Endosulfan I 0 94.9 0 0
gamma-Chlordane 70.5 0 0 0
- 4,4'-DDE 0 79.2 0 0
00 Dieldrin 0 105 0 0
Endrin 0 0 62.8 81.7
4,4'-DDD 0 0 0 84.0
Endosulfan II 76.0 70.4 0 0
4,4'-DDT 87.8 0 0 0
Endrin aldehyde 0 0 0 117
Endosulfan sulfate 0 113 0 0
4,4 '-Methoxychlor 0 94.4 0 0
-Single determination; 1-g LC-Florisil cartridges were used. The amount loaded to each cartridge was 10 p.g per compound.
TABLE 9. ELUTION PATIERNS AND PERCENT RECOVERIES OF THE ORGANOCHLORINE
PESTICIDES FROM SILICA CARTRIDGES•
Fraction 2 Fraction 3 Fraction 4

(5 mL 6 percent (5 mL 15 percent (S mL SO percent
Fraction 1 diethyl ether diethyl ether diethyl ether
Compound (3 mL hexane) in hexane) in hexane) in hexane)
alpha-BHC 0 98.0 0 0
gamma-BHC 0 99.4 0 0
· beta-BHC 0 85.0 0 0
Heptachlor 93.5 0 0 0
: delta-BHC 0 0 89.0 0
Aldrin 96.2 0 0 0
Heptachlor epoxide 0 95.1 0 0
Endosulfan I 0 93.1 0 0
gamma-Clilordane 107 0 0 0
- 4,4"-DDE 0 79.1 0 0
'° Dieldrin 0 102 0 0
Endrin 0 0 45.2 54.8
'4,4"-DDD 0 0 0 81.0
Endosulfan Il 0 94.2 0 0
4,4'-DDT 108 0 0 0
Endrin aldehyde 0 0 0 108
Endosulfan sulfate 0 105 0 0
4,4 "-Methoxychlor 0 80.8 36.0 0
-Single determination; 1-g LC-silica cartridges were used. The amount loaded to each cartridge was 10 µg per compound.
TABLE 10. ELUTION PATTERNS AND PERCENT RECOVERIES OF THE
ORGANOCHWRINE PESTICIDES AND AROCLOR 1260 FROM SILICA
CARTRIDGES•
Fraction 3
(5 mL hexane with
Fraction 1 Fraction 2 SO percent
Compound (3 mL hexane) (3 mL hexane) diethyl ether)
Aroclor 1260 101 0 0

alpha-BHC 0 59.5 61.1
gamma-BHC 0 0 101
beta-BHC 0 0 101
Heptachlor 101 8.1 0
delta-BHC 0 0 95.1
Aldrin 102 7.4 0
Heptachlor epoxide 0 0 103
gamma-Chlordane 75.1 8.1 0
Endosulfan I 0 0 103
4,4' -DDE 0 0 82.1
Dieldrin 0 0 117
Endrin 0 0 107
4,4'-DDD 0 0 68.4
Endosulfan II 0 59.8 40.2
4,4'-DDT 85.9 0 0
Endrin aldehyde 0 0 112
Endosulfan sulfate 0 90.4 0
4,4 •-Methoxychlor 0 0 103
1
Aroclor 1260 was spiked separately from the organochlorine pesticides. Single determination.
The amount loaded to the cartridge was 10 µg per compound.
20
cartridges. An additional 5 mL of hexane with 50 percent diethyl ether were passed through the
2.0-g cartridges to collect Fraction 3. The results are summarized in Tables 11 through 13. All
compounds, except endrin aldehyde, were recovered quantitatively (recovery >75 percent) in
the two or three fractions combined. The elution patterns seem to vary with the size of the
cartridge; however, they are very consistent within one cartridge size. For example, in the case
of the 0.5-g cartridges, 7 compounds, namely alpha-BHC, gamma-BHC, heptachlor, aldrin,
4,4 '-DDE, 4,4 '-DDD, and 4,4 '-DDT, were recovered in Fraction 1, and 13 compounds were
recovered in Fraction 2, demonstrating that some compounds are present in both fractions. The
number of compounds recovered in Fraction 1 from the 2-g cartridges decreased to three
(heptachlor, aldrin, and 4,4 '-DDE), and an additional 5 mL of hexane with 50 percent diethyl
ether were needed to recover delta-BHC, endosulfan II, endrin aldehyde, and endosulfan sulfate
from the 2-g silica cartridge (Table 13).
At the time we were evaluating the Florisil and silica cartridges for their applicability
to the cleanup of sample extracts containing organochlorine pesticides, we came across a
protocol using diol cartridges (4). The diol procedure specifies use of 0.5-g and 1-g cartridges,
and elution of the organochlorine pesticides with hexane with 10 percent acetone. We evaluated
this procedure using 0.5-g, 1-g, and 2-g cartridges charged with the target organochlorine
pesticides at 0.2 µg, 1.0 µg, and 2.0 µg per cartridge. Two fractions were collected from the
0.5-g and 1-g cartridges, and four fractions were collected from the 2-g cartridges. For the 1-g
cartridges charged at 2.0 µg per compound, we collected an additional fraction to verify that the
compounds were eluted quantitatively from the cartridge.
The data are summarized in Tables 14 through 16. At the 0.2-µg spike level, sixteen
compounds eluted in Fraction 1 from the 0.5-g cartridges, and only two compounds (endrin
aldehyde and endosulfan sulfate) eluted in Fraction 2. Small amounts (recovery <6 percent) of
delta-BHC and endosulfan II were found in Fraction 2 from the cartridges spiked at 2.0 µg per
cartridge. As the cartridge size was increased, more compounds were found in Fraction 2. For
example, in addition to delta-BHC and endosulfan II, endrin aldehyde and endosulfan sulfate
were detected in Fraction 2 from the 1-g cartridges spiked at O.S µg and 2.0 µg per cartridge.
In addition, beta-BHC and small amounts of gamma-BHC and 4,4 '-methoxychlor were detected
in Fraction 2 from the 1-g cartridges spiked with 2.0 p.g. Finally, the elution patterns for the 2-g
cartridges were quite different from those of the 0.5-g and 1-g cartridges, and they also varied
with the amounts spiked on the cartridges (Table 16).
The diol procedure gave quantitative recoveries of the 17 organochlorine pesticides

when hexane with 10 percent acetone was used to elute the analytes; however, PCBs also eluted
in Fraction 1. An experiment was performed in which diol cartridges were eluted, first with
3 mL hexane (Fraction 1), then with two 5-mL portions of hexane with 10 percent acetone
(Fractions 2 and 3). Under those conditions, PCBs and heptachlor, aldrin, endosulfan I,
4,4 '-DDE, and 4,4 '-DDT were recovered in Fraction 1, and the remainder of the pesticides
eluted in Fraction 2, with most of the endrin aldehyde and endosulfan sulfate eluting in
Fraction 3 (Table 17).
Matrix intcrferents such as com oil, diesel hydrocarbons, and elemental sulfur, were
added to hexane solutions containing the target analytes at known concentrations, and the
21
..
TABLE 11. PERCENT RECOVERIES AND E~UTION PATTERNS OF 17 ORGANOCHLORINE PESTICIDES FROM
0.5-g SILICA CARTRIDGES•
1e
N
Spiked at 0.2 µg per cartridge Spiked at 1.0 µg per cartridge Spiked at 2.0 µg per cartridge ~
0
Compound Fraction 1 Fraction 2 Fraction 1 Fraction 2 Fraction 1 Fraction 2 rn
w
alpha-BHC 86.3 101 35.3 20.8 76.7 72.1 34.3 38.3 87.1 85.8 35.3 36.4
gamma-BHC 0 16.0 J05 JO) 9.2 12. J 93.9 90.J 15.4 16.9 93.8 92.J
beta-BHC 0 0 113 113 0 0 98.9 95.6 0 0 104 103
Heptachlor 104 103 0 0 85.6 86.4 0 0 95.J 93.9 0 0
delta·BHC 0 0 106 107 0 0 96.4 91.6 0 0 94.6 94.1
Aldrin 91.8 90.8 0 0 78.1 78.J 0 0 85.4 84.4 0 0
Heptachlor epoxide 0 0 112 113 0 0 JO) 97.3 0 0 103 JOO
Endosutfan I 0 0 112 116 0 0 J03 97.7 0 0 105 104
4,4'-DDE 96.8 9'J.S 0 0 89.5 84.5 0 0 92.4 91.7 0 0
Dieldrin 0 0 109 111 0 0 96.3 92.3 0 0 93.5 92.4
Endrin 0 0 148 151 0 0 152 142 0 0 1 JO 106
4,4'-DDD 92.5 110 0 0 88.8 82.5 20.1 23.9 92.8 91.6 19.5 22.1
~
F.ndosutfan n 0 0 107 108 0 0 95.4 92.8 0 0 99.4 97.0
4,4'-DDT 101 107 0 0 93.3 89.6 0 0 94.2 91.8 0 0
F.ndrin aldehyde 0 0 82.8 90.0 0 0 74.9 72.9 0 0 82.9 83.2
Endosutfan sulfate 0 0 111 118 0 0 122 94.7 0 0 101 100
4,4 '-Metroxychlor 0 0 113 119 0 0 108 98.3 0 0 101 99.8
•Silica cartridges (Supclco lot SP0161) were used; each cartridge was conditioned with 4 mL hexane prior to use. Each
experiment was perfonned in duplicate. Each cartridge was spiked with 2 mL of a hexane solution containing the organochlorine
pesticides at the concentrations stated above. Fraction 1 was eluted with 5 mL hexane, Fraction 2 with 5 mL hexane with
SO percent diethyl ether. Vacuum manifold used was the Analytichem SPS24.
TABLE 12. PERCENT RECOVERIES AND ELUTION PATTERNS FOR 17 ORGANOCHLORINE PESTICIDES FROM
1-g SILICA CARTRIDGES•
.....
.....
Spiked at 0.2 µg per cartridge Spiked at 1.0 µg per cartridge Spiked at 2.0 µg per cartridge "'
~
0
Compound Fraction 1 Fraction 2 Fraction 1 Fraction 2 Fraction 1 Fraction 2 U)
w
alpha-BBC 0 0 92.8 96.3 0 0 99.6 96.4 3.9 8.5 102 105
gamma-BHC 0 0 91.5 94.5 0 0 97.2 94.2 0 0 95.0 96.3
bcta-BHC 0 0 79.3 81.5 0 0 101 95.9 0 0 102 106
Heptachlor 89.8 89.0 0 0 99.1 98.6 0 0 102 105 3.5 4.3
delta-BHC 0 0 82.5 84.8 0 0 96.8 93.5 0 0 91.7 95.4
Aldrin 89.5 88.8 0 0 97.9 97.1 0 0 100 102 2.3 2.9
Heptachlor epoxide 0 0 92.5 94.8 0 0 101 97.2 0 0 99.7 102
Endosulfan I 0 0 101 104 0 0 101 97.3 0 0 102 105
4,4'-DDB 91.0 90.3 0 0 102 102 0 0 105 109 0 0
Dieldrin 0 0 89.3 92.S 0 0 95.S 92.6 0 0 91.2 92.5
Endrin 0 0 94.8 98.0 0 0 151 145 0 0 104 107
~ 4,4'-DDD' 0 0 84.8 92.0 13.4 11.6 95.6 94.1 14.2 24.8 94.7 93.2
F.ndosulfan n 0 0 88.5 91.5 0 0 98.8 95.6 0 0 99.4 102
4,4'-DDT 87.5 84.5 0 0 100 99.4 0 0 94.7 98.2 7.5 5.5
F.ndrin aldehyde 0 0 50.0 51.5 0 0 59.3 59.2 0 0 67.4 70.9
Bndosulfan sulfate 0 0 94.5 97.5 0 0 98.2 95.3 0 0 99.1 102
4,4 '-Mcthoxychlor 0 0 91.8 95.0 0 0 104 100 0 0 97.4 100
•Silica cartridges (Supeloo lot SP0161) were used; each cartridge was conditioned with 4 rnL hexane prior to use. Each experiment
wu performed in duplicate. Each cartridge was spiked with 2 mL of a hexane solution containing the organochlorinc pesticides at
the concentrations stated above. Fraction 1 was eluted with 5 rnL hexane, Fraction 2 with 5 mL hexane with 50 percent diethyl
ether. Vacuum manifold used was the Analytichem SPS24.
TABLE 13. PERCENT RECOVERIES AND ELUTION PATTERNS OF 17 ORGANOCHLORINE PESTICIDES FROM
2-g SILICA CARTRIDGES•
~
Spiked at 0.2 µg per cartridge Spiked at 1.0 µg per cartridge Spiked at 2.0 µg per cartridge
"'
0
I-
0
Compound Fraction I Fraction 2 Fraction 3 Fraction I Fraction 2 Fraction 3 Fraction 1 Fraction 2 Fraction 3 (/)
w
alpha-BBC 0 0 93.3 91.5 0 0 0 0 98.2 93.6 0 0 0 0 103 104 0 0
gamma-BBC 0 0 92.5 89.8 0 0 0 0 98.2 93.9 0 0 0 0 98.3 99.3 0 3.4
beta-BBC 0 0 94.3 92.8 0 0 0 0 103 91.2 0 0 0 0 108 llO 0 0
Beptachlor 21.3 33.0 85.8 75.3 0 0 22.0 25.4 90.7 88.5 0 0 11.8 36.7 97.4 96.3 0 0
delta-BBC 0 0 59.3 64.8 32.0 25.5 0 0 92.0 83.9 6.7 14.1 0 0 89.6 81.6 14.0 30.9
Aldrin 76.S 82.8 31.0 22.8 0 0 66.4 76.1 36.4 43.0 0 0 39.0 88.2 48.9 39.3 0 0
BqUchlor epoxide 0 0 95.S 94.8 0 0 0 0 104 97.7 0 0 0 0 105 106 0 0
Endosulfm I 0 0 96.3 96.0 0 0 0 0 105 98.8 0 0 0 0 107 llO 0 0
4,4'-DDB 49.8 64.0 56.5 43.3 0 0 48.7 55.0 62.4 66.0 0 0 2.6 68.3 78.8 72.5 0 0
Dieldrin 0 0 93.0 92.8 0 0 0 0 99.4 95.1 0 0 0 0 98.6 99.8 0 0
P..ndrin 0 0 113 114 0 0 0 0 139 136 0 0 0 0 105 106 0 0
4,4'-DDD 0 0 97.3 98.8 0 0 0 0 105 100 0 0 0 0 108 109 0 0
Bndosulfm n 0 0 0 0 83.0 82.8 0 0 22.5 20.5 77.4 81.6 0 0 15.5 11.9 88.7 96.4
4,4'-DDT 0 0 95.0 95.5 0 0 0 0 103 97.2 0 0 0 0 103 105 0 0
N P..ndrin aldehfde 0 0 0 0 0 0 0 0 37.2 34.6 29.0 29.6 0 0 39.4 35.2 37.9 44.6
~
F.ndosulflll sulfate 0 0 0 0 74.5 76.3 0 0 0 0 88.1 90.2 0 0 0 0 97.2 104
4,4' -Methoxychlor 0 0 87.5 90.3 0 0 0 0 104 96.7 0 0 0 0 103 99.9 0 11.8
• Silica catridges (Supelco lot SP0204) were 119Cd; each cartridge was conditioned with 4 mL hexane prior to use. Each experiment was perfonned in duplicate.
Eich cartridge wu spited with 2 mL of a hexane 110lution containing the organochlorine pesticides at the concentrations stated above. Fraction 1 was eluted
with S mL he:une, Pnclion 2 with S mL hexane with SO percent diethyl ether, and Fraction 3 with 5 mL hexane with SO percent diethyl ether. Vacuum
mlllifold used wu the Analytichem SPS24.
TABLE 14. ELUTION PATIERNS AND PERCENT RECOVERIES OF 17 ORGANO-
CHLORINE PESTICIDES FROM 0.5-g DIOL CARTRIDGES•
;::::
Spiked at 0.2 µg per cartridge Spiked at 1.0 µg per cartridge Spiked at 2.0 µg per cartridge N
~
0
Compound Fraction 1 Fraction 2 Fraction 1 Fraction 2 Fraction l Fraction 2 (/)
w
alpha-BHC 83.3 83.0 0 0 115 117 0 0 105 106 0 0
garnma-BHC 79.8 79.8 0 0 115 113 0 0 105 99.0 0 0
beta-BHC 84.0 84.5 0 0 122 120 0 0 105 lot 0 0
Hcptachlor 58.8 58.3 0 0 84.8 80.9 0 0 76.2 81.8 0 0
delta-BBC n.5 77.0 0 0 112 11 t 0 0 102 94.5 4.8 5.4
Aldrin 53.0 52.8 0 0 82.5 79.2 0 0 72.2 76.9 0 0
Hcptaehlor cpoxidc 81.7 80.8 0 0 114 109 0 0 101 100 0 0
Endosulfan I 70.3 70.0 0 0 103 96.0 0 0 90.2 92.9 0 0
4,4'-DDB 55.8 55.0 0 0 87.4 82.6 0 0 74.0 78.9 0 0
Dieldrin 79.8 79.0 0 0 113 109 0 0 102 97.9 0 0
Endrin n.o 76.3 0 0 113 107 0 0 98.0 97.4 0 0
4,4'-DDD 81.8 82.3 0 0 122 117 0 0 tot 101 0 0
Endolulfan 11 80.5 80.3 0 0 115 114 0 0 102 97.8 0 3.3
4,4'-DDT 72.0 70.8 0 0 106 101 0 0 93.9 94.7 0 0
Endrin aldehyde 0 0 38.8 36.8 84.1 78.2 24.2 24.3 12.4 15.4 65.8 67.3
Bndosulfan sulfate 39.8 39.5 58.3 53.3 111 117 12.6 8.6 4.9 5.8 96.6 92.6
4,4 '-Mcthoxychlor 82.5 82.3 0 0 118 117 0 0 100 97.7 0 0
• Diol cartridges (Supclco lot SP0155) wen:: used; each cartridge was conditioned with 4 mL hexane with 10 percent acetone prior to use.
Eich experiment was perfonned in duplicate. Each cartridge was spiked with 2 mL of a hexane solution at the concentrations stated
above. Fractions 1 and 2 were each eluted with 5 mL hexane with 10 percent acetone. Vacuum manifold used was the Analytichem
SPS24.
TABLE 15. ELUTION PATTERNS AND PERCENT RECOVERIES OF 17 ORGANOCHLORINE PESTICIDES FROM 1-g
DIOL CARTRIDGES•
,....
N
N
Spiked at 0.2 µg per Spiked at 1.0 µg per g
cartridge cartridge Spiked at 2.0 µg per cartridge 0
fl)
w
Compound Fraction l Fraction 2 Fraction l Fraction 2 Fraction 1 Fraction 2 Fraction 3
alpha-BBC 86.3 97.5 0 0 113 95.8 0 0 107 107 0 0 0 0
gamma-BBC 80.3 89.8 0 0 107 90.0 4.8 4.7 102 101 4.1 4.6 0 0
beta-BBC 60.5 62.3 0 0 112 94.5 0 0 97.8 93.5 15.4 20.2 0 0
Beptachlor 80.5 92.0 0 0 107 90.9 0 0 103 104 0 0 0 0
delta-BBC 52.8 51.8 32.7 41.5 101 87.1 8.9 8.0 84.5 78.1 26.1 5.4 0 0
Aldrin 77.3 88.5 0 0 104 89.3 0 0 99.7 102 0 0 0 0
Beptachlor epoxide 81.8 94.0 0 0 110 93.6 0 0 105 104 0 0 0 0
Endosulfan I 85.3 98.0 0 0 114 96.1 0 0 104 103 0 0 0 0
4,4'-DDE 82.5 94.0 0 0 111 95.0 0 0 100 101 0 0 0 0
Dicldrin 80.5 92.0 0 0 106 90.7 0 0 102 100 0 0 0 0
~ Endrin 81.3 94.0 0 0 111 94.2 0 0 97.2 97.6 0 0 0 0
°' 4,4'-DDD 80.3 92.0 0 0 113 95.3 0 0 104 102 0 0 0 0
Endosulfan n 65.5 66.3 20.8 30.3 108 91.6 0 0 94.9 89.7 17.5 23.8 0 0
4,4'-DDT 81.0 92.8 0 0 110 94.4 0 0 102 100 0 0 0 0
Endrin aldehyde 0 0 50.3 46.5 50.8 41.3 54.0 55.9 15.8 11.7 75.0 71.7 20.9 21.1
Endosulfan sulfate 0 0 66.8 61.3 26.7 23.0 91.0 93.0 0 0 86.8 81.8 21.4 24.4
4,4 '-Methoxychlor 73.8 80.5 0 0 108 91.6 0 0 97.1 93.1 0 10.9 0 0
• Diol canridgcs (Supclco lot SP0216) were used; each cartridge was conditioned with 4 mL hexane with 10 percent acetone prior to use.
Each experiment was performed in duplicate. Each cartridge was spiked with 2 mL of a hexane solution at the concentrations stated
above. Fraction l, 2, and 3 were each eluted with 5 mL hexane with 10 percent acetone. Vacuum manifold used was the Analytichem
SPS24.
TABLE 16. ELUTION PATTERNS AND PERCENT RECOVERIES OF 17 ORGANO-
CHLORINE PESTICIDES FROM 2-~ DIOL CARTRIDGES•
(')
Spiked at 0.2 µg per cartridge Spiked at 1.0 µg per cartridge "~"'

0
Compound Fraction 1 Fraction 2 Fraction 3 Fraction 4 Fraction 1 Fraction 2 Cf)
w
alpha-BBC 0 0 97.5 97.5 0 0 0 0 93.1 81.4 30.1 30.7

gamma-BBC 0 0 88.5 87.0 0 15.0 0 0 31.1 29.3 88.0 70.6
beta-BHC 0 0 0 0 75.0 58.5 0 0 0 0 105 81.3
Heptachlor 96.0 99.8 0 0 0 0 0 0 107 99.7 0 0
delta-BBC 0 0 0 0 0 0 73.5 61.5 0 0 96.6 76.2
Aldrin 96.0 82.8 0 0 0 0 0 0 108 100 0 0
Beptachlor epoxide 0 0 88.5 91.5 0 0 0 0 99.4 90.0 16.6 15.3
Endosulfan I 60.0 49.0 40.5 48.0 0 0 0 0 105 99.3 7.2 0
4,4'-DDE 97.5 83.0 0 0 0 0 0 0 110 104 0 0
Dieldrin 0 0 90.0 91.5 0 0 0 0 95.6 84.9 15.6 15.5
Endrin 0 0 85.5 90.0 0 0 0 0 103 94.0 9.7 8.5
t-> 4,4'-DDD 0 0 93.0 93.0 0 0 0 0 65.5 55.0 60.9 51.0
...... Endosulfan II 0 0 0 0 70.5 45.0 27.0 49.5 0 0 102 78.8
4,4'-DDT 30.0 0 67.5 73.5 0 0 0 0 103 95.4 8.6 7.6
Endrin aldehyde 0 0 0 0 0 0 0 0 0 0 20.4 11.6
Endosulfan sulfate 0 0 0 0 0 0 0 0 0 0 8.1 0
4,4 '-Mcthoxychlor 0 0 0 0 77.0 78.0 0 0 0 0 102 76.7
(continued)
• Diol cartridges (Supelco lot SP0216) were used; each cartridge was conditioned with 4 mL hexane with 10 percent acetone
prior to use. Each experiment was performed in duplicate. Each cartridge was spiked with 2 mL of a hexane solution at the
concentrations stated above. Fractions l, 2, 3, and 4 were each eluted with 5 mL hexane with 10 percent acetone. Vacuum
manifold used was the Analytichem SPS24.
TABLE 16. (Concluded)•
~
N
Spiked at 1.0 µg per cartridge Spiked at 2.0 µg per cartridge g
0
Compound Fraction 3 Fraction 4 Fraction 1 Fraction 2 Fraction 3 Fraction 4 (/)
w
alpha-BBC 0 0 0 0 11.5 9.2 101 102 0 0 0 0

gamma-BBC 0 0 0 0 0 0 98.8 99.9 4.0 5.2 0 0
beta-BBC 0 0 0 0 0 0 43.4 28.1 68.7 83.0 0 0
Beptachlor 0 0 0 0 105 108 5.8 5.6 0 0 0 0
delta-BBC 0 0 0 0 0 0 8.2 3.8 82.9 77.6 15.2 30.0
Aldrin 0 0 0 0 104 108 3.4 3.6 0 0 0 0
Hcptachlor epoxidc 0 0 0 0 37.8 30.3 85.4 91.8 0 0 0 0
Endosulfan I 0 0 0 0 84.0 84.1 39.6 44.4 0 0 0 0
4,4'-DDE 0 0 0 0 103 106 4.7 4.4 0 0 0 0
Dicldrin 0 0 0 0 25.7 18.4 86.8 91.2 0 0 0 0
F.ndrin 0 0 0 0 45.8 37.4 73.l 80.3 0 0 0 0
4,4'-DDD 0 0 0 0 0 0 99.1 99.4 0 0 0 7.5
F.ndosulfan II 0 0 0 0 0 0 36.1 19.5 75.3 86.6 4.0 0
4,4'-DDT 0 0 0 0 62.6 59.3 61.6 67.3 0 0 0 0
Endrin aldehyde 64.3 61.4 12.8 17.4 0 0 1.5 7.9 0 0 0 0
Endosulfan sulfite 88.9 84.8 10.8 18.6 4.2 0 0 0 0 0 0 0
4,4' -Mcthoxychlor 0 0 0 0 0 0 84.1 77.2 19.9 29.5 0 0
• Diol cartridges (Supclco lot SP0216) were used; each cartridge was conditioned with 4 mL hexane with 10 percent acetone
prior to use. Each experiment was perfonned in duplicate. Each cartridge was spiked with 2 mL of a hexane solution at the
conoeruations stated above. Fractions l, 2, 3, and 4 were each eluted with 5 mL hexane with 10 percent acetone. Vacuum
manifold used was the Analytichcm SPS24.
TABLE 17. ELUTION PATTERNS AND PERCENT RECOVERIES OF 17 ORGANOCHLORINE PESTICIDES AND
AROCLOR 1260 FROM 1-g DIOL CARTRIDGES
,...
II)
Spiked with organochlorine pesticides at 0.2 µg Spiked with organochlorine pesticides at 0.2 µg "'
g
and Aroclor 1260 at 80 µg per cartridge and Aroclor 1260 at 2 µg per cartridge 0
en
w
Fraction 2 Fraction 3 Fraction 2 Fraction 3
(5 mL hexane (5 mL hexane (S mL hexane (S mL hexane
Fraction 1 with 10 percent with 10 percent Fraction 1 with 10 percent with 10 percent
Compound (3 mL hexane) acetone) acetone) (3 mL hexane) acetone) acetone)
Aroclor 1260 90 10 0 100 0 0
alpha-BHC 0 93 0 0 106 0
gamma-BHC 0 105 0 0 96 0
beta-BHC 0 103 0 0 100 0
Hcptachlor 112 0 0 102 0 0
dclta-BHC 0 97.3 0 0 113 0
Aldrin 116 0 0 110 0 0
Hcptachlor cpoxidc 0 97.3 0 0 112 0
~
Endosulfan I 58.5 71.5 0 59.2 93.2 0
4,4'-DDE 124 0 0 123 0 0
Dicldrin 0 108 0 0 112 0
Endrin 0 >100- 0 0 100 0
4,4'-DDD 0 99.5 0 0 100 0
Endosulfan D 0 >100- 0 0 100 0
4,4'-DDT >100- 0 0 100 0 0
Endrin aldehyde 0 39.5 60.5 0 35.0 65.0
Endosulfan sulfate 0 29.2 70.8 0 14.0 86.0
4,4 '-Mcthoxychlor 0 >100- 0 0 100 0
•eannot be quantitated accurately because of interference from Aroclor 1260.

solutions were then subjected to the silica or the dial cartridge cleanup procedure to establish
if any changes occurred in the target compound elution pattern and in their recoveries
caused by matrix interferents (Tables 18 and 19). These interferents were selected because they
mimic typical background contamination in certain environmental sample matrices that could
also be contaminated with the target compounds. For example, com oil would be representative
of fatty acid triglycerides, and diesel hydrocarbons of petroleum hydrocarbons. The data
presented in Tables 18 and 19 indicate that neither the com oil nor the diesel hydrocarbons
affected the elution patterns of the 17 organochlorine pesticides. Elemental sulfur, if present,
is eluted from the silica cartridge with S mL hexane and will interfere only with the gas
chromatographic analysis of heptachlor and aldrin on the DB-1701 column (Figure 4). 4,4 '.
DOE and 4,4 '-DDT also elute in Fraction 1, however, they can be quantified without any
difficulty on any of the two columns. The remainder of the 17 organochlorine pesticides are
retained on the silica cartridge and then eluted with hexane with 50 percent diethyl ether. The
dial cartridge procedure was also evaluated to determine whether elemental sulfur, if present,
can be separated from the organochlorine pesticides. We found that when the cartridge is
eluted with hexane with 10 percent acetone, the elemental sulfur elutes from the cartridge
together with the organochlorine pesticides and will interfere with the gas chromatographic
analysis on the DB-1701 column of compounds 1 through 6 in Table 1 (Figure 5). It is possible
that elemental sulfur could be removed as in the case of the silica cartridge, however, we have
not tested this yet.
5.2 PHTHALATE ESTERS
Florisil and alumina SPE cartridges were evaluated for their use in phthalate ester
analysis. These cartridges were chosen because the current SW-846 Method 8060 recommends
use of either Florisil (Method 3620) or alumina (Method 3610) for cleanup of sample extracts
containing phthalate esters. In Method 3620, Florisil (60/80 mesh) is activated for 16 hours at
140°C and then deactivated with water (3 percent by weight). The charged Florisil column is
eluted with hexane (40 mL) to remove interfering compounds; phthalate esters are then
recovered with 100 mL hexane with 20 percent diethyl ether. In Method 3610, neutral alumina,
activity Super I, W206 series, is activated for 16 hours at 400°C and the phthalate esters are
recovered with 140 mL of hexane with 20 percent diethyl ether.
We have evaluated both methods with hexane solutions containing the 16 phthalate
esters listed in Table 2. The percent recoveries of the 16 compounds are presented elsewhere
(5). Alumina cleanup is preferred over the Florisil cleanup since it allows recovery of all target
compounds by elution with hexane with 20 percent diethyl ether. When Florisil cleanup was
used, BMEP, BEEP, and BBEP could not be recovered at all, and DMP and DEP gave
recoveries of only 40 and 57 percent, respectively.
To improve the recoveries of the five phthalate esters mentioned above, we have taken
Florisil and alumina SPE cartridges of 0.5-g, 1.0-g, and 2-g size, charged them with the target
compounds and interferents, and eluted them with hexane with 10 percent acetone (for Florisil)
or hexane with 20 percent acetone (for alumina). We had at first attempted to elute the
phthalate esters from the alumina cartridge with hexane with 20 percent diethyl ether. Since
none of the phthalate esters was recovered after 10 mL solvent passed through the cartridge, we
changed the eluting solvent to hexane with 10 percent acetone and later to hexane with
20 percent acetone to improve the recovery of BMEP, BEEP and BBEP. The results of these
experiments are summarized in Tables 20, 21, and. 22.
30
TABLE 18. PERCENT RECOVERIES AND ELUTION PATIERNS OF 17 ORGANOCHLORINE PESTICIDES FROM
1-g SILICA CARTRIDGF...S IN THE PRESENCE OF CORN OIL AND DIESEL HYDROCARBONS•
~
N
Corn oil as interferents Diesel hydrocarbons as interferents
~
0
Compound Fraction 1 Fraction 2 Fraction 3 Fraction 1 Fraction 2 Fraction 3 (/)
w
alpha-BHC 0 0 121 119 0 0 0 0 115 116 0 0

gamma-BHC 0 0 124 122 0 0 0 0 118 120 0 0
beta-BHC 0 0 114 111 0 0 0 0 106 108 0 0
Heptachlor 119 123 0 0 0 0 115 113 0 0 0 0
delta-BHC 0 0 115 112 0 0 0 0 108 111 0 0
Aldrin 119 120 0 0 0 0 112 110 0 0 0 0
Heptachlor cpoxide 0 0 123 121 0 0 0 0 118 120 0 0
Endosulfan I 0 0 121 118 0 0 0 0 117 119 0 0
4,4'-DDE 113 120 0 0 0 0 120 118 0 0 0 0
Dieldrin 0 0 117 114 0 0 0 0 111 114 0 0
Endrin 0 0 143 142 0 0 0 0 150 156 0 0
~ 4,4'-DDD 0 13.3 109 106 0 0 14.2 16.5 106 108 0 0
~
Endosulfan II 0 0 113 110 0 0 0 0 109 111 0 0
4,4'-DDT 103 114 0 0 0 0 115 109 0 0 0 0
Endrin aldehyde 0 0 66.7 64.7 26.9 31.8 0 0 55.4 62.5 31.0 31.6
Endosulfan sulfate 0 0 108 105 0 0 0 0 98.2 103 0 0
4,4 '-Mcthoxychlor 0 0 110 107 0 0 0 0 105 107 0 0
•Silica cartridges (Supclco lot SP0161) were used; each cartridge was conditioned with 4 mL hexane prior to use. Each experiment was
pcrfonncd in duplicate. Each cartridge was spiked with 2 mL of a hexane solution containing the organochlorine pesticides at 0.5 µg/
mL, the com oil at 500 µg/mL, and the diesel hydrocarbons at 1000 µg/mL. Fraction 1 was eluted with 5 mL hexane, Fraction 2 with 5
mL hexane with SO percent diethyl ether, and Fraction 3 with 5 mL hexane with 50 percent diethyl ether. Vacuum manifold used was
the Analytichem SPS24.
TABLE 19. PERCENT RECOVERIES AND ELUTION PATTERNS OF 17 ORGANOCHLORINE PESTICIDES FROM
1-g DIOL CARTRIDGES IN THE PRESENCE OF CORN OIL AND DIESEL HYDROCARBONS•
Corn oil as interferents Diesel hydrocarbons as interferents ""

......
(\I
~
0
Compound Fraction 1 Fraction 2 Fraction 3 Fraction 1 Fraction 2 Fraction 3 U)
w
alpha-BHC 121 119 0 0 0 0 115 116 0 0 0 0
gamma-BHC 120 118 0 0 0 0 116 118 0 0 0 0
beta-BHC 108 106 0 0 0 0 102 104 0 0 0 0
Heptachlor 120 119 0 0 0 0 117 119 0 0 0 0
delta-BHC 108 107 0 0 0 0 108 110 0 0 0 0
Aldrin 115 113 0 0 0 0 111 117 0 0 0 0
Heptachlor epoxide 120 116 0 0 0 0 120 122 0 0 0 0
Endosulfan I 121 120 0 0 0 0 120 124 0 0 0 0
4,4'-DDE 115 115
. 0 0 0 0 116 122 0 0 0 0
Dieldrin 118 116 0 0 0 0 118 120 0 0 0 0
F.ndrin 111 111 0 0 0 0 116 120 0 0 0 0
~ 4,4'-DDD 112 110 0 0 0 0 115 118 0 0 0 0
t->
Endosulfan II 111 108 0 0 0 0 114 115 0 0 0 0
4,4'-DDT 110 110 0 0 0 0 114 117 0 0 0 0
Endrin aldehyde 28.6 26.8 73.0 76.8 0 0 22.8 0 69.8 42.6 0 0
Endosulfan sulfate 0 0 102 108 0 0 0 0 111 107 0 0
4,4' -Methoxychlor 100 99.0 0 0 0 0 98.6 100 0 0 0 0
• Diol cartridges (Supelco lot SP0206) were used; each cartridge was conditioned with 4 mL hexane with 10 percent acetone prior to use.
Each experiment was performed in duplicate. Each cartridge was spiked with 2 mL of a hexane solution containing the organochlorine
pesticides at O.S µg/mL, the com oil at 500 µ.g/mL, and the diesel hydrocarbons at 1000 µg/mL. Fractions l, 2, and 3 were each eluted
with 5 mL hexane with 10 percent acetone in hexane. Vacuum manifold used was the Analytichem SPS24.
,.,....
~)
0
._,
~
~
DB-608 ·-· DB-608
-
I-
~
,,,0
.:,, r-
z'
-E
,., 11)
t•l
Q)
"'
(II
...
IO
C•
f•J
.. .. N
0 ·=·IL
0: 0- l'l w
w I .,. If• <1 ,.., IJ
N
:~I~
~
<t f•I
..,
I'll
. 1•1
°' ..
~r. I ll I wts-
1- ~·
~Pl I 1111I111111 .,.l <tl l l l l l l I I I l I I I I I

• - IO
., °'
I') <t
~ DB-1701 :..:
u
DB-1701
-,
0
1-
-z °' r-'°
,....
10 f~ l'-
IO ID
E: 0- ••
• If) -0
z z
-~'4t
-~
:Ell>
Elfl
' '
E
E:
(.) .. U··
0
If•
l•l
0
<S>O:
'5)
·W
rt: '°
ro ro
•W
&N
<S>N
'°
Q
Q WN
Wfll J Wl'l
Wt<I J CL
0. :J lf)
lf) II..
t-:;:: I
t-zl
O:W
w
__J
Figure 4. GC/ECD chromatograms of a Method 8081 organochlorine pesticide standard

containing elemental sulfur, passed through a silica cartridge; Fraction 1 (left),
Fraction 2 (right). The GC operating conditions are given in Table 1
.,
~
(..)
DB-608
..
·-·
WC·
f-- ••
I- 1_t1
·I,_. ! 1' I
i I
•
: !
I 1
II I
!
I
i I r,
I
I I
I I
lIIIi !i!
v
f•J (j.
·-·
f--
DB-1701
Figure 5. GC/ECD chromatograms or a Method 8081 organochlorine pesticide standard

containing elemental sulfur, passed through a dlol au1rldge. Hexane with
10 percent acetone was used as eluant.
34
TABLE 20. ELUTION PATTERNS AND PERCENT RECOVERIES OF THE PHTHALATE
ESTERS FROM THE FLORISIL CARTRIDGES USING HEXANE WITH
10 PERCENT ACETONE•
0-~-g rnrt rldite 1-g cart ridge 2-g cart ridge
40-141plke llfl-µg spike I 211-l'R spike 411-µg spike llfl-µg spike 120-µg spike 40-µg spike llfl-pg spike 1211-l'g spike
ColllPMftd Fl"lld'- I Fl'llcllnn I "'r•dlt"' I •·ractlnn I 1''racllcm I •·rarllnn I l<'ractlnn I Fraction I •·racliun I
DMP 98.9 101 81.2 KO.II 7:l.9 76.4 •H.I 117.6 42.1 57.7 211.5 15.7 70.9 95.J 37.1 3'>.5 63.6 72.9
DEP 108 113 91.J CJ.\. I llU 115.3 1)1),5 95.1 111.2 117.] 7K.6 76.5 111 1)4.0 1110 IOI 1117 1117
DIOP 109 106 92.K 91.7 K7.K 91.K 1)4.1) Kii.ti 1111.7 1>2.1 I)(),, KR.I 114 JO] 92.2 92.8 lib.') K6.0
DBP 104 107 87.4 Kll.5 110.I KJ.I 100 105 111).J 117.4 117.') 115.11 toll IOK 91.4 92.4 112.5 110.1)
BMPP 106 114 9K.2 95.9 116.4 90.2 112 I)'). I 95.4 1J4 I 92.S K1J.2 115 116 94.11 95.11 IO:'i 911.5
BME.P' 16.0 15.6 11.9 14.K I0.7 15.'l
OAP I07 Ill 94.8 91.5 112.7 117.1) %.8 92.1 89.4 92.5 1111.1 K5.6 113 106 91.8 92.3 KJ.4 82.6
BEEP 96.6 97.6 74.7 69.3 65.K 71.6 96.0 91.1 • • • • • • • • • •
HEHP 99.6 98.4 75.6 75.9 65.l 611.9 IOI 90.8 70.6 70.2 Mi.I 63.9 83.9 93.8 68.9 84.3 77.8 77.5
DHP I05 1119 91.0 87.6 78.6 86.0 99.4 94.1 118.6 117.9 85.I 112.5 106 IOJ 86.4 90.9 110.6 711.3
BBP 108 1119 84.1 82.3 67.5 71.J 99.8 97.3 80.4 112.11 70.1 69.5 109 104 83.2 93.9 IOI 97.2
BBEP 113 117 98.5 94.3 83.2 91.4 I05 119.9 95.3 102 97.4 93.5 118 112 911.3 95.9 94.1 87.0
OEHP Ill Ill 92.1 87.6 76.5 84.5 95.6 87.4 68.0 74.7 47.1 50.2 II I 65.8 82.9 84.4 81.5 77.6
DCP 91.4 81.6 62.9 61.7 53.5 57.0 97.0 84.I 62.0 53.7 59.0 48.0 69.6 720 59.9 57.3 72.2 59.9
w OOP 120 114 102 93.2 83.3 95.4 99.9 94.3 911.1 97.9 98.5 93.0 114 115 I03 99.4 97.3 86.9
ONP 103 92.2 95.9 Ill 98.8 9K.t 100 98.3 94.8 118 115 IOI 99.3 92.8 88.S
°' 118 118 KJ.I
• Each artrict,e - preD01Mlitioned with 4 ml heunt! f'l"ior to use Each expaiment was performed in duplicate. Fraction l was eluted with 5 mL hexane with
10 percent llOetone; Fraction 2 with S mL heunc W1th 10 percent acetone A third fraction was collected from the 2-g cartridge by elution with 5 mL hexane with
I 0 percent llOetone.
•Additional BMEP _,recovered rrom the O.S-g Flomil cartridge hy eluting the cartridge with an additional 5 mL hexane with JO percent acetone (Fraction 2). The
recoveries in Fraction l were 70.l and 71.l percent for the 40-µg spike, 55.4 and 54.3 percent for the !10-µg spike, 53.4 and 54.l percent for the 120-µg spike.
• Compound not recovered in any or the three fractions.
•BEEP phthlllale was recovered by eluting lhe cartridge with an additional 5 mL hexane with of 10 percent acetone. Total recoveries were 75.I and 79.3 percent for
1he 80-f'g spike (1-g cartridge}. 57.3 and 56.5 percent for the 120-pg spike ( 1-g cartridge), 94.6 percent for the 40-pg spike (2-g cartridge), 55.4 and 62.0 percenl for
the 80-pg spike (2-g cartridge), 70.2 and 79.0 percent for the 120-pg spike (2-g cartridge).
TABLE 21. ELUTION PATTERNS AND PERCENT RECOVERIES OF THE PHTHALATE
ESTERS FROM ALUMINA CARTRIDGES USING HEXANE WITH 10 PERCENT
AND 20 PERCENT ACETONE•
Hexane with 10 percent acetone Hexane with 20 percent acetone
Fraction 1 Fraction 2 Fraction 1 Fraction 2

Compound (S mL) (S mL) (S mL) (S mL)
DMP 78.6 65.6 47.9 28.8 101 102 0 0

DEP 101 84.5 0 0 103 103 0 0
DIBP 94.0 75.8 0 0 105 104 0 0
DBP 101 88.1 0 0 109 107 0 0
BMPP 86.4 37.0 0 0 104 102 0 0
BMEP 0 0 31.5 40.3 66.6 61.6 38.8 34.8
OAP 63.6 57.3 0 0 106 100 0 0
BEEP 16.6 19.6 109 102 121 102 0 0
~ HEHP 68.5 56.9 0 0 103 99.3 0 0
°' DHP
BBP
99.9
93.8
89.3
89.6
0
10.3
0
5.4
112
106
105
100
0
0
0
0
BBEP 75.4 66.3 50.2 47.6 114 103 0 0
DEHP 99.1 88.3 0 0 102 83.l 0 0
DCP 73.3 67.0 0 0 99.0 90.5 0 0
DOP 97.9 120 0 0 118 107 0 0
DNP 89.5 113 0 0 93.5 101 0 0
• 1-g alumina cartridges (Supelco lot SP 0214) were used; each cartridge was preconditioned with.4 mL hexane prior
to use. Each experiment was performed in duplicate; the amount spiked was 40 µg per component per cartridge
(2 mL of 20 pg/mL in hexane).
TABLE 22. ELUTION PAITERNS AND PERCENT RECOVERIES OF THE PHTHALATE
ESTERS FROM THE ALUMINA CARTRIDGES OF VARIOUS SIZES USING
HEXANE WITH 20 PERCENT ACETONE•
0.5-11: cart ridge I .0-11: nrt ridge 2.11-g artrldge
40-lfl lflke 1111-pg spike 120-pg spike 40-µg spike llO-pg spike 120-pg spike 40-µg spike 116-µg spike 1211-pg spike
eo.,_..41 Fndloft I Fntdlon I Frlldlon I Fnctlon I Fntdlon I Fradlon I Fradlon I Fradlon I Fraction I
DMP 1116 11111 (11.11 72.6 69.5 71.3 108 117 lllO 92.1 115 I IJ 98.6 93.8 92.3 73.2 114.1 9:\.0
DEP 111 112 1(1.2 711.9 73.1 75.3 139 148 106 12..'i 126 127 106 IOI! 105 I02 112 I04
DIOP 92.5 1)4.3 79.11 110.6 116 115 77.5 85.4 'JJ.11 IOI! %.9 94.0 114.6 116.5 119 110 IJl).fl HlO
DBP IOI 1113 113.11 86.7 91.3 89.6 IOI 109 109 121 1113 IOI 95.4 94.6 1118 103 1)11.2 92.8
BMPP 98 96.4 IU.4 82.6 too 109 75.l 90.4 92.3 107 83.3 81.5 81.8 80.3 IOI 911.1 81.5 78.8
BMEP 98.8 1114 76.0 79.4 87.7 88.8 87.1 93.8 92.2 101 90.3 88.S • • • • • •
OAP 103 1114 83.6 83.2 99.3 98.7 92.4 101 103 116 95.0 93.0 82.4 84.4 98.6 94.9 87.7 83.3
BEEP 107 110 R0.9 84.6 95.2 94.5 96.5 105 97.7 109 103 96.6 8t.6• 67.fl' 76.fl' ss.s· 45.6' 10.3•
HEHP 102 104 68.3 72.0 78.1 69.8 81.1 104 90.3 110 87.4 86.2 74.9 78.8 94.1 87.9 78.5 74.2
DHP IOI 100 81.5 87.4 101 85.4 116 126 94.9 106 118 116 95.5 97.8 87.8 81.6 101 93.7
BBP 113 116 59.2 61.9 62.0 60.5 !03 110 99.1 106 104 103 89.3 91.0 96.8 92.8 94.5 88.4
BBEP 86.4 78.5 83.0 91.1 117 113 88.1 92.5 99.4 110 104 103 73.3 73.9 101 96.5 87.3 79.5
DEHP 112 112 77.3 87.8 96.6 91.3 99.4 107 100 113 93.5 92.0 85.6 87.0 99.1 93.1 90.2 85.6
OCP 100 102 63.9 62.3 73.5 72.6 99.3 105 92.4 106 90.5 89.9 57.4 59.1 82.l 71.1 60.7 57.5
w DOP 84.3 74.3 79.6 90.5 103 101 93.3 108 101 113 103 102 85.6 86.5 101 97.1 93.I 85.9
DNP 77.1 66.2 S0.7 89.S 96.4 94.7 106 114 103 tt4 lt3 110 88.9 91.5 100 96.t 102 92.9
"' • J. T. e.lter alumina cartridges: Lot 841714 for O.S-g sil.e, Lot 812505 for 1-g size, and Lot B41714 for 2-g size. Each cartridge was preconditioned with 4 mL hexane prior to use.
Bltch a:periment was performed in duplicate. Fraction I was eluted with 5 mL hexane with 20 percent acetone; Fraction 2 with 5 mL hexane with 20 percent acetone. A third
fraction was collected from the 2-g cartridge by elution with 5 mL hexane with 20 percent acetone.
"BMEP wu recovered from the 2-g alumina cartridge by eluting the cartridge with two additional 5-mL portions of hexane with 20 percent acetone (Fractions 2 and 3). The
recoveries in Fraction 2 were 77.6 and S0.9 percent (40-pg spike), 57.8 •nd 46.2 percent (80-pg spike), and 26.3 and 61.5 percent (120-µg spike). The recoveries in Fraction 3 were
38.1 percent (40-pg spike), 37.9 and 48.1 (80-µg spike), and 38.1 and 31.9 (120-pg spike).
•Additional BEEP was recovered from the 2-g aluminm cartridge by eluting the cartridge with an additional S mL hexane with 20 percent acetone (Fraction 2). The recoveries in
Fraction 2 were 13.3 and 30.9 percent (40-pg spike), 28.6 and 55.9 percent (80-pg spike), and 62.7 and 28.9 percent (120-µg spike).
The data shown in Table 20 indicate that all but two phthalate esters can be recovered
from a 0.5-g or a 1-g Florisil cartridge with 5 mL hexane with 10 percent acetone (Fraction 1)
and from a 2-g cartridge with 10 mL hexane with 10 percent acetone (no phthalate esters were
recovered in Fraction 1, therefore an additional fraction had to be collected). The two phthalate
esters that could not be recovered are BMEP and BEEP. When working with the 0.5-g Florisil
cartridge, these two phthalate esters were recovered almost quantitatively by eluting the cartridge
with an additional 5 mL hexane with 10 percent acetone; however, they could not be recovered
from either the 1-g or the 2-g Florisil cartridge under similar conditions.
The alumina cartridge was first eluted with 5 mL hexane with 10 percent acetone
(Table 21). Since BMEP was not recovered at all and BEEP had recoveries <20 percent in
Fraction 1, the cartridge was eluted with an additional 5 mL hexane with 10 percent acetone.
In addition, we also eluted the cartridge with hexane with 20 percent acetone. This allowed
quantitative recovery of 15 phthalate esters in Fraction 1. The oruy compound that had recovery
under 70 percent was BMEP (Table 21). The alumina cartridge procedure using hexane with
20 percent acetone was further evaluated with cartridges of 0.5 g, 1 g, and 2 g in size, charged
with the 16 phthalate esters at three spiking levels (Table 22). The results indicate that the
16 phthalate esters were recovered quantitatively with the exception of BMEP from the 2-g
cartridge.
Matrix interferents such as com oil, diesel hydrocarbons, elemental sulfur, and the
organochlorine pesticides listed in SW-846 Method 8081 were added to hexane solutions
containing the 16 phthalate esters at known concentrations, and the hexane solutions were then
subjected to the Florisil or alumina cartridge cleanup procedure (Table 23). These interferents
were selected because they mimic typical background contamination in certain environmental
sample matrices that could also be contaminated with the target compounds. For example, corn
oil would be representative of fatty acid triglycerides, diesel hydrocarbons of petroleum
hydrocarbons, and organochlorine pesticides of compounds of environmental significance that
would be expected to behave in the same way as the target anaJr.tes investigated in this study.
The data presented in Table 23 indicate that neither the com oil nor the diesel hydrocarbons
affected the elution patterns or the recoveries of the 16 phthalate esters from the Florisil or the
alumina cartridge. Corn oil was also removed from the Florisil cartridge with hexane with
10 percent acetone. Fortunately, its presence does not seem to affect the GC determination of
the 16 phthalate esters. This statement is true only for corn oil concentrations below 0.2 mg/mL
of solvent (or 1 mg per cartridge) because this is the maximum concentration we used. Diesel
hydrocarbons do not seem to cause problems with the GC quantification of the phthalate esters
because the GC detector is transparent to aliphatic hydrocarbons. Elemental sulfur, if present,
is eluted from the Florisil cartridge with hexane with 10 percent acetone (Figure 6) and from
the alumina cartridge with hexane with 20 percent acetone (Figure 7). Therefore, extracts that
are known to contain elemental sulfur should be subjected to sulfur cleanup (Method 3660) prior
to Florisil or alumina cartridge cleanup. Separation of the organochlorine pesticides will be
described later in this section.
The effect of interferents when the Florisil cartridges were eluted with hexane/diethyl
ether (1:1) is presented in Table 24. Com oil and the diesel hydrocarbons do not seem to
interfere with the determination of the 16 phthalate esters, except for DAP that could not be
quantified because of interference and BMEP and BEEP that bad low recoveries.
The organochlorine pesticides overlapped with the phthalate esters when the GC
analysis was performed on the DB-5 fused-silica capillary column; they have to be separated
prior to the GC analysis. Hexane with 50 percent diethyl ether did not give adequate recoveries
for 8 of the 16 phthalate esters (fable 24), but use of hexane ~th. 20 percent ~ethylene chloride
followed by hexane with 10 percent acetone gave quantitatiVe recovenes for 14 of the
16 phthalate esters (Table 25).
38
TABLE 23. PERCENT RECOVERIES OF THE PHTHAIATE ESTERS FROM FLORISIL
AND ALUMINA CARTRIDGES WHEN INTERFERENTS WERE PRESENT'
Florlsil cartridge (Fraction I) Alumina cartridge (Fraction I)
Diesel Diesel
Com oil hydrocarbons Corn oil hydrocarbons
Compound (1000 µg per cartridge) (2000 µg per cartridge) ( IOOO µg per cartridge) (2000 µg per cartridge)
DMP 119 123 106 111 105 104 92.5 94.4

DEP 133 133 123 129 120 119 92.5 94.4
DIBP 101 104 111 107 88.8 87.7 82.8 85.8
DBP 111 111 110 114 92.4 91.1 88.7 90.4
BMP 104 104 93.2 95.7 61.2 63.1 69.8 71.0
BME.- .. b b b
81.4 81.8 74.1 75.8
OAP 96.6 96.8 98.8 98.8 82.7 83.1 74.9 76.9
BEEP" 53.3 64.6 43.7 32.3 70.9 71.8 66.0 67.9
HEHP 89.8 91.2 87.1 86.6 74.3 82.9 71.1 73.1
DHP 108 106 103 104 99.8 98.9 90.3 91.5
w BBP 106 107 102 104 93.8 92.6 84.6 87.3
'° BBEP
DEHP
104
99.9
104
99.4
98.8
92.1
100
94.6
87.8
83.3
87.8
83.1
88.3
72.6
81.6
74.6
DCP 81.4 81.2 68.2 68.2 81.8 81.3 72.0 73.8
DOP 109 108 102 103 93.1 92.7 80.9 82.7
DNP 114 114 107 111 98.5 99.2 86.4 88.3
• 1-g cartridges were used for this experiment. Each cartridge was preconditioned with 4 mL hexane. Each experiment was performed in
duplicate. The Florisil cartridge was eluted with two 5-mL portions of hexane with 10 percent acetone (Fractions 1 and 2). The alumina
cartridge was eluted with two 5-mL portions of hexane with 20 percent acetone (Fractions 1 and 2).
11
BMEP was recovered from the Florisil cartridge. The recoveries in Fraction 2 were 81.9 and 95.6 percent when corn oil was present as
interferent and 71.5 and 62.3 percent when diesel hydrocarbons were the interferents.
c Additional BEEP was recovered from the FlorisiJ cartridge in Fraction 2. The recoveries in Fraction 2 were 41.6 and 31.7 percent when
com oil was present as interferent, and 56.8 and 63.4 percent when diesel hydrocarbons were the interferents.
v N I'-
I'- I'- (S)
CD v CD I'-
a-
~ I'- CD Cl'- v
0
-
f- fi
If)
(\J
--
-'-
Ii
!· DB-608
I-,.
I- lfl
!II ! I
I ~-· ,
I II I
r-
I
r.i
Go DB-1701
r·- 7
f·I)
-.
. I
Figure 6. GC/ECD chromatograms or a phthalate esters standard spiked with organochlorine

pesticides and elemental sulfur and eluted from the 1-g Florisll cartridge with hexane
with 10 percent acetone. GC conditions are presented in Table 2.
40
<;!"
>(N
-«--
&
13' -
&
CNf)
.. <;!"
M
M
COO' N <;!"
N I'- M
I- tft
r ,_. I II
IIII II III
I
I I I I
I I
iI' IIII
I I
I'T-DI IliJ '

I
i'
-lf'i
I I i I
I I I I I I '
I I
-
1(1
,.."_ r'
-r' Ci'
-D
.
-.
ll'o
I'-
DB-1701
C• 7
M M
Figure 7. GC/ECD chromatograms ora phthalate esters standard spiked with organochlorine
pesticides and elemental sulfur and eluted from the 1-g alumina cartridge with
hexane with 20 percent acetone. GC conditions are presented In Table 2.
41
TABLE 24. ELUTION PATIERNS AND PERCENT RECOVERIES OF PHTHALATE ESTERS FROM FLORISIL
CARTRIDGES WITH HEXANE WITH SO PERCENT DIETHYL ETHER•
Fraction I Fraction 2
With With
No With com With diesel organochlorine No With com With diesel organochlorine
Compound lnterferents oil hydrocarbons pesticides lnterferents oil hydrocarbons pesticides
DMP 94 94 78 82 116 to8 l)J 91 <5 <5 <5 <5 <5 <5 <5 <5
DEP 96 95 84 93 74 70 103 98 <5 <5 to <5 7.6 <5 6.2 6.4
DIBP 122 119 122 115 105 97 118 Ill <5 <5 <5 <5 <5 <5 19 22
DBP 116 114 • 105 124 113 • • <5 <5 <5 <5 <5 <5 <5 <5
BMPP 108 109 103 87 J()<J 96 • b
<5 <5 <5 <5 <5 <5 (I{) 72
2.6 96 38 19 128 109 32 <5 <5 20 32 22 I03 128
BMEP
DAP 95 101
. 103
. • b
<5 <5 <5 <5 6.1 7.2 74 87
BEEP 8.9 99 7.8 44 55 48 14 58 51 <5 66 54 62 58 53 54
HEHP 112 104 127 116 88 81 86 83 <5 <5 II 8.2 8.2 6.0 <5 <5
b
DHP 98 98 128 106 107 103 b
<5 <5 6.0 <5 <5 <5 17 20
BBP 111 117 122 117 118 112 <5 <5 <5 <5 <5 <5 6.8 7.4
BBEP 65 97 78 90 103 112 27 <5 25 to 9.6 10 58 69
....N DEHP
DCP
95
98
103
IOI
89
118
83
86
85
114
78
104
9I
100
86
96
<5
<5
<5
<5
<5
<5
<5
<5
<5
<5
<5
<5
<5
<5
<5
<5
DOP 106 109 114 80 114 I07 IOH 102 <5 <5 <5 <5 <5 <5 <5 <5
DNP 90 91 80 72 llM 1)5 1)4 90 <5 <5 <5 <5 <5 <5 <5 <5
•Aorisil cartridges (I g) were used. Fraction I was clutc<l with 5 ml hexane with 50 percent diethyl ether and Fraction 2 with an additional 5 ml hexane with
50 percent diethyl ether. Final volume of each fraction was 5 ml. The phthalate esters were spiked at 2,500 ng per cartridge.
"Nol able to determine because of interference.
TABLE 25. RESULTS OF THE FLORISIL CARTRIDGE CLEANUP EVALUATION
STUDY (PHTHALATE ESTER STANDARDS ONLY; ELUTION WITH
HEXANE/METHYLENE CHLORIDE (4:1) AND HEXANE/ACETONE (9:1))
Percent recovery
8712-013-10 8712-013-11 8712-013-12

Fraction Fraction Fraction
Compound I II I II I II
DMP 0 68.0 0 121 0 201

DEP 0 87.7 0 90.7 0 86.3
DIBP 0 107 0 140 0 108
DBP 0 103 23.5 129 0 131
BMPP 0 116 0 123 0 130
BMEP 0 36.0 0 39.1 0 20.7
DAP 0 75.0 0 130 6.6 76.0
BEEP 0 78.3 0 99.0 0 69.0
HEHP 0 118 0 134 0 127
DHP 0 72.0 0 61.0 0 53.0
BBP 0 91.0 0 102 0 102
BBEP 0 113 0 188 0 103
DEHP 0 1071 0 1131 0 1101
DCP 0 106 0 109 0 102
DOP 0 125 0 131 0 114
DNP 0 100 0 112 0 94.7
a Not corrected for method blank; if corrected, recovery would

become 0. Study conducted in the presence of OCPs indicated
that the OCPs are eluted in Fraction I.
43
Additional experiments were performed in order to develop a procedure that allowed
the determination of the phthalate esters in the presence of the organochlorine pesticides. The
experimental design is presented in Table 26. Tables 27 and 28 present the recovery data and
elution patterns of the 16 phthalate esters when the cartridges were eluted with hexane/
methylene chloride and then hexane/ethyl acetate. In absence of the organochlorine pesticides,
the phthalate esters were recovered from the Florisil cartridge with hexane with 10 percent ethyl
acetate. However only BMPP, HEHP, BBP, DCP, DOP, and DNP had satisfactory recoveries
(recovery > 70 percent). The remainder of the phthalate esters were either not recovered at all
(e.g., BBEP) or had very low recoveries. When the organochlorine pesticides were spiked
together with the phthalate esters on the Florisil cartridges and the cartridges were eluted with
various combinations of hexane/methylene chloride, most of the organochlorine pesticides were
eluted from the cartridges with hexane/methylene chloride. Nonetheless, we had difficulties in
quantifying the phthalate esters in the hexane/ethyl acetate fraction. High recoveries of some
of the 16 phthalate esters were attributed to interferents eluted from the cartridge by hexane
with 10 percent ethyl acetate and/or to contaminants in ethyl acetate that interfere with the
phthalate ester determination (Table 28).
Interferences in the determination of phthalate esters caused by the organochlorine

pesticides are presented in Table 29, and method blank analysis data for Florisil cartridges are
presented in Table 30.
The Florisil procedure was further evaluated using extracts of environmental samples
spiked with the 16 phthalate esters at known concentrations. The results presented in Table 31
indicate that recoveries were greater than 74 percent except for BEEP phthalate (recovery
ranges from 24 to 62 percent) and BMEP phthalate which could not be recovered at all in
Fraction 2.
When using these cartridges for the cleanup of extracts with the phthalate esters as
the target analytes, method blanks need to be obtained for each batch of cartridges used. The
SPE cartridges contain the adsorbent material in a polypropylene housing, and polyethylene frits
are used to hold the adsorbent material in place. Junk and co-workers (6) found C10 to Cis
isomeric alkenes, 2,6-di-tert-butyl-p-cresol, and alkyl phthalates in procedural blanks obtained by
washing the polypropylene housing or the polyethylene frits with ethyl acetate, methanol, and
water. We have analyzed Florisil SPE cartridges for the target analytes and found several
phthalate esters in procedural blanks (Table 32); however, their levels were not high enough to
interfere with the chromatographic determination of the organochlorine pesticides or the
phenols, and the preconditioning of cartridges should minimize sample contamination.
Furthermore, the volume of solvents needed to elute the interferents or the target analytes from
the cartridge is small (5 mL), and the residence time of the solvent in the cartridge is less than
5 min, making it quite desirable for use.
5.3 PHENOLS
Silica cartridges were evaluated for their use in the phenol analysis. These cartridges
were chosen because the current SW-846 Method 3630 recommends use of silica gel for cleanup
of sample extracts that were derivatized with pentatluorobenzyl bromide (PFBBr). More
specifically, a 4-g silica column is preeluted with 6 mL herane, the derivatized extract is loaded
on the column, the column is eluted first with hexane (6 mL), then with 10 mL hexane with
15 percent toluene (Fraction 1), 10 mL hexane with 40 percent toluene (Fraction 2), 10 mL
hexane with 75 percent toluene (Fraction 3), and 10 mL toluene with lS percent 2-propanol
(Fraction 4). Under these conditions, 9 derivatized phenols spread over the 4 fractions.
44
45
TABLE 26. (continued)
Amount
spiked (ng)
Sample Phthalate Fraction I Fraction Il

identification esters OCPs (S mL) (5 mL)
8712-013-23 0 0 Hexane/methylene Hexane/ acetone

chloride (85: 15) (9:1)
8712-013-24 500 0 Hexane/methylene Hexane/ethyl
chloride (85:15) acetate (9:1)
chloride (85:15) acetate (9: 1)
8712-013-30 500 0 Hexane/methylene Hexane/ ethyl
chloride (85: 15) acetate (9: 1)
chloride (85: 15) acetate (9:1)
8712-013-39 500 500 Hexane/methylene Hexane/ ethyl
8712-013-40 soo soo Hexane/methylene Hexane/ethyl
chloride (7S:2S) acetate (9:1)
8712-013-41 500 soo Hexane/methylene Hexane/ethyl
chloride (7S:2S) acetate (9:1)
8712-013-42 500 soo Hexane/methylene Hexane/ ethyl
(continued)
46
TABLE 26. (concluded)
Amount
spiked (ng)
Sample Phthalate Fraction I Fraction II

identification esters OCPs (5 mL) (5 mL)

chloride (85: 15) acetate (9:1)
{continued)
1
1-g Florisil cartridges were used. The 16 phthalate esters and the organochlorine
pesticides (OCPs) were spiked at 500 ng per component or not at all as indicated.
47
TABLE 27. RECOVERY OF PHTHALATE ESTERS FROM 1-g FLORISIL
CARTRIDGES BY ELUTION WITH HEXANE WITH
IS PERCENT, 25 PERCENT, AND 30 PERCENT METHYLENE
CHLORIDE (FRACTION I) AND HEXANE WITH 10
PERCENT ETHYL ACETATE (FRACTION 11) 8
Percent recovery
8712-013-24 8712-013-25 8712-013-26 8712-013-27 8712-013-2R R712-013-29 R712-013-30 8712-013-31 8712-013-32

Fraction Fraction Fraction Fraction Fraction Fraction Fraction Fraction Fraction
Compound I II I II I II I II I II I II I II I II I II
DMP 1.5 7.0 5.1 6.6 4.1 0 0 13.0 12.3 0 12.6 2.2 4.4 4.3 13.6 13.2 12.8 12.4
DEP 0 34.5 0 37.9 0 40.1 0 65.8 0 27.3 12.9 38.6 0 26.6 0 27.2 0 24.8
DIBP 0 98.0 0 60.4 0 64.2 0 64.6 0 60.7 0 89.8 0 58.6 0 53.6 0 56.l
DBP 13.1 65.0 13.5 80.0 0 85.0 0 112 0 83.7 0 69.8 0 49.8 0 52.4 0 51.9
BMPP 0 101 0 102 0 105 0 102 0 90.7 0 96.6 0 79.4 0 78.7 0 79.4
BMEP 0 0 0 21.0 0 32.8 0 23.4 0 24.2 0 24.2 0 0 0 18.9 0 18.2
DAP
...
00
BEEP
HEHP
0
0
13.7
156
6.0
91.0
0
0
0
161
6.2
90.0
0
0
0
166
5.0
101
0
0
0
143
6.8
110
0
0
0
179
0
120
0
0
14.7
184
17.6
89.3
0
0
0
159
0
115
0
0
0
108
120
0
0
0
0
103
0
IOI
DHP 49.0 40.1 40.2 42.5 43.3 44.3 46.2 50.9 46.2 44.9 80.5 51.3 0 50.7 0 47.2 0 49.2
BBP 4.0 73.0 0 81.0 0 89.0 27.3 95.4 24.7 84.4 29.2 93.4 3.7 JOI 6.5 106 t.5 103
BBEP 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
DEHP 0 54.0 0 46.0 0 56.0 0 31.3 0 36.2 0 36.0 0 50.0 0 43.9 0 44.9
DCP 0 125 0 91.5 0 110 0 llO 0 100 0 I08 0 142 0 142 0 148
DOP 0 94.2 0 95.3 0 107 0 108 0 99.8 0 I08 0 104 0 JOO 0 106
DNP 0 80.3 0 75.4 0 82.9 0 93.4 0 81.l 0 78.8 0 105 0 115 0 94.3
"The spiking level was 500 ng of each phthalate ester per cartridge.
TABLE 28. RECOVERY OF PHTHALATE ESTERS FROM 1-g FLORISIL CARTRIDGE IN
THE PRESENCE OF ORGANOCHLORINE PESTICIDES BY ELUTION WITH
HEXANE WITH 15 PERCENT, 20 PERCENT, AND 30 PERCENT
METHYLENE CHLORIDE (FRACTION I) AND HEXANE WITH 10 PERCENT
ETHYL ACETATE (FRACTION 11) 8
Percent Rttovery
8712-013-36 8712-013-37 8712-013-38 8712-013-39 8712-013-40 8712-013-41 8712-013-42 8712-013-43 8712-013-44

Fraction Fraction f<"raction Fraction Fraction Fraction Fraction Fraction Fraction
Co•pound II II II II II II II II II
DMP 16<1' 172h 174b 118 t 12 tot 120 113 tt4

DEP 49.5 51.5 60.0 63.2 56.3 56.7 40.2 51.1 34.9
DIBP 150" 105 I08 98.2 108 99.0 92.5 95.8 97.6
DBP 123 t2t tt5 lt8 t2t 108 109 106 102
BMPP 156<1' 74.9 72.7 78.8 tt6 ttO 109 t02 102
BMEP 138" 645b 224b 456b t62" t8~ 124 210" 36r
OAP 5,550" 5,620" 5,530" 1,420" 1,410" 850" 1,640" 454b 881b
BEEP ND ND ND 28.3 26.3 29.2 29.0 24.2 25.7
...
\0
HEHP
DHP
112
131'
102
123
103
129"
108
146b
113
120
110
113
110
126b
88.6
92.7
99.7
ltO
BBP 123 124 117 t2r 125 129" 117 106 121
BBEP 56<1 520b 530" 338" 362" 274b 33~ 17Jb 22r
DEHP 13~ tt9 112 15 lb t28" tt9 220" 18tb 249"
DCP 112 t04 97.8 I tO 110 112 103 94.3 107
DOP 117 118 109 t26b t23 126" 112 90.7 tt I
DNP 43.0 40.6 38.4 42.0 43.6 43.8 45.2 38.3 44.3
•The spiking level was 500 ng per phthalate ester per cartridge. The OCPs were also spiked at 500 ng per component per
cartridge.
" High recovery due to interferents eluted from the cartridge by hexane with lO percent ethyl acetate and/or contaminants in ethyl acetate.
TABLE 29. INTERFERENCES IN THE DETERMINATION OF PHTHALATE ESTERS
CAUSED BY ORGANOCHLORINE PESTICIDES
Conc.-l'ntrnlion (ng/nll.)"
8712..CH3-13 8712-013-14 8712-014-15 8712-0 IJ-33 8712-013-34 8712-013-35

Fraction Fraction Fraction l•raction Fraction Fraction
Com!!!nd II II II II I' II •• II
DMP NIY 2<10 NO 227 45.2 205 NO 208 B7 143

DEP ND ND ND ND ND J7.7 ND ND ND ND
DIBP 2.l.2 24.5 57.3 70.4 50.9 66.<1 45.6 20.4 30.3 36.3
DBP 64.1 34.0 26.2 30.0 27.8 2<>.7 28.6 20.8 ND ND
BMPP l,8IO 660 2,250 386 2,020 l'J.8 1,260 18.0 130 ND
BMEP 6,160 23.8 6,420 325 6,274 544 7,510 585 313 293
DAP 370 4,220 2,070 2,870 857 3,960 557 6,200 1,1 IO 491
BEEP ND ND ND 32.7 38.2 32.1 60.4 22.1 21.7 22.1
HEHP 3,070 30.9 3,270 69.9 3,120 251 3,540 21.7 19.9 150
DHP 42.2 122 52.6 103 (13.8 89.4 65.1 107 87.2 63.0
BBP 33.2 36.3 37.2 31.7 34.5 30.5 35.8 36.5 33.2 28.5
BBEP ND 586 31.(1 583 ND 606 ND 629 346 99.I
DEHP 48.4 70.4 53.0 129 69.3 112 65.9 219 124 76.6
VI DCP ND ND ND ND ND ND ND ND ND ND
0 DOP ND ND ND ND ND ND ND ND ND ND
DNP ND ND ND ND ND ND ND ND ND ND
8
The Florisil cartridges were charged only with OCPs. The various peaks detected in these fractions as phthalate esters are probably not only
11
contaminants in the OCP standards and other materials hut also OCPs eluting at the same retention times as the target analytes.
cAnalysis did not pass QC criteria, results are therefore not reported,
ND •• not detected; detection limit was approximately to ng/mL.
TABLE 30. RESULTS OF METHOD BLANK ANALYSES FOR THE FLORISIL
CARTRIDGES
Concentration (ng/mL) 8
8712-013-22 8712-013-23 8712-013-45 8712-013-46 8712-013-47

Fraction Fraction Fraction Fraction Fraction
Compound I II I n I n I II I n
DMP 40.7 151 51.9 200 12.4 . 55.4 17.0 33.2 24.2 32.4
DEP NDb ND ND ND ND ND ND ND ND ND
DIBP ND ND 22.8 22.1 ND ND ND ND ND ND
DBP ND 26.8 ND 30.1 ND 36.8 36.6 13.9 ND 33.1
BMPP ND ND ND ND ND ND ND ND ND 16.4
BMEP ND ND ND ND ND 18.5 ND ND ND 17.9
DAP 63.9 137 ND 139 ND ND 46.8 ND 61.8 ND
BEEP ND 16.3 18.8 18.2 ND 14.9 ND 14.8 ND 20.7
HEHP 33.9 18.6 18.3 ND ND 16.7 ND ND ND ND
DHP 50.6 49.8 ND 54.4 ND 40.0 ND 38.2 49.0 35.1
BBP 24.9 30.2 35.9 37.5 35.7 35.9 ND 35.6 27.1 24.7
BBEP ND ND ND ND ND ND 59.1 ND ND 56.7
DEHP 68.8 121 100 114 60.2 56.1 81.1 61.1 58.2 58.1
DCP ND ND ND ND ND ND ND ND ND ND
DOP 52.2 ND 64.1 ND ND ND ND ND ND ND
DNP ND ND ND ND ND ND ND ND ND ND
•The Florisil cartridge (1 g) was eluted with 5 mL hexane/methylene chloride (4:1) and
5 mL hexane/acetone (9:1) in the case of samples 8712-013-22, -23, and 5 mL of
85:15, 75:25, and 70:30 hexane/methylene chloride for samples -45, -46, and -47.
Fraction 2 for samples -45, -46, -47 was eluted with 5 mL hexane/ethyl acetate (9:1).
Final volume of each fraction was 5 mL.
bND -- not detected; detection limit was approximately 10 ng/mL.
51
TABLE 31. PERCENT RECOVERIES OF PHTHALATE ESTERS IN EXTRACTS FROM
VARIOUS MATRICES SUBJECTED TO FLORISIL CARTRIDGE CLEANUP
WITH HEXANE/METHYLENE CHLORIDE (4:1) AND HEXANE/
ACETONE (9:1) AS ELUANTs•
Sediment
Sandy loam ofundermed NBS NBS NBS
Compound soilb origin SRM-1572 SRM-1632a SRM-1633a
DMP 78 75 80 76 82
DEP 79 79 89 79 84
DIBP 79 82 90 108 86
DBP 74 78 84 83 83
BMPP 77 84 102 91 86
BMEP 0 0 0 0 0
DAP 82 86 100 76 89
BEEP 37 24 62 32 33
HEHP 80 88 95 93 81
DHP 78 88 86 92 80
BBP 82 99 114 102 98
BBEP 86 94 98 106 98
DEHP 74 85 108 88 112
DCP 91 96 106 98 95
DOP 80 92 104 95 88
DNP 84 96 106 111 92
a The spiking level was 50 ng/mL of extract for each compound. Data shown are for
Fraction 2 which was eluted with 5 mL hexane/acetone (9:1).
b Sandy loam soil from Puyallup, Washington, with the following characteristics: pH 5.9
to 6.0; 89 percent sand, 7 percent silt, 4 percent clay; cation exchange capacity 7
meg/ 100 g; total organic carbon content 1,290 ~ 185 mg/Kg.
52
TABLE 32. METHOD DETECTION LIMIT STUDY-FLORISIL
CARTRIDGES METHOD BLANKS
Concentration (ng/cartridge)8
Com2ound Re2.1 Re2.2 Re2.3 Re2.4 Re2.S Average SD

•
DMP 412 411 466 495 496 456 42
DEP 192 76.2 155 228 144 159 66
DIBP 94.7 96.6 107 119 107 105 10
DBP 129 116 142 162 132 136 17
BMPP 60.0 73.3 106 152 51.9 88.6 41
BMEP 303 134 302 291 282 262 72
DAP 28.4 40.3 140 33.6 22.0 52.9 49
BEEP 69.2 61.9 65.3 64.2 71.2 66.4 4
HEHP 43.9 16.2 40.3 12.9 4.7 23.6 17
DHP 32.9 29.3 31.6 35.8 33.2 32.6 2
BBP 16.6 16.1 16.6 24.3 18.2 18.4 3
BBEP 30.4 29.8 42.2 59.0 43.1 40.9 12
DEHP 295 267 332 320 243 291 37
DCP <10 <10 <10 18.2 <10 <10
DOP <10 <10 <10 13.8 <10 <10
DNP <10 <10 <10 <10 <10 <10
a Each Florisil cartridge (Supelco, Inc.) was eluted with 5 mL hexane

with 20 percent methylene chloride (Fraction 1) which was discarded,
followed by 5 mL of hexane/acetone (9:1) which was concentrated to
1 mL and analyzed by GC/ECD. The GC/ECD operating conditions
were as follows: 30 m x 0.25 mm ID DB-5 fused-silica capillary column
(0.25 µm film thickness); 120°C to 260°C (hold 15.7 min) at 15°C/min;
carrier gas helium at 21 psi; injector temperature 275°C; detector
temperature 320°C; splitless injection.
S3
We have taken 1-g silica cartridges, charged them with the PFB derivatives of
20 phenols, and eluted the cartridges with 4 mL hexane followed by 5 mL hexane with
25 percent toluene. Under these conditions, we got quantitative recoveries of 18 of the
20 compounds. When 0.5-g silica cartridges were evaluated at three spike levels (Table 33), we
found that the 18 phenols elute primarily in Fraction 1.
As the cartridge size increases, we see a crossover into Fraction 2 (Table 34), and when
the 2-g cartridges were used, 18 compounds were recovered quantitatively in Fraction 2
(Table 35).
Matrix interferents such as com oil, diesel hydrocarbons, and elemental sulfur were
added to hexane solutions of the target phenols at known concentrations, and the solutions were
then subjected to the silica cartridge cleanup procedure to establish if any changes occurred in
the compound elution pattern and in their recovery when matrix interferents were present
(Table 36). No change in compound recovery or elution pattern was observed.
The silica cartridge procedure for the phenols was tested with three extracts of
environmental samples spiked with the target compounds at known concentrations. After
spiking, the extracts were derivatized with PFBBr using the Lee, et al., procedure (2) and
cleaned by the silica cartridge cleanup procedure. The recovery data are presented in Table 37.
5.4 EVALUATION OF THE ASPEC SYSTEM
The Gilson ASPEC system (Automatic Sample Preparation with Extraction Columns)
was loaned to us for a period of three weeks by Gilson Medical Electronics, Inc. The ASPEC
system is designed to receive either 100-mg cartridges or 500-mg cartridges. The ASPEC
software comprises several prestored programs and 8 KB of user memory for free programming.
In the standard program, the user enters the parameters via a limited number of easy prompts
that indicate the conditioning step, washing step, elution step, and collected fraction mixing step.
We have used the standard program available with the instrument (File 165) and
modified it to allow the evaluation of the silica and diol cartridges for the cleanup of samples
containing organochlorine pesticides and Aroclor 1260 (Tables 38, 39, and 40) or organochlorine
pesticides and corn oil, diesel hydrocarbons, Aroclor 1260, and elemental sulfur (Table 41 ).
Furthermore, sample extracts (identified as SS-2, SS-5, SS-7 and SS-8) were processed using
the ASPEC system and 0.5-g diol cartridges (Tables 42 through 45).
Overall, the method reproducibility using the ASPEC system with the 0.5-g dial
cartridges is excellent. Thirteen out of 17 organochlorine pesticides had RSDs under 4 percent
(Table 40), and there was no crosscontamination when interferents were added such as com oil,
diesel hydrocarbons, and when sample extracts were used.
Slight modifications to the cartridge procedure had to be made when using the ASPEC
system. For example, the ASPEC system does not allow collection of more than one fraction
per extract. Since the silica cartridge procedure for the organochlorine pesticides calls for
elution of the cartridge with S mL hexane followed by S mL hexane with SO percent diethyl
ether, we first eluted the cartridges with 5 mL hexane which was discarded and followed with
3.S mL hexane with 50 percent diethyl ether (Table 38). Under those conditions, heptachlor,
aldrin, 4,4 •-DDE, and 4,4 ·-DDT were not recovered since they are eluted from the cartridge
with hexane. To collect Fraction 1, we had to elute all cartridges on the ASPEC rack with
S4
TABLE 33. ELUTION PATTERNS AND PERCENT RECOVERIES OF THE PFB
DERIVATIVES OF PHENOLS FROM O.S-g SILICA CARTRIDGES•
Spiked at 0.4 Ilg Spiked •l 0.2 l'g Spiked at 0.05 11g

per cartridge per cartridge per cartridge
eo.,..... Fractlcm I Fraction 2 Fraction 1 Fraction 2 Fraction I Fraction 2
Phenol 87.'.\ 1)().0 0 0 79.0 82.8 9.8 10.8 69.0 70.5 5.0 4.8
2-Methylphenol 103 103 0 0 96.8 IJ<J.3 0 0 88.'.\ lllU 0 0
3-Methylphenol 100 IOO 0 0 96.8 100 7.5 15.8 86.0 11<1.8 4.5 4.5
4-Methylphenol 94.9 85.1 5.1 14.9 88.8 93.3 16.3 0 76.5 11.5 I0.5 9.8
2,4-Dimethylphenol 100 100 0 0 108 111 0 0 90.8 91.0 0 0
2-Chlorophenol 87.l 73.6 12.9 26.4 87.3 94.3 24.8 18.3 76.5 77.0 13.5 l'.\.5
2,6-Dichlorophenol 113 llJ 0 0 112 114 0 0 92.3 92.8 0 0
4-Chloro-3-methylphenol 115 tl2 0 0 113 114 0 0 93.8 94.3 0 0
2,4-Dichlorophenol 88.9 76.6 I I.I 23.4 93.3 101 22.8 17.7 81.5 82.8 12.8 13.0
2,4,6-Trichlorophenol 119 121 0 0 116 120 0 0 97.3 96.8 0 0
2,3,6-Trichlorophenol 117 118 0 0 113 115 0 0 98.0 97.8 0 0
2-Nitrophenol ND" ND ND ND ND ND ND ND ND ND 64.0 42.3
2,4,S-Trichlorophenol 69.8 80.5 :m.2 29.5 122 126 0 0 90.8 90.5 0 0
2,3,S-Trichlorophenol 69.8 80.5 30.2 29.5 122 126 0 0 90.8 90.5 0 0
Vl 2,3,S,6-Tetrachlorophenol 103 100 0 0 107 110 0 0 104 104 0 0
Vl
2,3,4,6-Tetrachlorophenol 85.0 7<1.J 15.0 23.7 106 108 0 0 102 100 0 0
2,3,4-Trichlorophenol 89.5 91'.\ 19.4 31.5 54.0 68.5 51.3 39.6 64.0 55.8 40.7 48.5
2,3,4,S-Tetrachlotophenol 111 104 0 0 91.3 94.3 12.0 10.5 98.0 95.8 10.3 10.3
Pentachlorophenol 117 119 0 0 104 105 0 0 117 114 0 0
2,4-Dinitrophenol ND NO NO ND ND ND ND ND ND ND ND ND
• 0.5-g silica cartridges (Supelco lot SP0161) were used in this experiment. Each cartridge was conditioned with 4 mL hexane prior to use. Fraction I
was eluted with 5 mL hexane. Fraction 2 was eluted with 5 mL hexane with 25 percent toluene. The two values given for each fraction represent data
from duplicate experiments.
• ND •• not detected.
DERIVATIVES OF PHENOLS FROM 1-g SILICA CARTRIDGES•
Spiked at 0.4 µg Spiked at 0.2 µg Spiked at Cl.OS µg

per cartridge per <'art ridge per <'artridge
CoM!!!nd Fraction I Fra<'tion 2 Fraction I fo'ractlon 2 Fraction I Fradlon 2
Phenol 0 0 >5.<1
1 96.5 •J.8 10.I 74.0 62.3 26.5 23.5 41).5 52.0
2-Methylphenol 8.8 34.6 IOI 79 0 () 0 78.1 62.2 81.8 Kl.5 14.5 IJ.2
3-Methylphenol 0 0 112 II I () 0 87.7 72.6 28.3 21.K 6(,,0 70.0
4-Methylphenol () 0 I IJ 114 0 0 89.0 72.6 15.3 11.0 78.3 81.0
2,4-Dimethylphenol 0 17.6 115 104 0 II <J4.5 74.7 71.0 71.0 29.0 21UI
2-Chlorophenol 0 0 119 117 0 0 91.1 ?<di 0 0 9.'-8 94.5
2,6-Dichlorophenol 59.8 89.0 <•9.8 37.1 41.6 36.7 55.5 47.3 97.3 95.8 5.3 4.5
4-Chloro-3-methylphenol 0 0 119 110 0 0 94.5 78.1 64.0 63.0 37.0 36.8
2,4-Dichlorophenol 0 0 122 123 0 0 96.6 80.R 5.0 0 98.5 100
2,4,6-Trichlorophenol l 19 120 7.4 4.9 96.6 94.5 0 0 103 102 0 0
2.3,6-Trichlorophenol 96.8 109 31.3 14.5 73.3 67.5 22.9 25.5 103 101 5.3 5.3
2-Nitrophenol ND" ND ND ND ND ND ND ND ND ND ND ND
2,4,.S.Trichlorophenol 3.3 15.3 109 106 0 0 100 87.0 51.8 49.8 43.3 44.5
2.3,.S.Trichlorophenol 3.3 15.3 109 106 0 0 100 87.0 51.8 49.8 43.3 44.5
2,3.S,6-Tetr•chlorophenol 122 121 5.6 4.1 89.7 88.4 0 0 110 108 0 0
°'
°'
2,3,4,6-Tetrachlorophenol
2,3,4·Trichlorophenol
122
88.6
121
42.5
5.6
5.t
4.1
57.5
87.7
0
88.4
0
0
87.7
0
78.1
112
0
110
0
0
112
0
109
2.3,4.S-Tetrachlorophenol 0 0 118 119 0 0 89.0 82.9 16.8 12.8 93.3 98.8
Pentachlorophenol 118 116 6.1 6.3 86.3 85.6 0 0 126 122 5.8 5.3
2,4-Dinitrophenol ND ND ND ND ND ND ND ND ND ND ND ND
0
1-g silica cartridges (Supelc:o lot SP0161) were used in this experiment. Each cartridge was conditioned with 4 mL hexane prior to use. Fraction 1
was eluted with S mL hexane. Fraction 2 was eluted with 5 mL hexane with 25 percent toluene. The two values given for each fraction represent data
• ND -- not detected.
DERIVATIVES OF PHENOLS FROM 2-g SILICA CARTRIDGES8
Spiked al 0.4 µg Spiked al 0.2 µg Spiked al 0.05 µg

per rarlridge per rartridge per cartridge
eo.,.,... Fraction I l'~ractlon 2 Fraction I Fraction 2 Fraction I Fraction 2
Phenol 0 0 71UI 79.4 14.5 15.0 72.11 72.11 0 0 76.2 72.J

2-Methylphenol 0 0 77.11 117.2 () () 80.4 110.4 0 () 94.J 88.11
3-Methylphenol 0 0 79.2 87.2 () () 84.2 112.9 0 0 94.11 90.J
4-Methylphenol () () 7'J.2 87.2 0 () 80.4 111.0 0 0 87.J 81.0
2,4-Dimethylphenol 0 0 114.7 95.2 0 () 89.9 91.1 0 0 98.3 91.5
2-Chlorophenol 0 0 112.6 92.8 () 0 85.4 88.6 0 0 90.3 91.5
2,6-Dichlorophenol 0 0 85.4 s:u 0 0 91.1 91.8 ·O 0 100 90.5
4-Chloro-3-methylphenol 0 0 87.5 99.2 0 0 91.1 93.7 0 0 IOJ 91.8
2,4-Dichlorophenol 0 0 118.9 100 0 0 93.7 95.6 0 0 100 88.5
2,4,6-Trichlorophenol 0 0 90.3 JOO 0 0 98.8 100 0 0 105 92.5
2,3,6-Trichlorophenol 0 0 88.2 98.4 0 0 93.0 94.9 0 0 106 93.0
2-Nitrophenol ND" ND ND ND ND ND ND ND ND ND ND ND
2,4,S-Trichlorophenol 0 0 80.6 92.0 0 0 97.5 99.4 0 0 99.3 84.8
2,3,5-Trichlorophenol 0 0 80.6 92.0 0 0 97.5 99.4 0 0 99.3 84.8
v. 2,3,S,6-Tetrachlorophenol 0 0 100 96.0 0 0 90.5 90.5 0 0 110 98.0
....a 2,3,4,6-Tetrachlorophenol 0 0 100 96.0 0 0 89.9 91.8 0 0 109 95.3
2,3,4-Trichlorophenol 0 0 67.6 74.3 0 0 77.8 85.4 0 0 70.0 58.5
2,3,4,5-Tetrachlorophenol 0 0 87.5 98.4 0 0 85.4 88.4 0 0 111 100
Pentachlorophenol 0 0 85.4 89.6 0 0 87.3 91.1 0 0 122 102
• 2-g silica cartridges (Supeloo lot SP0161) were used in this experiment. Each cartridge was conditioned with 4 mL hexane prior to use. Fraction 1
was eluted with S mL hexane. Fraction 2 was eluted with 5 mL hexane with 2S percent toluene. The two values given for each fraction represent data
~ ND -- not detected.
TABLE 36. PERCENT RECOVERIES AND ELUTION PATTERNS OF PHENOLS FROM 1-g SILICA
CARTRIDGES IN THE PRESENCE OF CORN OIL AND DIESEL HYDROCARBONS
Com oil as lnterferent Diesel hydrocarbons as lnterferents
Compound Fraction 1 Fraction 2 Fraction 1 Fraction 2
Phenol 0 0 68.8 69.4 0 0 57.6 61.2

2-Methylphenol 5.0 0 85.9 87.9 0 7.0 77.9 80.6
3-Methylphenol 0 0 82.8 83.8 0 0 75.1 79.6
4-Methylphenol 0 0 71.0 68.6 0 0 62.0 68.2
2,4-Dimethylphenol 0 0 84.2 84.8 0 0 74.6 80.1
2-Chlorophenol 0 0 80.6 80.9 0 0 71.6 77.0
2,6-Dichlorophenol 35.8 18.9 63.1 72.8 9.9 30.6 69.0 64.2
4-Chloro-3-methylphenol 0 0 78.9 78.4 0 0 70.8 75.6
2,4-Dichlorophenol 0 0 80.7 80.3 0 0 71.4 77.6
2,4,6-Trichlorophenol 87.0 81.6 0 8.1 76.4 86.0 6.5 6.6
2,3,6-Trichlorophenol 61.6 45.5 33.2 48.7 34.9 57.1 46.2 37.2
~ 2-Nitrophenol NDb ND ND ND ND ND ND ND
2,4,5-Trichlorophenol 0 0 126 125 0 0 118 123
2,3,5-Trichlorophenol 0 0 126 125 0 0 118 123
2,3,5,6-Tetrachlorophenol 88.4 83.1 0 5.0 78.4 89.7 0 5.1
2,3,4,6-Tetrachlorophenol 93.6 83.4 4.7 9.9 80.0 93.3 7.9 8.1
2,3,4-Trichlorophenol 0 0 76.5 76.6 0 0 74.5 78.0
2,3,4,5-Tetrachlorophenol 0 0 82.0 81.8 0 0 74.4 81.6
Pentachlorophenol 74.9 70.7 0 0 66.5 76.4 5.3 4.8
2,4-Dinitrophenol ND ND ND ND ND ND ND ND
• t-g silica cartridges (J. T. Baker lot B51505) were used in this experiment. Each cartridge was conditioned
with 4 mL hexane prior to use. Fraction 1 was eluted with 5 mL hexane. Fraction 2 was eluted with 5 mL
hexane with 25 percent toluene. Spiking level was 0.4 p,g of derivatized phenols per cartridge.
bND -- not detected.
TABLE37. PERCENT RECOVERIES AND ELUTION PATTERNS OF PHENOLS FROM 1-g SILICA CARTRIDGES
IN THE PRESENCE OF MATRIX INTERFERENTS
~0
Sample 1 Sample 2 Sample 3 I-
a
I/)
Compound Fraction 1 Fraction 2 Fraction 1 Fraction 2 Fraction 1 Fraction 2 w
Phenol 0 0 67.6 68.3 0 0 72.8 66.3 0 0 64.8 63.4

2-Methylphenol 4.5 2.6 75.1 76.9 0 0 54.4 49.0 0 0 68.0 66.3
3-Methylphenol 0 0 74.3 74.4 0 0 85.1 48.6 0 0 68.6 66.9
4-Methylphenol 0 0 47.1 44.3 0 0 85.1 30.1 0 0 43.1 42.0
2,4-Dimethylphcnol 0 0 64.4 64.9 0 0 35.1 30.6 0 0 51.2 49.3
2-Clllorophenol 0 0 77.5 77.6 0 0 80.1 74.6 0 0 79.2 78.2
2,6-Dichlorophcnol 32.4 23.5 61.3 67.9 18.8 10.9 74.0 72.5 20.0 18.9 71.5 70.1
4-Cllloro-3-methylphcnol 0 0 74.9 15.5 0 0 78.6 72.3 0 0 77.4 76.3
2,4-Dichlorophenol 0 0 78.3 78.4 0 0 80.6 74.6 0 0 79.7 77.9
2,4,6-Trichlorophenol 78.6 77.3 5.6 10.2 77.1 70.8 13.4 10.3 76.3 74.7 11.6 11.0
2,3,6-Trichlorophenol 56.1 47.1 32.4 44.0 43.0 32.3 51.6 50.8 43.3 42.0 48.8 47.8
CA 2-Nitrophenol NDb ND ND ND ND ND ND ND ND ND ND ND
\0
2,4,5-Trichlorophenol 0 0 68.8 68.5 0 0 133 124 0 0 123 122
2,3,5-Trichlorophenol 0 0 68.8 68.5 0 0 133 124 0 0 123 122
2,3,5,6-Tetrachlorophenol 79.8 79.l 3.9 7.4 77.0 69.9 9.5 6.9 79.0 76.9 7.5 6.9
2,3,4,6-Tetrachlorophenol 83.6 80.5 5.2 10.4 76.6 68.6 10.6 87.4 86.9 12.1 11.6
2,3,4-Trichlorophenol 0 0 74.3 77.8 0 0 } 101 71.3 9.6 9.6 78.5 76.1
2,3,4,5-Tetrachlorophenol 0 0 80.1 81.4 0 0 80.6 72.9 0 0 85.1 82.0
Pentachlorophenol 68.4 68.4 3.7 6.2 60.9 56.2 6.8 5.1 77.6 76.9 1.5 3.7
• 1-g silica cartridges (J.T. Baker lot 51505) were used in this experiment Each cartridge was conditioned with 4 mL hexane prior to
use. Fraction 1 was eluted with 5 mL hexane. Fraction 2 was eluted with 5 mL hexane with 25 percent toluene. Spiking level was
0.4 µ.g of derivatized phenols per cartridge.
b ND - - Not detected.
TABLE 38. METHOD REPRODUCIBILI1Y USING THE ASPEC ROBOTIC SYSTEM 8
OCPs only OCPs and Arodor 1260
Average Percent Average Percent

Compound recovery RSD recovery RSD
alpha-BHC 46.8 6.2 89.1 1.6

gamma-BHC 89.8 2.9 91.1 4.4
beta-BHC 88.5 3.6 90.4 4.7
Heptachlor 0 0
delta-BHC 88.0 3.2 89.5 5.4
Aldrin 0 0
Heptachlor epoxide 91.6 7.6 89.1 5.0
Endosulfan I 88.8 3.8 88.8 5.3
4,4'-DDE 0 0
Dieldrin 86.7 3.4 88.6 5.4
Endrin 106 4.5 110 5.8
4,4'-DDD 25.4 8.6 72.7 5.5
Endosulfan Il 74.9 3.4 76.6 5.3
4,4'-DDT 0 17.2 96
Endrin aldehyde 35.3 5.4 32.7 7.5
Endosulfan sulfate 78.5 4.3 77.4 5.6
4,4 '-Methoxychlor 89.2 8.2 86.8 6.3
8
0.5-g silica cartridges (J. T. Baker) were used for this experiment. Each cartridge was
conditioned with 4 mL hexane (speed 5; air volume 100 µL). Standard in hexane
(1 mL) was added to the cartridge (height 0, speed 4, air volume 100 µL). The
cartridge was washed with 5 mL hexane (speed 5, air volume 100 µL) and eluted with
3.5 mL hexane with 50 percent diethyl ether (speed 4, air volume 200 µL). Finally, to
clean the lines, the cartridge was rinsed with 1 mL hexane with 50 percent diethyl
ether (speed 8) and the rinse was discarded. Spiking level was 1 µg per cartridge for
the OCPs and 10 µg per cartridge for Aroclor 1260. Number of determinations was 4.
60
TABLE 39. METHOD REPRODUCIBILITY USING THE ASPEC ROBOTIC SYSTEM 8
Average recovery (percent RSD)
OCPs only OCPs and Aroclor 1260
Fraction Fraction Fraction Fraction

Compound 1 2 1 2
alpha-BHC 0 84.7 (2.6) 0 84.0 (1.7)

gamma-BHC 0 87.1 (2.5) 0 85.6 (1.3)
beta-BHC 0 84.4 (1.4) 0 82.2 (1.1)
Heptachlor 83.7 (3.6) 0 71.4 (7.8) 21.4 (49)
delta-BHC 0 81.5 (2.5) 0 79.4 (2.6)
Aldrin 82.6 (4.8) 0 79.9 (1.4) 0
Heptachlor epoxide 0 82.2 (3.0) 0 83.0 (2.5)
Endosulfan I 0 82.0 (3.3) 0 84.1 (2.5)
4,4'-DDE 86.2 (5.7) 0 80.5 (3.3) 8.5 (85)
Dieldrin 0 78.8 (3.2) b 80.8 (2.6)
Endrin 0 88.7 (3.0) b 91.5 (3.2)
4,4'-DDD 0 82.4 (2.8) 0 81.6 (1.3)
Endosulfan II 0 80.5 (2.8) b 79.6 (1.7)
4,4'-DDT 67.8 (12.3) 15.4 (93) 82.9 (2.2) b
Endrin aldehyde 0 21.2 (8.8) b 17.7 (2.9)
Endosulfan sulfate 0 73.2 (4.6) b 43.4 (2.2)
4,4 '-Methoxychlor 0 78.5 (3.2) b 80.4 (2.0)
1
0.5-g silica cartridges (J. T. Baker) were used for this experiment. Each
cartridge was conditioned with 4 mL hexane (speed 5; air volume 100 µL ).
Standard in hexane (1 mL) was added to the cartridge (height 0, speed 4, air
volume 100 µL). The cartridge was eluted with 3.5 mL hexane (Fraction 1,
speed 4, air volume 200 µL) followed by 3.5 mL hexane with 50 percent diethyl
ether (Fraction 2, speed 4, air volume 200 µL). Finally, to clean the lines, the
cartridge was rinsed with 1 mL hexane with 50 percent diethyl ether (speed 8)
and the rinse was discarded. Spiking level was 1 µg per cartridge for the OCPs
and 10 µg per cartridge for Aroclor 1260. Number of determinations was 4.
blnterference from Aroclor 1260.
61
TABLE 40. METHOD REPRODUCIBILITY USING
THE ASPEC ROBOTIC SYSTEM•
Average Percent
Compound recovery RSD
alpha-BHC 86.1 3.0

gamma-BHC 87.1 2.9
beta-BHC 81.9 3.3
Heptachlor 86.1 3.2
delta-BHC 83.8 3.2
Aldrin 86.2 3.2
Heptachlor epoxide 86.0 3.3
Endosulfan I 85.3 3.6
4,4'-DDE 85.4 3.4
Dieldrin 86.3 3.3
Endrin 108 4.5
4,4'-DDD 84.0 3.7
Endosulfan II 84.6 3.3
4,4'-DDT 84.7 3.6
Endrin aldehyde 52.9 4.9
Endosulfan sulfate 58.1 10
4,4 '-Methoxychlor 79.4 4.6
1
0.5-g diol cartridges (Supelco, Inc.) were used for
this experiment. Each cartridge was conditioned
with 4 mL hexane with 10 percent acetone (speed 5,
air volume 100 µL). Standard in hexane (1 mL) was
added to the cartridge (height 0, speed 4, air volume
100 µL). The cartridge was eluted with 3.5 mL
hexane with 10 percent acetone (speed 4, air
volume 200 µL). Finally, to dean the lines, the
cartridge was rinsed with 1 mL hexane with
10 percent acetone (speed 8) and the rinse was
discarded. Spiking level was 1 pg per cartridge. All
fractions were adjusted to 5 mL final volume.
Number of determinations was 19.
62
TABLE 41. EVALUATION OF MATRIX INTERFERENTS USING THE ASPEC
ROBOTIC SYSTEM•
Percent recovery
Aroclor 1260
Compound Com oil Diesel hydrocarbonsb and sulfur
alpha-BHC 93.2 98.8 90.0 108 110

gamma-BHC 95.0 100 93.8 112 113
beta-BHC 80.2 85.4 78.4 85.5 87.5
Heptachlor 95.6 101 94.4 110 113
delta-BBC 87.4 92.2 87.0 97.4 99.0
Aldrin 92.8 98.6 92.2 104 107
Heptachlor epoxide 91.6. 97.0 92.8 96.7 98.3
Endosulfan I 89.6 94.8 91.8 93.7 95.7
4,4'DDE 89.0 94.4 93.4 106 111
Dieldrin 89.6 94.6 91.0 107 110
Endrin 117 126 132 89.4 91.0
4,4 '-DDD 85.6 91.2 89.8 93.4 94.7
Endosulfan II 82.0 86.8 85.2 97.7 99.7
4,4'-DDT 82.6 88.0 86.2 127 130
Endrin aldehyde 42.6 42.8 43.0 54.1 54.1
Endosulfan sulfate 47.4 39.0 44.0 43.7 41.3
4,4 '-Methoxychlor 78.4 84.2 80.0 101 102
1
0.5-g dial cartridges (Supelco Inc.) were used for this experiment. Each cartridge was
conditioned with 4 mL hexane with 10 percent acetone (speed 5, air volume 100 µL).
Standards in hexane (1 mL) containing OCPs at 1 µg/mL and com oil at 500 µg/mL or diesel
hydrocarbons at 500 µg/mL or Aroclor 1260 at 0.66 µg/mL or elemental sulfur at 166 µg/mL
were added to the cartridge (height 0, speed 4, air volume 100 µL). The cartridge was eluted
with 3.5 mL hexane with 10 percent acetone (speed 4, air volume 200 µL). Finally, to clean
the lines, the cartridge was rinsed with 1 mL hexane with 10 percent acetone (speed 8) and the
rinse was discarded.
bDuplicate experiments were also pedormed in this case but one fraction was lost.
63
TABLE 42. PERCENT RECOVERIES OF 17 ORGANOCHLORINE
PESTICIDES SPIKED INTO SS-2 SOIL EXTRAcr8
Unspiked Percent recoven:

sample
Compound (µg/kg) Fraction 1 Fraction 2
alpha-BHC <170 82.1 0

gamma-BHC <170 81.2 0
beta-BHC <170 76.7 0
Heptachlor <170 73.8 0
delta-BHC <170 40.2 52.8
Aldrin <170 88.7 0
Heptachlor epoxide <170 79.4 0
Endosulfan I <170 68.1 0
b
4,4'-DDE 1,100 0
Dieldrin <170 76.7 0
Endrin <170 92.2 0
b
4,4'-DDD 2,800 0
Endosulfan II <170 80.4 0
b
4,4'-DDT 2,200 0
Endrin aldehyde <170 25.2 38.9
Endosulfan sulfate <170 64.5 0
4,4 '-Methoxychlor <170 80.0 0
c c
Diazinon 320
c c
Et hi on 210
4,100 c c
Ziram
c c
CarbaryI 20
a Spiking level is equivalent to 330 µg/kg of sample. 0.5-g diol

cartridges (Burdick and Jackson) were used for this experiment.
Each cartridge was conditioned with 4 mL hexane (speed 5, air
volume 100 µL). Sample extract (1 mL) was added to the
cartridge (height 0, speed 4, air volume 100 µL). The cartridge
was eluted with 3 mL hexane for Fraction 1 and 3.5 mL hexane
with 10 percent acetone for Fraction 2 (speed 4, air volume
200 µL ). Finally, to clean the lines, the cartridge was rinsed with
1 mL hexane with 10 percent acetone (speed 8) and the rinse
was discarded. Single determination.
b Not able to determine recovery because the amount spiked is
lower than the background level.
~ot spiked.
64
PESTICIDES SPIKED INTO SS-S SOIL EXTRACT
Unsplked Percent recoven:

sample
Com2ound (µsikg) Fraction 1 Fraction 2
alpha-BHC <170 85.4 0

gamma-BHC <170 83.6 0
beta-BHC <170 80.1 0
delta-BHC <170 42.8 53.8
Aldrin <170 70.4 0
b
4,4'-DDE 780 0
Endrin <170 90.3 0
b
4,4'-DDD 2,200 0
Endosulfan II 210 65.3 0
b
4,4'-DDT 1,300 0
Endosulfan sulfate 260 50.8 14.8
4,4 •-Methoxychlor <170 72.5 0
c c
Benomyl 200
c c
Carbophenothion 1,400
c c
Ethion 650

Each cartridge was conditioned with 4 ml hexane (speed 5, air
volume 100 µL). Sample extract (1 ml) was added to the
cartridge (height 0, speed 4, air volume 100 µl). The cartridge
200 µL). Finally, to clean the lines, the cartridge was rinsed with
b Not able to determine recovery because the amount spiked is
~ot spiked.
65
PESTICIDES SPIKED INTO SS-7 SOIL EXTRACT'
Unspiked Percent recove!l'.

sample
Compound (µg/kg) Fraction 1 Fraction 2
alpha-BHC <170 80.1 0

gamma-BHC <170 76.4 0
beta-BHC <170 72.4 0
delta-BHC <170 40.1 46.7
Aldrin <170 65.7 0
4,4'-DDE 720 b 0
Endrin <170 110 0
4,4'-DDD 470 b 0
Endosulfan II 300 38.3 0
4,4'-DDT 680 b 0
Endosulfan sulfate <170 73.5 18.3
4,4 '-Methoxychlor <170 89.3 12.3
c c
CarbaryI 130
c c
Diazinon 260
c c
Ethion 130
c c
Ziram 2,100

volume 100 µL). Sample extract (1 mL) was added to the
cartridge (height 0, speed 4, air volume 100 l'L). The cartridge
200 µL). Finally, to clean the lines, the cartridge was rinsed with
bNot able to determine recovery because the amount spiked is
c Not spiked.
66
PESTICIDES SPIKED INTO SS-8 SOIL EXTRACT
Unspiked Percent reoove!l'.

sample
Com~ound (µg/kg) Fraction 1 Fraction 2
alpha-BHC <170 83.4 0

gamma-BHC <170 81.3 0
beta-BHC <170 75.8 0
delta-BBC <170 42.0 48.9
Aldrin <170 68.1 0
Heptachlor epoxide <170 101 0
Endosulfan I <170 110 0
b
4,4'-DDE 860 0
Dieldrin <170 107 0
Endrin <170 95.7 0
4,4'-DDD <170 76.0 0
Endosulfan II <170 77.2 0
b
4,4'-DDT 1,130 0
Endrin aldehyde <170 51.8 0
Endosulfan sulfate <170 45.8 40.9
4,4 •-Methoxychlor <170 60.6 17.3
c c
Benomyl 200
c c
Carbary! 480
c c
Carbophenothion 3,800
135,000 c c
Diazinon
c c
Malathion 230
c c
Ziram 1,200
a Spiking level is equivalent to 330 p.g/kg of sample. 0.5-g diol

volume 100 p.L). Sample extract (1 mL) was added to the
cartridge (height 0, speed 4, air volume 100 µL). The cartridge
with JO percent acetone for Fraction 2 (speed 4, air volume
200 µL ). Finally, to clean the lines, the c8rtridge was rinsed with
bNot able to determine recovery because the amount spiked is
c Not spiked.
67
hexane, then proceeded to the next solvent which was hexane with 50 percent diethyl ether.
Another modification made to the cartridge procedure affected the volume of solvent needed
to elute the compounds from the cartridge. The ASPEC system cannot handle fractions larger
than approximately 3.5 mL because the capacity of the collection vials is 4 mL. Nonetheless,
compound recoveries are good for both hexane with 50 percent diethyl ether (Table 39) and
hexane with 10 percent acetone (Table 40) and the method reproducibility is acceptable.
Additional work is needed to fully evaluate the ASPEC system.
68
REFERENCES
1. Test Methods for Evaluating Solid Waste; Laboratory Manual -- Physical/Chemical

Methods, SW-846, 3rd Edition, Vol lB, U.S. Environmental Protection Agency,
Washington, DC, November 1986.
2. Lee, H. B., Weng, L. D., and Chau, A.S.Y., "Chemical Derivatization Analysis of Pesticide
Residues, IX, Analysis of Phenol and 21 Chlorinated Phenols in Natural Waters by
Formation of Pentafluorobenzyl Ether Derivatives," J. Assoc. Off. Anal. Chem. 67, 1086-
1090, 1984.
3. Lopez-Avila, V., Schoen, S., Milanes, J., and Beckert, W. F., "Single-Laboratory Evaluation
of EPA Method 8080 for Determination of Chlorinated Pesticides and Polychlorinated
Biphenyls in Hazardous Wastes," J. Assoc. Off. Anal. Chem. 41, 375-387, 1988.
4. Viar and Co., Protocol for SAS 4214-QC, November 1988.
5. Lopez-Avila, V., Constantine, F., Milanes, J., and Gale, R., "Single-Laboratory Evaluation
of Method 8060 Phthalate Esters," Final Report for EPA Contracts 6803-3226 and
68-03-3511, Work Assignments 2-14, 3-16, and 0-11, November 1989.
6. Junk, G. A., Avery, M. J., and Richard, J. J., "Interferences in Solid-Phase Extraction Using
C16 Bonded Porous Silica Cartridge," Anal. Chem. 60, 1347-50, 1988.
69
Appendix A
EVALUATION OF SAMPLE EXTRACT

CLEANUP USING SPE CARTRIDGES
LITERATURE REVIEW
TABLE OF CONTENTS
Section ~
1 INTRODUCTION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A-1
2 SPE CARTRIDGE TECHNOLOGY . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A-2

2.1 SPE CARTRIDGES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A-2
2.2 APPARATUS FOR HANDLING MULTIPLE SPE CARTRIDGES . . . . . A-4
2.3 AUTOMATED DEVICES.................................... A-4
3 SPE TECHNIQUE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A-10
4 APPLICATIONS ............................................... A-15
REFERENCES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A-26
ill
FIGURES
Number
A-1 SPE cartridge. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A-3
A-2 Analytichem International SPS24 and original VacElut manifold. Figure taken
from Analytichem International brochure on SPE cartridges. . . . . . . . . . . . . . . A-5
A-3 J&W SPE vacuum manifold. Figure taken from J&W Scientific brochure on
SPE cartridges. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A-6
A-4 Visiprep vacuum manifold. Figure taken from 1989 Supelco chromatography
catalog 27 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A-7
A-5 VacElut SPS24. Figure taken from Analytichem International brochure on

SPE cartridges . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A-8
A-6 Building method file and BenchMate Workstation. Figure taken from Zymark
brochure on the BenchMate system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A-9
A-7 SPE technique ................................................. A-10
A-8 Types of interactions between the analyte and adsorbent. Figure taken from
Reference 18 .................................................. A-14
A-9 Separation of standard compounds on silica cartridges (3 mL). Figure taken

from Reference 3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A-21
A-10 Separation of standard compounds on C18-cartridge (3 mL). Figure taken

from Reference 3 .............................................. A-21
iv
TABLES
Number Page
A-1 Guide to Selecting SPE Cartridges for a Particular Application . . . . . . . . . . . . . A-12
A-2 Summary of Extract Cleanup Procedures that Employ SPE Cartridges ....... A-16
A-3 Recoveries of Pesticides from Lake Sediment Using Extraction Solvent and SPE
Cartridge Combinations .......................................... A-18
A-4 Percent Recoveries of the Aroclors Using Florisil and Silica Cartridges ...... A-19
A-5 Recoveries of Pesticides from Different Sediment Types Using Acetonitrile as

Extraction Solvent and the Cts SPE Cartridges with the Methylene Chloride/
Acetonitrile/Hexane (50:3:47) Elution Mixture ......................... A-20
A-6 Percent recoveries of 21 Organophosphate Pesticides from Diol Cartridges .... A-24
A-7 Extraction and Cleanup of Triazines from Soil, Muscle Tissue, and Corn Oil . . A-25
v
SECTION 1
INTRODUCTION
This literature review report summarizes the relevant literature published recently on
the use of solid-phase extraction (SPE) cartridges in environmental analysis. The literature
review was performed using the computerized Chemical Abstracts search. Furthermore, issues
of Analytical Chemistry, the Journal of Chromatography, the Journal of Chromatographic
Science, the Association of Official Analytical Chemists Journal, the Journal of High Resolution
Chromatography, the LC•GC Magazine, and the Chromatographia, from 1984 to 1989, were
searched to gather references that were not retrieved during the Chemical Abstracts search.
Fourteen articles (References 1 through 14) were judged to be scientifically relevant to

the objectives of this study and were retrieved from the literature. Other references
(References 15 through 28) were also retrieved, because they were dealing with the use of SPE
cartridges in preconcentrating organics from water samples or other applications. However, they
were not summarized in this literature review when the information presented in these
references did not deal specifically with extract cleanup/fractionation.
The literature review summary presented in this report addresses the following:
• The SPE cartridge technology and apparatus needed for sample processing using
the SPE cartridge
• The SPE technique
• Applications.
A·l
SECTION 2
SPE CARTRIDGE TECHNOWGY
2.1 SPE CARTRIDGES
A typical SPE cartridge consists of a polypropylene syringe body with a barrel-type

cartridge, two polyethylene frits (20-µm pores) or stainless steel frits, and the adsorbent material
(Figure A-1 ). Typical volumes are 1 mL, 3 mL, and 6 mL that accommodate 100 mg to 2000 mg
adsorbent material. The average capacity is approximately 5 percent of adsorbent mass, or
5 mg/100 mg of adsorbent. A Luer tip allows easy attachment of the cartridge to adapters,
stopcocks, and vacuum manifolds or workstations. Large reservoir capacity (LRC) columns are
available for processing larger-volume samples. Figure A-1 shows various types of cartridges
that are available commercially.
Silica-gel-filled cartridges and silica-based bonded-phase cartridges seem to dominate

the market, but polymeric cartridges are also getting quite popular. Interaction Chemicals of
Mountain View, California, has developed a line of polymeric materials known as Polysorb
MP-1, MP-2, MP-3 polymers that are spherical, porous, and crosslinked and are based on
styrene-divinyl benzene or vinyl pyridine. The MP-1, MP-2, and MP-3 can be used to remove
large amounts of fats, waxes, hydrocarbons, and surfactants from complex matrices. MP-2 and
MP-3 can be used in either charged or noncharged mode; thus, their capacity depends upon
solvent pH. Polysorb packings have 35-µm particles and have a narrow particle size distribution.
Their capacity is approximately 100 µg per 100 mg packing. The polymer can be used over a
pH range of 0 to 14. Solvents such as methanol, acetonitrile, and tetrahydrofuran can be used
in any amount to condition, process, or elute samples. Hydrocarbons and chlorinated solvents
can also be used, but these may swell the polymer, causing slightly slower elution times. Finally,
one other advantage of these polymeric materials is that they can be reused. These polymers
are chemically stable and can be washed with strong acid or base to completely remove any
materials left on the cartridge. The number of times the cartridges can be reused depends on
the sample matrix and the instrument sensitivity.
A unique SPE phase Cyclobond I was developed by Astec, Whippany, New York. This
adsorbent material is prepared by covalent coupling of #-cyclodextrin to 40-µm silica particles.
The Jl-cyclodextrin has a toroid structure with seven glucose units; the primary and secondary
hydroxyls are outside the cavity, while the internal void is hydrophobic. The hydrophobic part
of the analyte enters this cavity and is held by electrostatic attraction. No preconditioning of
the Cyclobond I cartridge is needed because the surface is hydrophilic.
The SPE cartridges are available from various manufacturers (e.g., J. T. Baker Inc.,
Supelco, Burdick & Jackson, Alltech, Analytichem International, J&W Scientific Inc., etc.).
Additional information can be found in Reference 1.
A-2
c;:===:::;::;;:i- STURDY DOUBLE-RIDGED LIP m
RESERVOIR-HIGH QUALITY, MEDICAL PROVIDES A CONSISTENT SEAL
GRADE POLYPROPYLENE MINIMIZES WHEN USED WITH ROBOTIC ~
0
INTERFERENCE FROM PLASTICIZERS. WORK STATIONS (/)
w
WIDE 518-INCH OPENING FOR
EASE OF AUTOMATED ALIGNMENT
AND SAMPLE INTRODLICTION
RESERVOIR
LARGE 10 ml POLYPROPYLENE
RESERVOIR
BONDESL (SEPRALYTE) SORBENT -

HIGH CAPACfTY, 60 ANGSTROM
POROSITY BONDED SILICA SORBENTS,
40 MICRON MEAN PARTICLE SIZE FOR
OPTIMAL FLOW RATES.
UPPER AN> LOWER FRrTS-20 pm
POROSITY POI.YETHYLENE ..... - t t - - - BONDESll (SEPRALYTE) SORBENTS 11111111111Hf- UPPER
LUER Tl'-EASLY ATIACl-£0 TO - - - L J FRrr
ADAPTERS, STOPCOCKS AND VAC . "·· SPE
ELUT OR VAC ELUT SPS 24 SAMPLE PACKING
PROCESSING STATION.
Ullllllllt+---LOWER
FRrr
LUER TIP IS EASILY ATIACHED TO
ANAL mCHEM CARTRIDGE ADAPTERS, STOPCOCKS AND SAMPLE
PROCESSING STATIONS
INTERACTION
CHEMICALS CARTRIDGE
AllTECH CARTRIDGE
Figure A-1. SPE cartridge.

2.2 APPARATUS FOR HANDLING MULTIPLE SPE CARTRIDGES
Several devices are available for handling multiple cartridges. They include the VacElut
SPS24 (Analytichem International) that can handle up to 24 cartridges simultaneously, the
original VacElut from Analytichem International that handles up to 10 cartridges (Figure A-2),
J&W's SPE Vacuum Manifold for 20 cartridges (Figure A-3), the Visiprep Vacuum Manifold
from Supelco Inc. for 12 cartridges (Figure A-4), Alltech's 12-port manifold, Adsorbex SPU
24-port vacuum manifold from EM Science, the Baker-to SPE and SPE-21 systems (J. T. Baker),
and Spe-ed Mate-10 or Spe-ed Mate-30 of Applied Separations.
In general, a vacuum manifold consists of a heavy-duty glass basin that will not discolor,
fog, or dissolve when exposed to organic solvents such as tetrahydrofuran. The Analytichem and
the EM Science devices have two operating positions that allow a switch to be made between
the waste and the collect steps in a matter of seconds. Replaceable stainless steel sample
delivery tips provide the cleanest possible extracts, and a series of collection racks allows use of
the appropriate collection vials. A built-in vacuum bleed valve and gauge is part of the manifold
and a vacuum trap consisting Qf a 500-mL or larger vacuum flask, 1/4-inch vacuum tubing, and
a vacuum source are needed to operate the system. Individual valves on the Visiprep vacuum
manifold cover allow precise control of the flow through the cartridges.
Another interesting device that is available commercially is the Visidry Drying

Attachment from Supelco Inc. This device is attached to the vacuum manifold and can dry up
to 12 cartridges simultaneously, or it can evaporate solvent from up to 12 fractions at one time
in the same containers. Gas flow to each tube can be independently adjusted, preventing sample
loss through splashing.
A detailed diagram of a vacuum manifold is shown in Figure A-5.
2.3 AUTOMATED DEVICES
We had the opportunity to see three of the automated devices that are available
commercially for processing samples prior to analysis. These devices include: the Millilab
Workstation (Waters), the BenchMate (Zymark Corp), and the ASPEC (Gilson Medical
Electronics Inc). Each of these devices will be described in detail below. Another system, the
Advanced Automated Sample Processor (AASP), was developed by Analytichem International
and is currently marketed by Varian Associates. This is the first device for automated SPE;
however, the system is considered only semiautomated because the sample is loaded off line.
Ten cassettes consisting of 10 sample cartridges each can be processed with this system at a time.
When the cartridge is clamped in a compression chamber, it becomes part of the HPLC
flowstream and is placed on line with the HPLC column.
The Millilab workstation consists of two modules, a transport system, and a fluidics
module ( 15). The transport module consists of a robotic arm moving in the :x, y, and z directions
and has a probe with a double-walled tube joined by an inflatable tip. The tip fits into a female
Luer fitting on the cartridge, taking hold or releasing the cartridge by inflating or deflating.
Cartridges, samples, and receiving tubes are positioned on the work surface of the transport
module in racks with preset coordinates that are retained in the memory of the control system.
The fluidics module provides the necessary solvents, sensor controls, and the external
communication interfaces. Two standard test tube sizes are used with this workstation: 16 mm x
100 mm with a capacity up to 15 mL, and 10 mm x 75 mm with a capacity up to 4 mL. Racks
are available that hold 84 of the larger size or 120 of the smaller size tubes.
A-4
In the '\\ASTE' posiuon. Place thumbs on tabs and Rotate lid to the In the 'COLLECT'
column condmoning and lift lid with fingel'5. 'COLLECT' position. position, the sample
waste sol\'ents flol' delivery tips direct the
through a l'~IQl'E purified eluant into the
WASTE Dl\"ERSIO!'\ sample collection tubes
Fl'SSEL to an external with NO CROSS -
\'acuum trap. keeping the CONTAMINATION.
sample collecuon area clean.
Figure A-2. Analyticbem International SPS24 and original VacElut manlfold. Figure taken
.
fi'om Analyticbem International brochure on SPE cartridges.
A·S
Removable stainless steel
A variety of reservoirs. ;olvent guides
stopcocks and adapters
are available ...,.....,,.
Two position cover

simplifies extraction
and elution steps
A rugged
polypropylene
basin - ·L• Built-in vacuum gauge
and bleed valve
Clear, chemical resistant •
window allows visual
inspection during
extraction
Figure A-3. J&W SPE vacuum manifold. Figure taken from J&W Sdentlllc brochure on SPE
cartridges.
A-6
A Supelclean tube c.1n bl
JO•ned 10 a 20ml IC•t No
5. 702' l 0< 60ml (Cat No
5. 70221 reservoir. • 1ml
IC at No 5· 70231 0t 3ml
!Cat No 5- 70241 ftl!rltlOf>
tube. or another Supelclan
tube via an adaPtO< IC1t No
5. 70201
Via'9fei> Sohd Phase

E•trlCtion Vecuum Manifold
IC11 No S· 7030)
•Patent P9nd1n; •us Pat No O 289,861
Figure A-4. Visiprep vacuum manifold. Figure taken from 1989 Supelco chromatography catalog 27.
A-7
0 Stainless Steel Delivery Tips
~ Silicone Lid Seal

c:===============:i~ (Upper Lid Seal)
@ 24-Place Molded Cover [ WASTE COLLECT ,~ LowerLid

~C~~c..-------~~-~-~~~or-""~Washer
f
~c:=:====================::::::;:i
f~~--
'- t:::\ Foam Base Seal
@ Waste Funnel "-i..:::J (Lower Lld Seal)
re
Waste'lbwer
Elastic Lid Fastenel"'
@ Vacuum Release Knob - - - -

@ Glass Vacuum Basin WARNING: If glass
damaged in
is
any way. do not
use Contact AnatytlChem or
your dlSlnbutor
\AC ELUT" SPS 24

0 Vacuum Hose Fitting
Figure A·S. VacElut SPS24. Figure taken from Analyticbem International brochure on SPE
cartridges.
A-8
The BenchMate Workstation Model B220 with liquid management system, membrane
filtration, solid-phase extraction, and HPLC injection is similar to the Millilab Workstation. The
system can use up to six solvents and works only with syringe-barrel-type cartridges. Delivery
of liquids is achieved by precision syringes through a unique 12-port valving technology. The
capacity of the BenchMate is 50 tubes/rack x 4 ra.cks (tube size 16 x 100-mm). It can be used
with 200-mg and 500-mg cartridges.
The BenchMate can be operated either in Autostart or Personal Computer (PC) co~trol
mode. In the Autostart mode, the method is set up and saved to a disk on an off-line PC; the
disk is then loaded into the BenchMate Workstation, and the Autostart button is depressed. In
the PC control mode, an IBM-compatible PC is connected to the workstation, and the method
is set up on the PC. To set up a method to run on the BenchMate Workstation, a series of
menu screens prompt for information such as the type of operations, their sequence, number of
samples, transfer volumes, solvent addition volumes, etc. Figure A-6 exemplifies how to build
a method with the BenchMate Workstation.
Another workstation, ASPEC from Gilson, also uses an x, y, and z robot-like arm for
adding samples, conditioning cartridges (100 mg and 500 mg), and collecting fractions. The
system uses positive pressure (2 to 3 psi) to push solvent through the cartridge. The system is
compatible with most standard disposable cartridges, can process a maximum of 108 samples
without operator intervention, and can accommodate up to 5 different solvents for maximum
selectivity. ASPEC software allows the selection of the proper volume and flowrate for each
solvent used in cartridge preconditioning, elution, rinsing, etc., and can choose between a
sequential and a batch mode of operation.
The complexity of the systems that are available commercially appears to have slowed
their acceptance rate. The few laboratories we have talked to indicated that considerable capital
investment, setup time, and need for a skilled chemist to operate this type of equipment are
required, and that these factors make the use of these systems very expensive. Nonetheless, we
feel that automation of the labor-intensive sample preparation step is much needed.
-·-· -··-·-
I ,,_..__,.~ - .....,_,
... 1 . . . . . . . . . ..-c>e
...,---····-·
1, - · - · · - - - -
·
-· ---t•••lllO<
1- · - ....... 2 . . . . . . . . J . . .
I,-·· ----.... ----=-..

La.1 .... . . . - • • -....
.-- · 1-... _
· c-. ...._., _._ . . . , ... ~""
MIO<
t.e
i
Figure A-6. Building method me and BencbMate Workstation. Figure taken from Zymark
brochure on the BencbMate system.
A-9
SECTION 3
SPE TECHNIQUE
The SPE technique utilizes the principle of selective retention of compounds from a
liquid matrix onto a solid adsorbent. The elution conditions for the SPE cartridges are typically
chosen so that the target analytes are retained onto the adsorbent while the coe:xtracted
materials are washed off from the cartridge with the eluent. Alternatively, the coe:xtracted
materials are retained while the target analytes are eluted from the cartridge. Figure A·7
outlines the steps involved in this process.
The SPE technique is useful in two general areas: in the removal of matrix interferents
that might interfere with the determination of the target analytes, and in trace enrichment. The
former application which has had very limited evaluation is of interest to this study; the latter
application has been dealt with for some time, and there are numerous reports on this subject
••.
•
D D
COSDITIOSISG RETEJ'l.TION RINSE ELl'TION
Conditioning the • Adsorbed isolate A Rinse the eundesired
sorbcnt prior to e Undesired matrix columns components
sample application constiruenu to remove remain
ensures rcpro- A Other undesired undesired • Purified and
duciblc rciention matrix matrix concentrated
of the compound components components isolate read~·
of interest (the for analysis
isolate)
FJpre A-7. SPE technique.
A-10
matter ( 16-27). Applications reported for the removal of matrix interferents include those using
Florisil, alumina, and silica gel. Applications reported for trace enrichment include mostly
bonded-phase silicas, of which C18-bonded silica has had the largest number of applications.
Cartridges available commercially for trace enrichment are shown in Table A-1.
Junk et at. (28) performed procedural blanks on the SFE cartridges to establish the
background levels of organic contaminants. Experimental data reported by Junk et al. (28)
indicated the presence of alkanes, alkenes, various plasticizers and antioxidants; the levels of
these contaminants varied from lot to lot. Hence, these cartridges must be checked for
background contamination prior to use.
Some of the potential pitfalls with the SPE technique are associated mainly with the
adsorbent material, although the eluent cannot be totally ignored. Differences in bonded-phase
materials purchased from different manufacturers can cause changes in compound elution
patterns and recoveries. If a method is not rugged then conditions should be chosen that may
allow some leeway in both solvent and bonded-phase composition (23).
Essentials of the SPE technique are:
• Conditioning of the cartridge prior to the application of the sample is needed to

remove contaminants due to packaging and handling processes and to activate the
packing. Conditioning will leave the adsorbent material in a state that is
compatible with the loading solvent and the analytes of interest. To ensure that
the packing does not get dry between conditioning and sample addition, about
1 mm of the conditioning solvent should remain on the upper frit. H the packing
gets dry, the conditioning procedure must be repeated.
• In the loading step, the sample is passed through the cartridge, and the analytes
of interest are retained by the adsorbent material. For the analytes to be retained
by a polar adsorbent, the solvent in which they are dissolved must be relatively
nonpolar. For example, in case of alumina, Florisil or silica cartridges, which
contain polar materials, the analytes are dissolved in hexane, which is a nonpolar
solvent. In the case of Cwbonded silica, which is a nonpolar adsorbent, the
analytes must be dissolved m an aqueous solution in order for the C 18-bonded
silica to retain them.
• In the rinsing step, undesirable sample components are washed off, leaving the
target analytes on the cartridge. This step is not always performed, especially
for multiresidue analysis, since some target compounds may be washed off with
undesirable sample components.
• Cartridge elution is typically performed with S to 10 bed volumes of solvent. The

bed volume per 100 mg adsorbent of 40-µm particles with 60-A pores is
approximately 120 1.&L Therefore, the optimal solvent volume for a 500-mg
cartridge is 0.6 to 1.2 mL The solvent volume should be kept to a minimum to
minimize elution of undesirable sample components. This means that solvent
polarity should also be taken into consideration. Furthermore, when different
solvents are considered for cartridge elution, each solvent that is passed through
the cartridge must be miscible with the prior solvent.
A·ll
TABLE A-1. GUIDE TO SELECTING SPE CARTRIDGES FOR A PARTICULAR APPLICATION
Analyte Typical
fun<."tional elution Typical
Bond clut groups Matrix IDIYcnts applications
Nonpolar Ct8 •• Octadccyl llxdroohohic i:roul!li Aqueous Methanol Drugs of abuse

extnction CS- Octyl Ammalic rings Waler Acctonitrile Pepi ides
C2- Ethyl Alkyl chains Duffers Ethyl acetate Pesticides
CH - Cydohexyl Biological fluids Chloroform Therapeutic
PH - Phenyl Acidic methanol ~~
CN - Cyanopropyf Hexane
CN •• Cyanopropyf ( endcapped)
Polar . CN - Cyanopropyl Hxdll!J!bitic a:ou&:!! Nonpolar Methanol Vitamin D
extraction 20H - Diol Hydroxyls Hexane lsopropanol Mctaholites
SI - Silica Amines Oils Acetone L.pd separation,,
NH2 - Aminopropyl Heteroatoms (S,O,N) Chloroform Oil additives
PSA - Primary/secondary amine Lipids Carbohydrates
-..,
~
Calion adlange
extraction
sex - Benzenesulfonic acid
(Strong)
PRS - Propylsulfonic acid
(Stong)
~
Amines
Pyrimidines
Acmcous
Water
Acidic bulfen
Biological fluids
Alkaline buffer
High ionic
strength buffer
Phenols
Catecholamines
Herbicides
Pharmaceuticals
CBA - Carboxylic acid (weak)

Anion achmnge SAX - Quaternary amine Ani2m Aguequs Acidic buffer Organic acids
eatnction (Strong) Carhoxylic acids Water Vitamins
PSA - Primary/secondary amine Sulfonic acids Alkline buffen High ionic Fatty acids
NH2 - Aminopropyl (weak) Phosphates Biological fluids strength buffer Phosphates
DE!A •• Diethylaminopropyl (weak)
Qwalent PBA - Phenylboronic acid VK;inal sli2I~ Aqueous Acidic methanol Nucleotides
extradion Alkaline buffen Nudeosides
Biological fluids Carbohydrates
Catecholamines
•Data taken from Analytichem International brochure on SPE cartridges.

• In developing a method involving the SPE technique, consideration must be given
to the properties of the analyte, the adsorbent, and the sample matrix. The
analyte could interact with the adsorbent through hydrogen bonding, electrostatic
interaction, and van der Waals forces. Hydrogen bonding may occur when
functional groups such as carbonyl, amino, and hydroxyl are present. Electrostatic
interaction may occur when there are sulfonates, carboxylates, and amines present.
van der Waals forces or dispersive interactions occur among alkyl and aromatic
groups. Figure A-8 outlines some of these interactions.
• The matrix plays a very important role in the method development. The overall
characteristics of the matrix need to be defined (e.g., is it aqueous or organic
solvent; major constituents such as lipids, surfactants, pigments, etc. need to be
identified.) Once the major constituents are identified, then the particular
adsorbent that will differentiate between the interferents and the analyte needs
to be selected.
A-13
NON·POL.AA INTERACTIONS POL.AR INTERACTIONS
Sort>ents lnte,.ctlona Sort>entl
DIPOLE/DIPOLE
VANDERWMLS HYDROGEN· BONDING
VANDERWMLS
IONIC INTERACTIONS llULTIPU INTERACTIONS

Sort>ents Interactions lotiMMrt Interaction•
~ Si~ ELECTROSTATIC.
PAS. ) - Sl/'-./'J,.l...- ELECTROSTATIC )- Non-POL.AR
* 50i0
CSA:
0
. e •
SI~ 0 •tt.N-R ELECTROSTATIC
Q~'
All tlondeCI 1ilicu •tblt Polar interac:tion1
Cl'9 to tr1e po1ar lilica IUClltratt
)-
Figure A-8. Types of interactions between the analyte and adsorbent. Figure taken from
Reference 18.
A-14
SECTION 4
APPLICATIONS
Table A-2 summarizes the various applications of the SPE cartridge technology for
extract cleanup as reported in the listed references.
The SPE technique was applied to the cleanup of sediment and fish tissue extracts
containing organochlorine pesticides and organophosphorus pesticides (2). Cartridges containing
500 mg Florisil, C18-bonded silica, or silica were employed. Florisil cartridges were used in the
cleanup of lake sediment extracts in hexane, and C18-bonded silica cartridges were used in
cleanup of lake sediment extracts in acetonitrile. The results shown in Table A-3 indicate that
hexane in combination with Florisil cleanup is a poor choice, since recoveries of gamma-BHC,
chlorpyrifos, dieldrin, DDE, and DDT are less than 32 percent. Methylene chloride-acetonitrile-
hexane (50:3:47) was the solvent of choice in eluting the organochlorine pesticides from the C18-
cartridge (Table A-4), and there seemed to be no matrix effects when extracts of loamy fine
sand, organic detritus, or very fine sand were processed through the cartridge (Table A-5).
Both silica and C18-bonded silica were used to fractionate petroleum hydrocarbons
according to their polarity (3). Very polar oil components, such as asphaltenes, were retained
on the silica cartridges when hexane, dichloromethane, and isopropanol were used as the eluting
solvents. The separation characteristics of the C18-bonded silica are different from those of the
silica. For example, the aromatic compounds are eluted from the silica cartridges in the first
fractions, and the aliphatic compounds are eluted later (Figures A-9 and A-10). The C18-phases
are sensitive to substituent effects. For example, one to two additional methyl groups have about
the same increasing effect on the retention as has an additional ring annellation (3).
Florisil and C18-bonded silica cartridges were used successfully to clean up extracts of
plant material containing chlorthalonil, endosulfan I, endosulfan II, and captan (4). Of the two
types of cartridges, Florisil gave the higher recoveries under the conditions used.
C18-bonded silica and aminopropyl-bonded silica were used in tandem to clean up

extracts obtained from marine sediment and animal tissue (5). The c;,-bonded silica retained
lipids and long-chain hydrocarbons, while the aminopropyl cartridge retained amines and organic
acids. The effect of column order was not evaluated; however, the authors reported that the ion
exchange capacity of the aminopropyl-bonded silica was reduced by any nonpolar material in the
sample extract if it preceded the C18-cartridge.
A quick cleanup method for waste solvents was reported by Pedersen and Higgins (6).
A sample of a waste solvent was diluted with hexane and applied to a 350-mg Florisil column.
A major portion of the PCBs and most organochlorine pesticides passed through. Dieldrin,
endosulfan, and endrin were retained on the Florisil column and were recovered with
hexane/methyl-isobutyl ketone (94:6).
A-15
TABLE A-2. SUMMARY OF EXTRACT CLEANUP PROCEDURES THAT EMPLOY SPE
CARTRIDGES
Compound Matrix Extraction solvent SPE cartridge Eluting solvent Reference
gamma-BHC Sediment Acetonitrile c,a·bonded silica Methylene chloride/ acetonitrile/hexanc 2

chloropyrifos Fish tissue Hexane Florisil (50:3:47)
Dieldrin
DOB
DDT
Alkanes Crude oil Hexane Silica Hexane 3

Alkenes Methylene chloride/hexane
Benzenes Methylene chloride/ isopropanol
2-Ring aromatics
3-Ring aromatics
~ Ring aromatics
Asphaltcnc:s Hexane C 18-bonded silica Acetonitrile/water (9:1) 3
Cholesterol lsopropanol/acetonitrile
-
Fatty acid esters lsopropanol/hexane
~ Phthalate eaten
°' Chlorthalonil Plant material Acetone Florisil Hexane/diethyl ether (1:1) 4

Endolulfan I
Bndolulfan II
Captan C 18-bonded silica Acetonitrile 4
PAH1 Marine sediment Acetonitrile C 18-bonded silica Acetonitrile s

Organochlorine pestiddes Animal tissue in series with
aminopropyl-bonded
silica
Orpnochlorine pesticides Waste solvent Hexane or hexane/methyl Florisil Hexane/methyl isobutyl ketone (94:6) 6
isobutyl ketone (50:50)
PCBs Transformer oil Isooctane Florisil Isooctane 7
continued)
TABLE A-2. (Concluded)
Compound Matrix Extraction solvent SPE cartridge Eluting solvent Rererence
Pentachlorophenol Adipose tis.,.ue Hexane Silica Hexane/chloroform 8
Polybrominated blphenyls Adipose tissue Hexane c,8-bondcd silica Acctonitrile/hexane 9

Florisil
Chlorinated hydrocarbons Sandy loam Hexane Florisil Hexane/diethyl ether (1:1) 10

phthalate esters sediment Hexane/acetone (9:1)
NBS standard Hexane/methylene
reference chloride (various combinations)
materials (pine
needles, river
sediment, citrus
leaves, coal, coat
-
flyash)
>•
" Carbofuran
Metaluyl
Soil Acetone, HCl-KCI buffer,
panitioning with
Silica Hexane/acetone (19:1) Hexane/acetone (1:1) 11
Simazine methylene chloride;

solvent exchange to
benzene
Organophosphorus Diol Hexane 12

pesticides Hexane/acetone (9:1) Hexane/acetone (8:2)
Triazines Soil See Table A-7 sex Acetonitrile/0.1 M K1HPO, 13

Muscle tissue c,,-silica (50:50)
Com oil Diol
Organochlorine pesticides Sludge Methylene Florisil Hexane/diethyl ether (50:50) 14

chloride/acetone (50:50)
TABLE A-3. RECOVERIES OF PESTICIDES FROM LAKE SEDIMENT USING
EXTRACTION SOLVENT AND SPE CARTRIDGE COMBINATIONS•
Percent
Compound Extraction solvent Column Eluting solvent recovery
gamma-BHC Hexane Florisil Methylene chloride/ 32.3

Chlorpyrifos acetronitrile/hexane 17.2
Dieldrin (50:3:47) 20.0
DDE 10.5
DDT 20.8
gamma-BHC Acetonitrile C18-bonded silica Methylene chloride/ 87.4

Chlorpyrifos acetonitrile/hexane 48.6
Dieldrin (50:3:47) 79.3
DDE 76.7
DDT 90.8
a
Data taken from Reference 2.
A-18
TABLE A-4. PERCENT RECOVERIES OF THE AROCLORS
USING FLORISIL AND SILICA CARTRIDGES•
Percent
Compound Eluting solvent recovery
gamma-BHC Acetonitrile 52.1

Chlorpyrifos 17.1
Dieldrin 21.6
DDE 9.3
DDT 30.2
gamma-BHC Methylene chloride/ 87.4

Chlorpyrifos acetonitrile/hexane 48.6
Dieldrin (50:3:47) 79.3
DDE 76.7
DDT 90.8
gamma-BHC Hexane 81.4

Chlorpyrifos 37.3
Dieldrin 5.0
DDE 78.1
DDT 51.3
•Data taken from Reference 2.
A·19
TABLE A-5. RECOVERIES OF PESTICIDES FROM DIFFERENT
SEDIMENT 1YPES USING ACETONITRILE AS
EXTRACTION SOLVENT AND THE C18 SPE CARTRIDGES
WITH THE METHYLENE CHLORIDE/ACETONITRILE/
HEXANE (50:3:47) ELUTION MIXTURE•
Sediment sample Compound Percent recovery
Loamy gamma-BHC 87.4

fine Chlorpyrifos 48.6
sand Dieldrin 79.3
DDE 76.7
DDT 90.8
Organic gamma-BHC 64.5

detritus Chlorpyrifos 37.9
Dieldrin 58.6
DDE 47.3
DDT 51.8
Very fine gamma-BHC 75.1

sand Chlorpyrifos 46.1
Dieldrin 62.2
DDE 66.6
DDT 67.3
1
A-20
======================================================================~
Compound class Fl F2 F3 F4 FS ~
~--~------~------~~~--~--~--~~~------~----~~~------~~a
Alkanes xxxxxx ffl
Alkenes xxxxxx
Benzenes xxxxxx
2-Ring aromatics xxxxxx
3-Ring aromatics xxxxxx
4-6-Ring aromatics xxxxxx
Asphaltenes retained
Cholesterol xxxxxx
Fatty acid esters xxxxxx
Phthalates xxxxxx
•canridge Fl F2 F3 F4 F5
3-mL column 2 mL 2 mL 10% 2 mL20 % 2mL 2 mL 1:1
hexane methylene methylene methylene methylene chloride/
chloride chloride chloride isopropanol
1-mL column 0.5mL 0.5mL 1mL10% 1 mL 1 mL 1:1
hexane hexane methylene methylene methylene chloride/
chloride chloride isopropanol
Figure A-9. Separation of standard compounds on silica cartridges (3 mL).

Figure taken from Reference 3.
I Fl F2 Fla F3
g
~
II Fl F2 F3 0
~--~---C_o_m~p~o_u_n_d_c_la_s_s~--~--------------------------~------~--------ffl
1-2-Ring arom. with alkyl <C4 xxxxxx
3-Ring arom. with alkyl <C3 xxxxxx
4-Ring arom. with alkyl <C2 xxxxxx
5-Ring arom. with alkyl <C 1 xxxxxx
6-Ring arom. xxxxxx
1-6-Ring arom. with alkyl >than above xxxxx..... .
>6-Ring arom. xxxxxx. ........... .
<n·C12 xxxxx
n-C 12 to n-C 20
>n-Cio xxxxx
Phthalates depending on sidechain
1
Elution system Fl F2 F2a F3
I 3.5 mL 9:1 3 mL 1:9 3 mL 1:1 4 mL 1:1
acctonitrilc/water isopropanoJ/ isopropanoJ/ isopropanoJ/
acetonittile acctonitrile hexane
II 3mL 3 mL 1:4 4 mL 1:1
acctonitrile isopropanoJ/ isopropanoJ/
acetonittile hexane
Figure A-10. Separation or standard compounds on C11-cartridge (3 mL).

Figure taken from Reference 3.
A·21
The SPE technique was applied successfully to the determination of PCBs in transformer
oil (7). A 0.2-g transformer oil sample was applied to a 500-mg Florisil cartridge prewetted with
500 µL isooctane. Without this prewetting, approximately 20 percent of PCBs present in the sample
were found to bind irreversibly to Florisil. PCBs were eluted from the Florisil cartridge with five
2-mL portions of isooctane. Dilution of the transfonner oil with isooctane prior to loading it to the
Florisil cartridge did not result in improved recoveries. On the contrary, this required additional
silanized glassware (7).
Ansari and Hendrix (8) reported that pentachlorophenol can be separated from human
adipose tissue using silica gel cartridges (300 to 500 mg) and hexane (17 mL). With an
intermediate elution step (hexane/chloroform 1:1, 5 mL), recovery of pentachlorophenol increased
to 97 percent; however, more fat was also removed from the cartridge (8). The C 1 -cartridge was
also evaluated for this application; however, pentachlorophenol could not be resolve~ from fat when
methanol/water (9:1) was used to elute the C 18-cartridge (8).
A similar application was reported by Hu et al. (9) for the cleanup of adipose tissue
extracts containing polybrominated biphenyls. Removal of fat was four times as high with the
C18-cartridge than with the Florisil cartridge. Sequential extraction of adipose tissue extracts
through both cartridges in either sequence removed 94 to 96 percent of the fat and gave recoveries
of 96 to 99 percent for polybrominated biphenyls. In this case, the cartridges were eluted with
40 mL acetonitrile or 10 mL hexane.
Disposable cartridges containing 1 g Florisil were investigated for the cleanup of extracts
obtained from various environmental matrices (10). Elution patterns and recoveries were
determined for 22 chlorinated hydrocarbons and 16 phthalate esters in the presence of interferents
such as corn oil, diesel hydrocarbons, organochlorine pesticides, and chlorinated phenols. Hexane
(5 mL) recovered 18 chlorinated hydrQCarbons from the 1-g Florisil cartridge. Collection of a
second fraction from the Florisil cartridge by elution with hexane/diethyl ether (1:1) helped recover
the four BHC isomers that could not be recovered with hexane; however, their elution patterns
were difficult to reproduce, especially when interferents were present. When hexane/acetone (9:1)
was used as eluent, recoveries of the 22 compounds were > 90 percent, except hexachlorobenzene
at 78 percent. The cleanup procedure developed by Lopez-Avila et al. (10) was tested for
chlorinated hydrocarbons with nine environmental matrices, including relatively clean matrices such
as a sandy loam soil and highly contaminated matrices such as Detroit River sediment and Bloody
Run Creek sediment. The results indicated that the cleanup procedure works, regardless of the
complexity of the matrix, and more than two-thirds of the measurements showed recoveries
> 75 percent.
Lopez-Avila et al. (10) also reported a Florisil cartridge procedure for the separation of
phthalate esters from organochlorine pesticides with hexane containing 26 percent methylene
chloride. The phthalate esters were retained on the Florisil cartridge while the organochlorine
pesticides were eluted; the phthalate esters were then recovered with hexane/acetone (9:1).
A method for the cleanup of soil extracts containing carbofuran, metalaxyl and simazine
was reported by Getzin et al. ( 11 ). In this method, pesticide residues were extracted from soil
with acetone/aqueous buffer (9:1) at pH 2, and then partitioned into methylene chloride/carbonate
buffer (pH 10.7). The solvent was then exchanged to benzene. The benzene extract was passed
through a silica cartridge already preconditioned with benzene. Interfering compounds were washed
off with hexane/acetone (19:1), and the pesticides were ·eluted with hexane/acetone (1:1).
A-22
Elution patterns and recoveries of 21 organophosphorus pesticides from a diol cartridge
were reported by Hatcher et al. (12). Seven organophosphorus pesticides, chlorpyrifos, demeton,
disulfoton, fenthion, ethylparathion, phorate, and ronnel were eluted from the diol cartridge with
hexane. Hexane/acetone (9:1) was used to recover azinphos methyl, bolstar, coumaphos, ethoprop,
EPN, malathion, merphos, methyl parathion, and sulfotepp. Dimethoate and fensulfothion required
a more polar solvent (e.g., hexane/acetone 8:2), while monocrotophos and 1EPP were not
recovered at all from the diol cartridge (Table A-6).
Triazines were selectively eluted from three different types of cartridges (SCX,
C18-bonded-silica, and diol), depending on the sample matrix (13). The procedures are outlined
in Table A-7. A strong cation exchange cartridge (SCX) was used for the soil matrix because soil
contains a large number of charged species that can be selectively retained or eluted by the
benzene-sulfonylpropyl packing. To retain the triazines on the SCX cartridge, they were first
protonated by the addition of 1 percent acetic acid to the extract. The extract was then transferred
to the cartridge. The sulfonyl group of the sex material is negatively charged and therefore retains
the protonated atrazine. After rinsing the cartridge with 1 percent acetic acid, acetonitrile, water,
and 0.1 M K2HP04 to eliminate matrix interferents, triazines were eluted with acetonitrile/0.1 M
K2HP04 (50:50). In the case of the C18-bonded-silica, the lipids were strongly retained by the C18-
chain while the triazines were eluted with methanol. In the case of com oil cleanup on the diol
cartridge, which is very polar, the triazines will be retained by hydrogen bonding and can be later
eluted with methanol.
Cleanup of sludge samples spiked with organochlorine pesticides was reported by Supelco
researchers (14). The adsorbent material, LC-Florisil, was conditioned with methylene
chloride/acetone (50:50) prior to use, and the packing material was allowed to dry under gentle
vacuum ( 15 mm Hg) for 3 min. The sludge extract in acetone (with traces of methylene chloride)
was applied to the cartridge and allowed to pass through under gravity only. This was followed by
vacuum drying of the cartridge. The organochlorine pesticides were recovered using three 1-mL
portions of hexane/diethyl ether (50:50). Compounds were recovered quantitatively (recovery
>93 percent), and method precision varied from 4.4 to 12 percent for 12 determinations.
A-23
TABLE A-6. PERCENT RECOVERIES OF 21 ORGANOPHOSPHATE PESTICIDES
FROM DIOL CARTRIDGES•
Hexane/acetone Hexane/acetone
Compound Hexane (9:1) (8:2)
Azinphos methyl 100

Bolstar 4.2 102
Chlorpyrifos 100
Coumaphos 105
Dem et on 123
Dimethoate 55
Disulfoton 95
Ethoprop 2.5 107 1.9
EPN 12 98
F ensulfothion 3.0 60
Fenthion 101
Malathion 116
Merphos 29 75
Monocrotophos NDb
Parathion-ethyl 100
Parathion-methyl 101
Ph orate 95
Ronn el 101
Sulfotep 116
TEPP ND
Tetrachlorvinphos 100
1
Data taken from Reference 12. A 500-mg diol cartridge was used for this
experiment.
bND -- not detected.
A-24
TABLE A-7. EXTRACTION AND CLEANUP OF TRIAZINES FROM
SOIL, MUSCLE TISSUE, AND CORN OIL•
Soll: 500 mg sex cartridge

Extraction: 100 g soil shaken in 90% acetonitrile
Precondition: S mL 1% acetic acid
Load: 5 mL filtered extracted diluted with 25 mL 1% acetic acid
Rinse: 2 mL 1% acetic acid
1 mL acetonitrile
1 mL water
1 mL 0.lM K2HP04
Elution: 2 mL acetonitrile/0.1 M K2HP0.(50:50)
Muscle tissue: 500 mg C11 cartridge

Extraction: 100 g tissue homogenized in 100 mL methanol
Precondition: 5 mL methanol
5 mLwater
Load: 5 mL filtered extracted diluted with 50 mL water
Rinse: 2 mL water
Elution: 2 mL methanol
Com oil: 500 mg dlol cartridge

Extraction: None
Precondition: 5 mL methanol
5 mL hexane
Load: 5 mL com oil diluted with 50 mL hexane
Rinse: 2 mL hexane
Elution: 2 mL methanol
1
A-25
REFERENCES
1. Majors, R. E., "New Devices and Instrumentation for Sample Preparation in Chromatog-
raphy," LC·GC 7(2), 92-96, 1989.
2. Marble, L. K., and Delfino, J. J., "Extraction and Solid Phase Cleanup Methods for
Pesticides in Sediment and Fish," American Laboratory 22-32, November 1988.
3. Theobald, N., "Rapid Preliminary Separation of Petroleum Hydrocarbons by Solid-Phase

Extraction Cartridges," Analytica Chimica Acta 204, 135-144, 1988.
4. Bicchi, C., D'Amato, A., Tonutti, I., and Barbina, M. T., "Use of Prepacked Cartridges in
the Clean-up of Plant Material in Residual Pesticide Analysis," Chromatographia 20 (4),
219-222, 1988.
5. Ozretich, R. J., and Schroeder, W. P., "Determination of Selected Neutral Priority Organic
Pollutants in Marine Sediment Tissue, and Reference Materials Utilizing Bonded-Phase
Sorbents," Anal. Chem. 58, 2041-2048, 1986.
6. Pedersen, B. A., and Higgins, G. M., "A Novel Cleanup Technique for Organochlorine
Pesticides and PCBs in a Complex Organic Matrix," LC·GC 6(11), 1017-1018, 1988.
7. The Supelco Reporter, "Solid Phase Extraction of PCBs from Transformer Oil,"
Volume VII, No. 4, July 1988.
8. Ansari, G. A. S., and Hendrix, P. Y., "Rapid and Convenient Separation of

Pentachlorophenol from Human Fat Using Silica Sep-Pak Cartridges," J. Chrom. 346, 435-
439, 1985.
9. Hu, L.A., Ansari, G. A. S., Treinen Maslen, J., and Reynolds, E. S., "Efficient Clean-up
of Fat Samples by Sep-Pak Cartridges for Polybrominated Biphenyl Analysis," J. Chrom.
241, 419-422, 1982.
10. Lopez-Avila, V., Milanes, J., and Beckert, W. F., "Cleanup of Environmental Sample
Extracts UsingAorisil Solid-Phase Extraction Cartridges," J. Chrom. Sci. 27, 209-215, 1989.
11. Getzin, L W., Cogger, C. G., and Bristow, P. R., "Simultaneous Gas Chromatographic
Determination of Carbofuran, Metalaxyl, and Simazine in Soils: J. Assoc. Off. Anal.
Chem. 72, 361-364, 1989.
12. Hatcher, M., Marsden, P., and Taylor, V., "Analysis of Organophosphorus Pesticide by
Capillary GC/FPD and GC/MS," Proceedinp of the U.S. EPA Symposium on Waste
Testing and Quality Assurance, Vol Il, p. G-70, 1988. .
A-26
13. J & W Scientific, "Extraction of Triazines Using Solid Phase Extraction Cartridges," The
Separation Times 3(1), 4-9, 1989.
14. The Supelco Reporter, "Reliable Solid Phase Extraction Procedure for Low Levels of
Pesticides in Sludge Samples," Vol. VIll, No. 4, 1989.
15. Chladek, E., and Marano, R. S., "Use of Bonded Phase Silica Sorbents for Sampling of
Priority Pollutants in Wastewaters," J. Chrom. Sci. 22, 313-319, 1984.
16. Fallick, l.G., "A New Streamlined Approach to Automated Filtration and Solid Phase
Extraction for Automated Sample Preparation Workstation," J. Anal. Purific. 24-27,
February 1987.
17. Andrews, J. S., and Good, T. J., "Trace Enrichment of Pesticides Using Bonded-Phase
Sorbents," American Laboratory 14, 73-75, 1982.
18. Harris, P. A., "Rationale of Method Development," The Second Annual International
Symposium on Sample Preparation and Isolation Using Bonded Silicas, January 14-15,
1985, Philadelphia, PA.
19. Barber, T., "The Use of Bonded and Unhanded Silica for the Rapid Separation of
Additives from Complex Mixtures," The Second Annual International Symposium on
Sample Preparation and Isolation Using Bonded Silicas, January 14-15, 1985, Philadelphia,
PA.
20. Wells, M. J.M., and Michael, J. L., "Reversed-Phase Solid-Phase Extraction for Aqueous
Environmental Sample Preparation in Herbicide Residue Analysis," J. Chrom. Sci. 25,
345-350, 1987.
21. Baker, J. T., "Solid Phase Extraction Sample Preparation," 1988.
22. Wolkoff, A. W., and Creed, C., "Use of Sep-Pak C18 Cartridges for the Collection and
Concentration of Environmental Samples,~ J. Liquid Chrom. 4(8), 1459-1472, 1981.
23. Ferris, I. G., and Haigh, B. M., "A Rapid and Sensitive HPLC Procedure for the
Determination of Atrazine Residues in Soil-Water Extracts," J. Chrom. Sci. 25, 170-173,
1987.
24. Hurst, W. 1., "Bonded Solid-Phase Extraction Columns for the Sample Preparation of
Food Materials," LC.GC 6(3), 216-218, 1988.
25. Bardalaye, P. C., and Wheeler, W. B., "Solid-Phase Extraction and Capillary Gas
Chromatographic Determination of Triazine Herbicides in Water," Intern. J. Environ.
Anal. Chem. 25, 105-113, 1986.
26. The Supelco Reporter, "Highly Reproduetble Sample Recovery Using Solid Phase
Extraction,• Vol. VD, No. S, September 1988.
27. Sherma, J., "Determination of Organochlorine Insecticides in Waters by Quantitative TLC

and C-18 Solid Phase Extraction," J. Liquid Chrom. 11(9 & 10), 2121-2130, 1988.
A-27
28. Van Home, K. C., "Method Development-Sample Matrix Considerations," The Second
International Symposium on Sample Preparation and Isolation Using Bonded Silicas,
January 14-15, 1985, Philadelphia, PA.
29. Junk, G. A., Avery, M. J., and Richard, J. J., "Interferences in Solid-Phase Extraction
Using C-18 Bonded Porous Silica Cartridges," Anal. Chem. 60(13), 1347-1350, 1988.
A·28
Appendix B
METHOD 3670 -- SAMPLE EXTRACT CLEANUP

USING SPE CARTRIDGES
DRAFT PROTOCOL
METHOD 3670
SAMPLE EXTRACT CLEANUP USING SPE CARTRIDGES
1.0 SCOPE AND APPLICATION
1.1 This protocol specifies cleanup procedures using solid-

phase extraction cartridges that contain Florisil, alumina, diol
or silica. These materials are used for general column
chromatography prior to gas chromatographic analysis. Florisil, a
registered trade name of the Floridin Co., is a magnesium silicate
with acidic properties. Alumina is a highly porous and granular
form of aluminum oxide. It is available in three pH ranges (basic,
neutral, and acidic). Silica gel is an amorphous silica with weakly
acidic properties.
1. 2 Specific applications: This method includes guidance for

cleanup of sample extracts containing the following analyte groups:
Methods 8080/8081 organochlorine pesticides and polychlorinated
biphenyls, Method 8060 phthalate esters, Method 8120 chlorinated
hydrocarbons, and Method 8040 phenols.
2.0 SUMMARY OF METHOD
2.1 Florisil, alumina, diol or silica solid-phase extraction

cartridges containing 40-um particles (60-A pores) are recommended
for use. These cartridges consist of serological-grade
polypropylene tubes, 6 mL in volume, each ·packed with 1 g of
adsorbent. The material is held between two polyethylene frits
(20-um pores). Each cartridge is prewashed with 4 mL hexane or
hexane with 10 percent acetone (as specified in this protocol for
various type of cartridges) immediately prior to use. Aliquots of
1 to 2 mL of sample extracts in hexane are loaded onto the
cartridges which are then eluted with suitable solvent (s). A
vacuum manifold is required in order to get reproducible results.
The collected fractions are further concentrated prior to gas
chromatographic analysis.
3.0 INTERFERENCES
3.1 A reagent blank should be performed for the compounds of

interest prior to the use of this method. The level of
interferences must generally be below the method detection limit
before this procedure is performed on actual samples. However,
phthalate esters were detected in Florisil cartridge method blanks
at levels ranging from 10 to 406 nq per cartridge, with 5 phthalate
esters in the 105 to 460 ng range. Complete removal of the
phthalate esters from Florisil and alumina cartridges does not seem
possible.
3.2 More extensive procedures than those outlined in this

method may be necessary for reagent purification.
B-1
4.0 APPARATUS AND MATERIALS
4.1 Vacuum manifold, VacElute Manifold SPS-24 (Analytichem

International) or Visiprep (Supelco, Inc.) or equivalent,
consisting of glass vacuum basin, collection rack and funnel,
collection vials, replaceable stainless steel delivery tips, built-
in vacuum bleed valve and gauge. The system is connected to a
vacuum pump or water aspirator through a vacuum trap made from a
500-mL sidearm flask fitted with a one-hole stopper and glass
tubing.
4.2 Cartridges, Florisil, alumina, dial or silica (40-um

particles, 60-A pores), 1 g; cartridges consist of serological-
grade polypropylene tubes, 6 mL in volume; the adsorbent is held
between two polyethylene or stainless steel frits (20-um pores).
Cartridges of 0.5 g and 2.0 g are also available and could be used,
however, the compound elution patterns need to be verified when
cartridges are used the are different in size from those specified
in this method.
4.3 Kuderna-Danish (K-D) apparatus
4.3.1 Concentrator tube: 10 mL, graduated (Kontes K-

570050-1025 or equivalent) • Ground-glass stopper is used to
prevent evaporation of extracts.
4.3.2 Evaporation flask: 500 mL (Kontes K-570001-0500

or equivalent). Attach to concentrator tube with springs.
4. 3. 3 Snyder column: Three-ball macro (Kontes K-503000-

0121 or equivalent).
4.3.4 Snyder column: Two-ball macro (Kontes K-569001-

0219 or equivalent).
4.4 Muffle furnace.

4.5 water bath: Heated, with concentric ring cover, capable
of temperature control (±5°C). The bath should be used in a hood.
4. 6 Boiling chips: Solvent-extracted, approximately 10/40
mesh (silicone carbide or equivalent).
5.0 REAGENTS
5.1 Diethyl ether: Pesticide quality or equivalent.
5.1.1 Must be free of peroxides as indicated by EM Quant

test strips (available from EM Laboratories, Elmsford, NY 10523).
5.1.2 Procedures recommended for removal of peroxides

are provided with the test strips. After cleanup, 20 mL ethyl
alcohol preservative must be added to each liter of diethyl ether.
B-2
5.2 Hexane, acetone, methylene chloride, toluene: Pesticide
quality or equivalent.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic

Analytes, Section 4.1.
7.0 PROCEDURE
7.1 Cartridge Set-up and Conditioning

7.1.1 Arrange the cartridges on the manifold in the
closed-valve position.
7.1.2 Turn vacuum pump on and set pump vacuum to 10
inches of mercury. Do not exceed the manufacturer's recommendation
for manifold vacuum. Flow rates can be controlled by opening and
closing cartridge valves.
7.1.3 Condition the cartridges by pipetting 4 mL hexane
onto each cartridge. Slowly open the cartridge valves to allow
hexane to pass through the sorbent beds to the lower frits. Allow
a few drops per cartridge to pass through the manifold to remove
all air bubbles. Close the valves and allow the solvent to soak the
entire sorbent beds for 5 min. Do not turn off the vacuum.
7.1.4 Slowly open cartridge valves to allow the hexane
to pass through the cartridges. Close the cartridge valves when
there is still at least 1 mm solvent above the sorbent bed. Do not
allow cartridges to get dry. If this happens, repeat the
conditioning step.
7.2 General extract cleanup procedure
7.2.1 Allow extract to reach room temperature if it was
in cold storage.
7.2.2 Inspect the extract visually to ensure that there
are no particulates or phase separations and that the volume is as
stated in the accompanying documents, and verify that the solvent
is compatible with the cleanup procedure. If crystals of sulfur are
visible or if the presence of sulfur is suspected, proceed with
Method 3660.
7.2.3 Pipet 2 mL of extract onto each cartridge. Open
the cartridge valves to allow the extracts to pass through the
cartridge beds at approximately 2 mL/min. When the entire extracts
have passed through the cartridges, but before the cartridges get
dry, rinse the sample vials.with additional 0.5 mL solvent portions
and add the rinses to the corresponding cartridges. Close the
cartridge valves and turn off the vacuum after the solvent has
passed through,· ensuring that the cartridges never get dry.
13-3
7.2.4 Place clean 5-mL vials or volumetric flasks into
the sample rack corresponding to the cartridge positions.
7. 2. 5 Attach solvent-rinsed stainless steel solvent

guides to manifold cover and align with collection vials.
7.2.6 Add the first eluting solvent(s) to each
cartridge.
7.2.7 Turn vacuum pump on. Adjust pump pressure to 10

inches of mercury. Allow solvent to soak the sorbent beds for 1 min
or less. Slowly open the cartridge valves and collect eluates into
the collection vials (if the procedure calls for collection of
Fraction l) or discard.
7.2.8 Close cartridge valves, replace collection vials,

and add the second eluting solvent(s) to each cartridge to collect
Fraction 2. Slowly open cartridge valves and collect eluates.
7.2.9 Bring the total volume of each fraction to 5 mL

by adding additional solvent. If this final volume is too dilute
for gas chromatographic analysis then the fractions collected have
to be concentrated to 1 mL or less, using either nitrogen blowdown
or a micro-Snyder column. Measure the final volumes of the
fractions collected with a syringe.
7.2.10 Transfer the fractions to autosampler vials for

gas chromatographic analysis.
7.3 Organochlorine pesticides
7.3.1 Reduce the sample extract volumes to 2 mL prior

to cleanup. The extract solvent must be hexane.
7.3.2 Use 1-g silica cartridges (whenever

polychlorinated biphenyls are known to be present) or diol
cartridges and perform the steps described in Section 7.1. Hexane
is used to condition the silica cartridges, and hexane with 10
percent acetone is used to condition the diol cartridges.
7.3.3 Add the extracts to the cartridges. Follow step

by step the instructions given in Section 7.2. Silica cartridges
are eluted first with 5 mL hexane to collect Fraction 1 and then
with 5 mL hexane with 50 percent diethyl ether to collect Fraction
2. Diol cartridges are eluted with 10 mL hexane with 10 percent
acetone. Adjust the volumes of the fractions collected to whatever
volume is required (see Method 8081) and analyze. Tables 1 and 2
show compound recoveries for the 1-g silica and the 1-g dial
cartridges, respectively.
B-4
7.4 Phthalate esters
7.4.1 Reduce the sample extract volumes to 2 mL" prior
7. 4. 2 Use 1-g Florisil or alumina cartridges and perform
the steps described in Section 7.1. Hexane is used to condition
the cartridges.
by step the instructions given in Section 7.2. If organochlorine
pesticides are known to be present in the extract, use Florisil
cartridges. Elute the Florisil cartridges with hexane with 20
percent methylene chloride to remove the organochlorine pesticides.
The phthalate esters are recovered with 10 mL hexane with 10
percent acetone. Alumina cartridges are eluted with 10 mL hexane
with 20 percent acetone. Adjust the volumes of the fractions
collected to whatever volume is required (see Method 8061) and
analyze. Table 3 and 4 show compound recoveries for the 1-g
Florisil and the 1-g alumina cartridges, respectively.
7.5 Chlorinated hydrocarbons
7.5.2 Use 1-g Florisil cartridges and perform the steps
described in Section 7 .1. Hexane is used to condition the Florisil
cartridges.
by step the instructions given in Section 7.2. Florisil cartridges
are eluted with 5 mL hexane with 10 percent acetone. Adjust the
volumes of the fractions collected to whatever volume is required
(see Method 8121) and analyze. Table 5 shows compound recoveries
for the 1-g Florisil cartridges.
7.6 Phenols
7.6.2 Use 2-g silica cartridges and perform the steps
described in Section 7.1. Hexane is used to condition the silica
cartridges.
by step the instructions given in Section 7.2. Silica cartridges
are eluted first with 5 mL hexane which is discarded (Fraction 1).
The phenols are eluted with 5 mL hexane with 25 percent toluene.
If smaller cartridges are used, then Fraction 1 cannot be discarded
since it contains some of the phenols. Adjust the volumes of the
fractions collected to whatever volume is required ( see Method
B-5
8041) and analyze. Table 6 shows compound recoveries for the 2-g
silica cartridges.
8.0 QUALITY CONTROL
8.1 Before any samples are cleaned up using the solid-phase
extraction cartridges, the efficiency of the cartridge must be
verified. A recovery check must be performed using standards of
the target analytes at known concentration. Only lots of
cartridges that do meet the recovery criteria for the spiked
compounds can be used to process the samples.
8.2 A check should also be performed on each individual lot
of cartridges and for every 300 cartridges of a particular lot.
9.0 REFERENCES
1. Lopez-Avila, v., Milanes, J., Dodhiwala, N.S., and Beckert,
w. F."Cleanup of Environmental Sample Extracts Using Florisil
Solid-Phase Extraction cartridges", J. Chrom. Sci. 27, 209-
215, 1989.
B-6
TABLE 1. PERCENT RECOVERIES AND ELUTION PATTERNS FOR 17
ORGANOCHLORINE PESTICIDES FROM 1-g SILICA CARTRIDGES a
alpha-BHC 0 98.7 2.3

gamma-BHC 0 94.8 1.9
beta-BHC 0 94.3 3.0
Heptachlor 97.3 1.3 0
delta-BHC 0 90.8 2.5
Aldrin 95.9 1.0 0
Heptachlor epoxide 0 97.9 2.1
Endosulfan I 0 102 2.3
4,4 1 -DDE 99.9 1. 7 0
Dieldrin 0 92.3 2.0
Endrin 0 117 2.6
4,4'-DDD 10.7 41 92.4 3.3
Endosulfan II 0 96.0 2.2
4,4'-DDT 94.1 2.0 0
Endrin aldehyde 0 59.7 2.6
4,4'-Methoxychlor 0 98.0 2.4
Aroclor 1016 124
Aroclor 1221 93.5
Aroclor 1232 118
Aroclor 1242 116
Aroclor 1248 114
Aroclor 1254 108
Aroclor 1264 112
aSilica cartridges (Supelco,Inc. lot SP0161) were used; each

cartridge was conditioned with 4 mL hexane prior to use. The
organochlorine pesticides were tested separately from PCBs. For
organochlorine pesticides, each experiment was performed in
duplicate at three spiking levels (0.2 ug, 1.0 ug, and 2.0 ug per
compound per cartridge). Fraction 1 was eluted with 5 mL hexane,
Fraction 2 with 5 mL hexane with 50 percent diethyl ether. PCBs
were spiked at 10 ug per cartridge and were eluted with 3 mL
hexane. The value given for PCBs is the percent recovery for
single determination.
B-7
ORGANOCHLORINE PESTICIDES FROM 1-g DIOL CARTRIDGESa
alpha-BHC 101 8.3

gamma-BHC 95.0 8.4
beta-BHC 86.7 8.5
Heptachlor 96.2 8.4
delta-BHC 75.9 8.2 20.4 45
Aldrin 93.5 8.1
Heptachlor epoxide 98.1 8.5
Endosulfan I 100 9.0
4,4 1 -DDE 97.3 8.3
Dieldrin 95.2 8.2
Endrin 95.9 9.0
4,4'-DDD 97.8 8.9
Endosulfan II 86.0 8.2 15.4 30
4,4'-DDT 96.7 8.3
Endrin aldehyde 19.9 21 58.9 3.7
4,4 1 -Methoxychlor 90.7 8.2
Aroclor 1260 90.0 10.0
aDiol cartridges {Supelco, Inc. lot SP0216) were used; each

cartridge was conditioned with 4 mL hexane with 10 percent acetone
prior to use. The organochlorine pesticides were tested separately
from PCBs. For organochlorine pesticides, each experiment was
performed in duplicate at three spiking levels ( 0.2 ug, 1.0 ug,
and 2.0 ug per compound per cartridge). Each fraction was eluted
with 5 mL hexane with 10 percent acetone. Aroclor 1260 was spiked
at so ug per cartridge. The value given for Aroclor 1260 is the
percent recovery for single determination.
B-8
PHTHALATE ESTERS FROM 1-g FLORISIL CARTRIDGESa
Fraction 2
Average Percent·
Dimethyl phthalate 130 52

Diethyl phthalate 88.2 2.5
Diisobutyl phthalate 118 16
Di-n-butyl phthalate 121 13
Bis(4-methyl-2-pentyl) phthalate 123 5.7
Bis(2-methoxyethyl) phthalate 31.9 31
Diamyl phthalate 93.7 34
Bis(2-ethoxyethyl) phthalate 82.1 19
Hexyl 2-ethylhexyl phthalate 126 6.4
Dihexyl phthalate 62.0 15
Benzyl butyl phthalate 98.3 6.5
Bis(2-n-butoxyethyl) phthalate 135 34
Bis(2-ethylhexyl) phthalate 110 2.7
Dicyclohexyl phthalate 106 3.3
Di-n-octyl phthalate 123 7.0
Dinonyl phthalate 102 8.7
aFlorisil cartridges (Supelco, Inc.) were used; each cartridge was

conditioned with 4 mL hexane prior to use. Each experiment was
performed in triplicate. The spiking level was 500 ng per compound
per cartridge. Fraction 1 was eluted with 5 mL hexane with 20
percent methylene chloride, Fraction 2 with 5 mL hexane with 10
percent acetone. No phthalate esters were detected in Fraction 1.
B~
PHTHALATE ESTERS FROM 1-g ALUMINA CARTRIDGESa
Fraction 1
Average Percent
Dimethyl phthalate 108 4.6

Diethyl phthalate 129 6.6
Diisobutyl phthalate 92.6 7.3
Di-n-butyl phthalate 107 5.6
Bis(4-methyl-2-pentyl) phthalate 88.3 9.8
Bis(2-methoxyethyl) phthalate 92.2 5.0
Diamyl phthalate 100 6.4
Bis(2-ethoxyethyl) phthalate 101 6.3
Hexyl 2-ethylhexyl phthalate 93.2 13
Dihexyl phthalate 113 5.4
Benzyl butyl phthalate 104 3.9
Bis(2-n-butoxyethyl) phthalate 99.5 4.7
Bis(2-ethylhexyl) phthalate 101 6.1
Dicyclohexyl phthalate 97.2 6.2
Di-n-octyl phthalate 103 7.5
Dinonyl phthalate 110 5.2
aAlumina cartridges (J.T.Baker) were used; each cartridge was

performed in duplicate at three spiking levels (40 ug, 80 ug, and
120 ug per compound per cartridge). Fraction 1 was eluted with 5
mL hexane with 20 percent acetone.
B-10
CHLORINATED HYDROCARBONS FROM 1-g FLORISIL CARTRIDGESa
Fraction 1
Average Percent
Hexachloroethane 95.4 2.0

1,3-Dichlorobenzene 101 2.3
Benzyl chloride 101 1.5
1,3,5-Trichlorobenzene 98.4 2.2
Hexachlorobutadiene 94.8 2.0
Benzal chloride 99.2 0.8
Benzotrichloride 90.0 6.5
Hexachlorocyclopentadiene 103 3.3
1,2,4,5-Tetrachlorobenzene 98.0 2.3
2-Chloronaphthalene 94.8 1.4
Pentachlorobenzene 104 1.5
Hexachlorobenzene 78.4 1.1
alpha-BHC 100 0.4
garnrna-BHC 99.0 0.7
beta-BHC 95.4 1.8
delta-BHC 96.8 2.7
aFlorisil cartridges {Supelco, Inc.) were used; each cartridge was

conditioned with 4 mL hexane prior to use. Five replicate
experiments were performed. Spiking level was 1.0 ug per cartridge
for hexachloroethane,hexachlorobutadiene,hexachlorocyclo-
pentadiene, penta- and hexachlorobenzene; 10 ug per cartridge for
tri- and tetrachlorobenzenes, benzal chloride, benzotrichloride,
and the BHC isomers; 100 ug per cartridge for dichlorobenzenes and
benzyl chloride; and 200 ug per cartridge for 2-chloronaphthalene.
Fraction 1 was eluted with 5 mL hexane with 10 percent acetone.
B-11
TABLE 6. PERCENT RECOVERIES AND ELUr:iaION PATTERNS FOR 18 PHENOLS
FROM 2-g SILICA CARTRIDGES
Fraction 2
Average Percent
Phenol 74.1 5.2

2-Methylphenol 84.8 5.2
2,4-Dimethylphenol 91.8 5.6
2-Chlorophenol 88.5 5.0
2,6-Dichlorophenol 90.4 4.4
4-Chloro-3-methylphenol 94.4 7.1
2,4-Dichlorophenol 94.5 7.0
2,4,6-Trichlorophenol 97.8 6.6
2,3,5,6-Tetrachlorophenol 97.5 5.3
Pentachlorophenol 96.2 8.8
asilica cartridges (Supelco, Inc.) were used; each cartridge was

performed in duplicate at three spiking levels (0.05 ug, 0.2 ug,
and 0.4 ug per compound per cartridge). Fraction 1 was eluted
with 5 mL hexane and was discarded. Fraction 2 was eluted with
5 mL hexane with 25 percent toluene.
B-12

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United States Environmental Monitoring EPA/600/4-89/049 t/.

--.._ Viorica Lopez-Avila, Janet Benedicto, and June Milanes

Contract Number 68-03-3511

ENVIRONMENTAL MONITORING SYSTEMS LABORATORY

U.S. Environmental Protection Agency

Fractionation and cleanup of sample extracts prior to instrumental analysis is used to

5 RESULTS AND DISCUSSION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13

5.1 ORGANOCHLORINE PESTICIDES AND

APPENDIX A -- EVALUATION OF SAMPLE EXTRACT CLEANUP

1 GC/ECD chromatograms of Method 8081 organochlorine pesticides

3 GC/ECD chromatograms of the PFB derivatives of phenolic compounds

4 GC/ECD chromatograms of a Method 8081 organochlorine pesticide

5 GC/ECD chromatograms of a Method 8081 organochlorine pesticide

7 GC/ECD chromatograms of a phthalate esters standard spiked with

1 Retention times and relative retention times of organochlorine pesticides

3 Retention times and relative retention times of the PFB derivatives of

4 Samples used in method development . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9

5 Elution patterns and percent recoveries of the organochlorine pesticides

6 Elution patterns and percent recoveries of the organochlorine pesticides

7 Percent recoveries of the Aroclors from Florisil and silica cartridges . . . . . . . 17

8 Elution patterns and percent recoveries of the organochlorine pesticides

9 Elution patterns and percent recoveries of the organochlorine pesticides

10 Elution patterns and percent recoveries of the organochlorine pesticides

11 Percent recoveries and elution patterns of 17 organochlorine pesticides

12 Percent recoveries and elution patterns of 17 organochlorine pesticides

13 Percent recoveries and elution patterns of 17 organochlorine pesticides

14 Elution patterns and percent recoveries of 17 organochlorine pesticides

15 Elution patterns and percent recoveries of 17 organochlorine pesticides

16 Elution patterns and percent recoveries of 17 organochlorine pesticides

17 Elution patterns and percent recoveries of 17 organochlorine pesticides and

18 Percent recoveries and elution patterns of 17 organochlorine pesticides

19 Percent recoveries and elution patterns of 17 organochlorine pesticides

23 Percent recoveries of the phthalate esters from Florisil and alumina

24 Elution patterns and percent recoveries of phthalate esters from Florisil

25 Results of the Florisil cartridge cleanup evaluation study (phthalate ester

26 Experimental design for Florisil cartridge cleanup method development . . . . . 45

27 Recovery of phthalate esters from 1-g Florisil cartridges . . . . . . . . . . . . . . . . 48

28 Recovery of phthalate esters from 1-g Aorisil cartridges in the presence

29 Interferenc~ in ~~ determination of phthalate esters caused by

30 Results of method blank analyses for the f1orisil cartridges . . . . . . . . . . . . . . 51

31 Percent recoveries of phthalate esters in extracts from various matrices

32 Method detection limit study -- Florisil cartridges method blanks . . . . . . . . . . 53

33 Elution patterns and percent recoveries of the PFB derivatives of phenols

35 Elution patterns and percent recoveries of the PFB derivatives of phenols

38 Method reproducibility using the ASPEC robotic system . . . . . . . . . . . . . . . . 60

39 Method reproducibility using the ASPEC robotic system . . . . . . . . . . . . . . . . 61

40 Method reproducibility using the ASPEC robotic system . . . . . . . . . . . . . . . . 62

41 Evaluation of matrix interferents using the ASPEC robotic system . . . . . . . . . 63

42 Percent recoveries of 17 organochlorine pesticides spiked into SS-2 soil

43 Percent recoveries of 17 organochlorine pesticides spiked into SS-5 soil

44 Percent recoveries of 17 organochlorine pesticides spiked into SS-7 soil

45 Percent recoveries of 17 organochlorine pesticides spiked into SS-8 soil

Fractionation or cleanup of sample extracts prior to instrumental analysis for organic

• Bonded-phase silicas and polymeric materials such as those available from

a. Vacuum manifold -- VacElute manifold SPS24 (Analytichem International) or Visiprep

d. Autosampler -- Varian, Model 8000

c. Com oil -- Stock solution was prepared in hexane at 1.1 mg/mL.

1 alpha-BHC , 9.79 0.912 10.22 0.953