KETONES II 2553

FORMULAS: TABLE 1 MW: TABLE 1 CAS: TABLE 1 RTECS: TABLE 1

METHOD: 2553, Issue 1 EVALUATION: PARTIAL Issue 1: 15 March 2003

OSHA : Table 1 PROPERTIES: Table 1

NIOSH: Table 1
ACGIH: Table 1

COMPOUNDS/ (1) 2-Heptanone: Methyl-n-amyl ketone (4) 5-Methyl-3-heptanone: Ethyl amyl ketone
SYNONYMS: (2) 3-Heptanone: Ethyl butyl ketone (5) Camphor: 2-Camphanone, Gum Camphor
(3) Mesityl oxide: 4-Methyl-3-penten-2-one

SAMPLING MEASUREMENT

SAMPLER: SOLID SORBENT TUBE TECHNIQUE: GAS CHROMATOGRAPHY, FID

(Anasorb CMS, 150/75 mg) [1]
ANALYTE: Table 1
FLOW RATE: 0.01 to 0.2 L/min
DESORPTION: 1 mL of 2% isopropanol in CS 2 with
VOL-MIN: 1L agitation [1]
-MAX: 25 L
INJECTION
SHIPMENT: Routine VOLUME: 1 µL

SAMPLE TEMPERATURE
STABILITY: 30 days @ 5°C [1] -INJECTION: 225°C [1]
-DETECTOR: 300°C [1]
BLANKS: 10% of samples -COLUMN: 55°C (3 min hold) to 190°C (8°C/min) [1]

ACCURACY CARRIER GAS: Helium (4.8 mL/min) [1]

RANGE STUDIED: Not Determined. COLUMN: Capillary, fused silica, 30-m x 0.32-mm
ID; 1.00 µm film crossbond trifluoro-
BIAS: Not Determined. propylmethyl polysiloxane or equivalent
[1]
OVERALL
CALIBRATION: Solutions of analytes in desorption
PRECISION ( Ö r T ): Not Determined.
solvent
ACCURACY: Not Determined.
RANGE: See Table 2 [1]

ESTIMATED LOD: See Table 2 [1]

PRECISION ( þ r ): See Table 2 [1]

APPLICABILITY: For a 10-L air sample, the working range for 2-heptanone is 0.86 to 24.8 ppm (4.0 to 121 mg/m3 ); for 3-
heptanone is 0.43 to 12.9 ppm (2.0 to 60.3 mg/m3 ); for mesityl oxide is 0.22 to 6.89 ppm (0.9 to 22.6 mg/m3 ); for 5-methyl-3-
heptanone is 0.21 to 6.29 ppm (1.1 to 33.0 mg/m3 ); and for camphor is 0.14 to 4.84 ppm (0.9 to 30.2 mg/m3 ) [1].

INTERFERENCES: Any compound having the same retention times as the analytes of interest.

OTHER METHODS: This method was developed as part of an update of NIOSH Method 1301 (Issue 2, 15 August 1994) [2]
which combined the NIOSH Methods: S10, S12, S13, S15, and S16 from the 2nd edition of the NIOSH Manual of Analytical
Methods [3,4]. Improvements included: lower LOD/LOQ values, improved DE recovery results (at lower levels) by using
Anasorb CMS and 2% IPA in CS 2 , a 30 day storage stability study, and the replacement of the packed column with a Rtx-200
fused silica capillary column.

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REAGENTS: EQUIPMENT:

1. 2-Hep tanone, reagen t grade (98% ). 1. Sam pler: glass tube, 7 cm long, 6-mm OD, 4-
2. 3-Hep tanone, reagen t grade (98% ). mm ID, flame-sealed ends, containing two
3. Mes ityl oxide, reagent grade (98% ). sec tions o f Anaso rb C MS (front = 150 m g;
4. 5-Methyl-3-heptanone , reagent grade (97% ). back = 75 mg) separated by a 2-mm urethane
5. Cam phor, reagent grade (99% ). plug. A silylated glass wool plug precedes the
6. Ca rbon disulfide, low b enze ne g rade .* front section and a 3-mm urethane plug
7. Iso propanol. follows the back se ction. Tubes are
8. Helium, prepurified and filtered. com m ercially available (S KC # 226-12 1).
9. Hydrogen, prepurified and filtered. 2. Personal sa m pling pum p, 0.01 to 0.2 L/m in,
10. Air, compressed and filtered. with flexible connecting tubing.
11. Desorption solvent: 2% isopropanol in carbon 3. Gas chromatograph, FID, integrator, and Rtx-
disulfide (v/v). 200 fused silica capillary column.
12. DE s tock solution: Add kn own am ount of 4. GC autosam pler vials, 2-m L glass, with PTF E-
analyte to desorption solvent in 10-m L lined crimp caps.
volumetric flask. 5. Syringes, 10-µL, 25-µL, and 1-mL.
6. Pipets, 3-mL and 5-m L, with pipet bulb.
7. Volumetric flasks, 250-mL and 10-mL.
* See SPECIAL PRECAUTIONS

SPECIAL PRECAUTIONS: Carbon disulfide is tox ic and a fire/explosion haza rd (flas h po int = -30 °C).
Isop ropa nol is flam m able. All work sho uld be perform ed in a ventilated fum e ho od.

SAMPLING:

1. Calibrate each personal sampling pump with a representative sampler in line.

2. Break the ends of the sampler imm ediately prior to sampling. Attach sampler to personal sampling
pump with flexible tubing.
3. Sam ple at a known flow rate between 0.01 and 0.2 L/min for a total sample size of 1 to 25 L.
4. Ca p the sam plers and pac k secu rely for shipm ent.

SAMPLE PREPARATION:

5. Place the front (include the initial glass wool plug) and back sorbent sections of the sampler in
separate vials. Discard the foam plugs.
6. Add 1.0 mL of the 2% isopropanol/carbon disulfide desorption solvent to each vial. Securely attach
crim p caps to each vial.
7. Allow to desorb for 30 m inutes with oc cas ional agitation.

CALIBRATION AND QUALITY CONTRO L:

8. Ca librate daily with at leas t six wo rking standa rds to cover the an alytical range. If nece ssa ry,
additional standards may be added to extend the calibration curve.
a. Add known amounts of each analyte to the desorption solvent solution in 10-mL volumetric flasks
and dilute to the m ark. Mix well.
b. Analyze together with samp les and blanks (steps 11 and 12).
c. Prepare c alibration graph (pe ak area versus µg analyte).
9. Determine desorption efficiency (DE) at least once for each lot of Anasorb CMS used for sampling in
the calibration rang e (ste p 8).
a. Prepare three tubes at each of five levels plus three media blanks.

NIOSH Manual of Analytical Methods (NMAM), Fourth Edition

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b. Inject a known amount of DE stock solution directly onto the front sorbent section of each
Anasorb CMS with a microliter syringe.
c. Allow the tubes to air equilibrate for several minutes, then cap the ends of each tube and allow to
stan d overnight.
d. Deso rb (steps 5-7) and a nalyze together with standards and blanks (steps 11 and 12).
e. Prepare a graph of DE versus µg analyte recovered.
10. Analyze three quality control blind spikes and three analyst spikes to ensure that the calibration
graph and DE gra ph are in control.

MEASUREMENT:

11. Set gas chromatograph according to manufacturer’s recomm endations and to conditions given on
page 2553-1. Inject a 1-µL sample aliquot manually using the solvent flush technique or with an
auto sam pler.
NOTE: If pea k area is abo ve the linear ra nge of the working standard s, dilute w ith solve nt,
reanalyze and apply the appropriate dilution factor in the calculations.
12. Measure peak areas.

CALCULATIONS:

13. Determ ine the ma ss, µg (correc ted for DE) of an alyte found in the sam ple front (W f) and back (W b)
sorbent sec tions, and in the average m edia blank front (B f) and back (B b) sorben t sec tions.
NO TE: If W b > W f/10, report breakthrough and possible sample loss.
14. Calculate conce ntration, C, of analyte in the air volume sam pled, V(L):

NO TE : :g/L= m g/m 3

EVALUATION OF METHOD:

This method updates NMAM 1301, which was identified as a problematic gas chromatographic method
from a survey of external users of the NIOSH Manual of Analytical Methods. This new method, by use of
capillary column chrom atography coupled with an improved solid sorbent sampler and modified desorption
solvent, resulted in improvements in LOD/LOQ, sample recovery and storage stability compared to NMAM
1301. The average D E recovery was im proved for all analytes at levels lowe r than those rep orted in
NMAM 1301, ranging from 95% for mesityl oxide to 100% for 3-heptanone. All samples were stable for 30
days with recoveries ranging from 94% for camphor to 99% for 2-heptanone. The complete summ ary of
results is in Table 2.

REFERENCES:

[1] Pende rgrass S M [1 999 ]. Ketones II Method Develop m ent B ack up D ata R epo rt, unpublish ed d ata,
NIOSH/DART.
[2] NIOS H [1994]. Ketones II: Method 1301. In: Eller PM , Cassinelli ME, eds. NIOS H M anual of
Analytical Metho ds, 4 th ed. C incinn ati, OH : National Ins titute for O ccu pation al Safety and Health,
DHHS (NIOSH) Publication No. 94-113.

NIOSH Manual of Analytical Methods (NMAM), Fourth Edition

 KET ON ES II: MET HO D 255 3, Issue 1, dated 15 M arch 200 3 - Page 4 o f 4

[3] NIO SH [1977]. Metho ds S 10, S 12, S 13, S 15, and S 16. N IOS H M anu al of Analytical M etho ds, 2 nd,
ed., V. 2. Cincinnati, OH: N ational Institute for Occup ational Safety and Health, DHEW (NIOS H)
Publication No. 77-157-B.
[4] NIO SH [1977]. Do cum enta tion of NIO SH Valida tion T ests , S10 , S12 , S13 , S15 , and S16 .
Cincinnati, OH: National Institute for Occupational Safety and Health, DHEW (NIOSH) Publication
No. 77-185.

M ETH OD W RITT EN B Y:

Stephanie M. Pendergrass, NIOSH/DART

TABLE 1. GENERAL INFORMATION

Compound/ Fo rm ula Expo sure Lim its mg/m 3= Properties

(Synonyms) (M .W .) 1 ppm
CAS # NIOSH OSHA ACGIH
@ NTP
RTECS REL (ppm) PEL (ppm) TLV (ppm)

Methyl-n-amyl-ketone C7 H1 4 O 100 100 50 4.67 liquid; d 0.820 g/mL;

(2-Heptanone) (114.19) BP 151 o C; VP 0.27
(CAS # 110-43-0) kPa (2 mm Hg)
RTECS MJ5075000

Ethyl butyl ketone C7 H1 4 O 50 50 50 4.67 liquid; d 0.818 g/mL;

(3-Heptanone) (114.19) BP 148 o C; VP 0.53
(CAS # 106-35-4) kPa (4 mm Hg)
RTECS MJ5250000

Mesityl oxide C6 H1 0 O 10 25 15 4.01 liquid; d 0.822 g/mL;

(4-methyl-3-penten-2-one) (98.15) BP 129 o C; VP 1.1
(CAS # 141-79-7) kPa (8 mm Hg)
RTECS SB4200000

5-Methyl-3-heptanone C8 H1 6 O 25 25 25 5.00 liquid; d 0.822 g/mL;

(Ethyl amyl ketone) (128.21) BP 159 o C; VP 0.27
(CAS # 541-85-5) kPa (2 mm Hg)
RTECS MJ7350000

Camphor C1 0 H1 6 O 2 2 2 6.22 solid; spec. gr. 0.992

(CAS # 76-22-2) (152.24) @ 25 o C; MP 174 o C;
RTECS EX1225000 VP 0.024 kPa (0.18 mm Hg,
1470 mg/m3); sublimes
Note: All densities and vapor pressures are at 20°C unless otherwise stated.

TABLE 2. ANALYTICAL RESULTS [1]

Analyte LOD Precision Range DE (Avg) Storag e Stability

(µg) (S r) (µg) (at 5 oC after 30 Days)

2-heptanone 0.5 0.025 40-1206 0.970 0.994

3-heptanone 0.7 0.031 20-603 1.004 0.984

mesityl oxide 0.3 0.014 9-276 0.950 0.993

5-methyl-3-heptanone 0.7 0.032 11-330 0.987 0.990

camphor 0.7 0.043 9-302 0.970 0.939

NIOSH Manual of Analytical Methods (NMAM), Fourth Edition