Ketones II (1301)

by National Institute for Occupational Safety and Health

KETONES II

TABLE 1

MW: TABLE 1

METHOD: 1301, Issue 2

CAS: Table 1

RTECS: Table 1

EVALUATION: FULL COMPOUNDS (3) and (5): PARTIAL

OSHA/NIOSH/ACGIH: Table 1

COMPOUNDS: (Synonyms in Table 1)

1301

Issue 1: 15 February 1984 Issue 2: 15 August 1994

PROPERTIES: Table 1

(1) camphor (2) mesityl oxide

(3) 5-methyl-3-heptanone (4) methyl-(n-amyl)-ketone

SAMPLING

(5) ethyl butyl ketone

MEASUREMENT

SAMPLER:

SOLID SORBENT TUBE (coconut shell charcoal, 100 mg/50 mg)

FLOW RATE:

0.01 to 0.2 L/min

VOL-MIN: -MAX:

1L 25 L

SHIPMENT:

routine

TECHNIQUE:

GAS CHROMATOGRAPHY, FID

ANALYTE:

compounds above

DESORPTION:

1 mL 1% methanol in CS 2; stand in 30 min

INJECTION VOLUME: COLUMN: SAMPLE STABILITY:

unknown

FIELD BLANKS:

2 to 10 field blanks per set

5 µL

stainless steel (3 m x 3-mm ID), 10% FFAP on 80/100 Chromosorb W-AW

TEMPERATURE-INJECTOR: -DETECTOR: -COLUMN:

200 °C 300 °C 100 to 200 °C @ 10 °C/min

CARRIER GAS:

N 2 or He, 30 mL/min

CALIBRATION:

standard solutions of analyte in elution solvent

ACCURACY RANGE STUDIED:

see EVALUATION OF METHOD

BIAS:

see EVALUATION OF METHOD

ˆ rT): OVERALL PRECISION (S METHOD ACCURACY:

see EVALUATION OF

RANGE AND PRECISION:

see EVALUATION OF METHOD

ESTIMATED LOD: 0.05 mg per sample

see EVALUATION OF METHOD

APPLICABILITY: This method was developed to give better desorption than obtainable with carbon disulfide extraction of the charcoal. This method can be used in paint and resin manufacturing plants.

INTERFERENCES: None reported. Alternate columns, e.g., 4 m 10% SP-2100/0.1% Carbowax 1500 on Supelcoport 100/120 or DB-1 fused silica capillary may be used.

OTHER METHODS: This method combines and replaces Methods S10, S12, S13, S15 and S16 [1].

NIOSH Manual of Analytical Methods (NMAM), Fourth Edition, 8/15/94 KETONES II: METHOD 1301, Issue 2, dated 15 August 1994 - Page 2 of 5 REAGENTS: 1.

2. 3. 4. 5.

EQUIPMENT:

Eluent: Carbon disulfide* (chromatographic grade) with 1% (v/v) methanol (chromatographic grade). Analytes, reagent grade. Nitrogen, prepurified. Hydrogen, dry. Air, filtered.

See SPECIAL PRECAUTIONS.

1. Sampler: glass tube, 7 cm long, 6-mm OD, 4-mm ID, flame-sealed ends, containing two sections of 20/40 mesh activated (600 °C) coconut shell charcoal (front = 100 mg; back = 50 mg) separated by a 2-mm urethane foam plug. A silylated glass wool plug precedes the front section and a 3-mm urethane foam plug follows the back section. Pressure drop across the tube must be less than 3.4 kPa at the sampling flow rate. Tubes are commercially available. 2. Personal sampling pump, 0.02 to 0.2 L/min, with flexible connecting tubing. 3. Gas chromatograph, FID, integrator and column (page 1301-1). 4. Vials, 2-mL glass, PTFE-lined crimp caps. 5. Syringe, 10-µL, readable to 0.1 µL. 6. Pipet, 1-mL, with pipet bulb. 7. Volumetric flasks, 10-mL.

SPECIAL PRECAUTIONS: Carbon disulfide is toxic and an acute fire and explosion hazard (flash point = -30 °C); all work done with it must be performed in a fume hood.

SAMPLING: 1. 2. 3. 4.

Calibrate each personal sampling pump with a representative sampler in line. Break the ends of the sampler immediately before sampling. Attach sampler to personal sampling pump with flexible tubing. Sample at an accurately known flow rate between 0.01 and 0.2 L/min for a total sample size of 1 to 25 L. Cap the samplers with plastic (not rubber) caps and pack securely for shipment.

SAMPLE PREPARATION: 5. 6. 7.

Place the front and back sorbent sections of the sampler in separate vials. Discard the glass wool and foam plugs. Add 1.0 mL eluent to each vial. Attach crimp cap to each vial. Allow to stand 30 min with occasional agitation.

CALIBRATION AND QUALITY CONTROL: 8.

9.

Calibrate daily with at least five working standards over the range 0.01 to 0.5 mg camphor; and 0.05 to 5 mg of the other analytes per sample. a. Add known amounts of analyte to eluent in 10-mL volumetric flasks and dilute to the mark. b. Analyze together with samples and blanks (steps 11 and 12). c. Prepare calibration graph (peak area vs. mg analyte). Determine desorption efficiency (DE) at least once for each batch of charcoal used for sampling in the calibration range (step 8). Prepare three tubes at each of five levels plus three media blanks. NIOSH Manual of Analytical Methods (NMAM), Fourth Edition, 8/15/94 KETONES II: METHOD 1301, Issue 2, dated 15 August 1994 - Page 3 of 5 a. Remove and discard back sorbent section of a media blank sampler. b. Inject a known amount of analyte directly onto front sorbent section with a microliter syringe. c. Cap the tube. Allow to stand overnight. d. Desorb (steps 5 through 7) and analyze together with working standards (steps 11 and 12). e. Prepare a graph of DE vs. mg analyte recovered. Analyze three quality control blind spikes and three analyst spikes to insure that the calibration graph and DE graph are in control.

10.

MEASUREMENT: 11.

Set gas chromatograph according to manufacturer's recommendations and to conditions given on page 1301-1. Inject sample aliquot manually using solvent flush technique or with autosampler. NOTE: If peak area is above the linear range of the working standards, dilute with CS 2, reanalyze, and apply the appropriate dilution factor in calculations. Measure peak area.

12.

CALCULATIONS: 13.

Determine the mass, mg (corrected for DE) of analyte found in the sample front (W f) and back (W b) sorbent sections, and in the average media blank front (B f) and back (B b) sorbent sections. NOTE: If W b > W f/10, report breakthrough and possible sample loss. Calculate concentration, C, of analyte in the air volume sampled, V (L):

14.

EVALUATION OF METHOD: Laboratory testing with spiked samples and samples collected from atmospheres generated by syringe pump/air dilution and verified by FID continuous monitor [2]. Results were:

S/A Breakthrough 1 Overall Range Precision ˆ rT (mg/m 3) (L) S

Method [1,2]

Range (mg per sample)

DE 2-

Sr

Camphor

S10

0.02 to 0.40

0.97

0.018

6 to 25

>48

Mesityl oxide

S12

0.10 to 3.0

0.81

0.014

45 to 210

5-Methyl-3-heptanone

S13

0.15 to 4.0

0.90

0.014

Methyl-(n-amyl)-ketone

S15

0.5 to 10.0

0.82

Ethyl butyl ketone

S16

0.25 to 7.0

0.94

Compound

1 2

Bias (%)

Accuracy (±%)

0.074

0.9

10.5

>48

0.071

7.0

22.8

60 to 270

>36

0.10

13.1

31.0

0.012

200 to 925

>36

0.066

4.9

15.0

0.022

100 to 460

>24

0.086

-3.1

26.3

5% breakthrough, 0.2 L/min at high end of concentration range in dry air. Averaged over mass range shown.

NIOSH Manual of Analytical Methods (NMAM), Fourth Edition, 8/15/94 KETONES II: METHOD 1301, Issue 2, dated 15 August 1994 - Page 4 of 5 REFERENCES: [1] NIOSH Manual of Analytical Methods, 2nd. ed., V. 2, S10, S12, S13 and S15, S16, U.S. Department of Health, Education, and Welfare, Publ. (NIOSH) 77-157-B (1977). [2] Documentation of the NIOSH Validation Tests, S10, S12, S13 and S15, S16, U.S. Department of Health, Education, and Welfare, Publ. (NIOSH) 77-185 (1977).

METHOD REVISED BY: Ardith Grote, NIOSH/DPSE; methods originally validated under NIOSH Contract CDC-99-74-45.

NIOSH Manual of Analytical Methods (NMAM), Fourth Edition, 8/15/94 KETONES II: METHOD 1301, Issue 2, dated 15 August 1994 - Page 5 of 5

TABLE 1. GENERAL INFORMATION Exposure Limits, ppm Compound (Synonyms) CAS RTECS

Formula (M.W.)

OSHA

NIOSH

ACGIH TLV STEL

mg/m 3/ppm @NTP

Camphor (CAS #76-22-2) RTECS EX1225000

C10H16O (152.24)

2

2

2 3

6.22

d2

d9 im 9Ll/.o g 0s@ C

° 52

C4°M

P 2 V 0 8aP 14k7 .1 0 .0 m mm H

m

g/g0741

Mesityl oxide (4-methyl-3-penten-2-one) (CAS #141-79-7) RTECS SB4200000

CH 3COCH=C(CH 3)2; C 6H10O (98.15)

25

10

15 25

4.01

dP

Biu 9q 21

Ci°P

V1l .aP 1k 8(m L2;2/8d )ggH .0

5-Methyl-3-heptanone (Ethyl amyl ketone) (CAS #541-85-5) RTECS MJ7350000

CH 3CH 2COCH 2CH(CH 3)CH 2CH 3; C 8H16O (122.22)

25

25

25 --

5.00

dP

Biu9q51

C

i°P V 72 la P .k0 2(m L2;2/8d )ggH .0

Methyl-(n-amyl)-ketone (2-Heptanone) (CAS #110-43-0) RTECS MJ5075000

CH 3CO(CH 2)4CH 3; C 7H14O (114.19)

100

100

50

4.67

dP

Biu1q51;C i°P V 7l2a P .k0 2(m L0;2/8d )ggH .0

Ethyl butyl ketone (3-heptanone) (CAS #106-35-4) RTECS MJ5250000

CH 3CH 2CO(CH 2)3CH 3; C 7H14O (114.19)

50

50

50

4.67

dP

Biu8 q41

C

i°P V 35 la P .k0 4(m L8;1/8d )ggH .0

• NOTE: All densities and vapor pressures are at 20 °C unless stated otherwise.

NIOSH Manual of Analytical Method (NMAM), Fourth Edition, 8/15/94