KETONES II 1301

TABLE 1 MW: TABLE 1 CAS: Table 1 RTECS: Table 1

METHOD: 1301, Issue 2 EVALUATION: FULL Issue 1: 15 February 1984

COMPOUNDS (3) and (5): PARTIAL Issue 2: 15 August 1994

OSHA/NIOSH/ACGIH: Table 1 PROPERTIES: Table 1

COMPOUNDS: (1) camphor (3) 5-methyl-3-heptanone (5) ethyl butyl ketone

(Synonyms (2) mesityl oxide (4) methyl-(n-amyl)-ketone
in Table 1)

SAMPLING MEASUREMENT

SAMPLER: SOLID SORBENT TUBE TECHNIQUE: GAS CHROMATOGRAPHY, FID

(coconut shell charcoal, 100 mg/50 mg)
ANALYTE: compounds above
FLOW RATE: 0.01 to 0.2 L/min
DESORPTION: 1 mL 1% methanol in CS 2; stand in 30
VOL-MIN: 1L min
-MAX: 25 L
INJECTION VOLUME: 5 µL
SHIPMENT: routine
COLUMN: stainless steel (3 m x 3-mm ID), 10%
SAMPLE FFAP on 80/100 Chromosorb W-AW
STABILITY: unknown
TEMPERATURE-INJECTOR: 200 °C
FIELD BLANKS: 2 to 10 field blanks per set -DETECTOR: 300 °C
-COLUMN: 100 to 200 °C
@ 10 °C/min

CARRIER GAS: N 2 or He, 30 mL/min

ACCURACY
CALIBRATION: standard solutions of analyte in elution
RANGE STUDIED: see EVALUATION OF METHOD solvent

BIAS: see EVALUATION OF METHOD RANGE AND PRECISION: see EVALUATION OF METHOD

OVERALL PRECISION (ŜrT): see EVALUATION OF ESTIMATED LOD: 0.05 mg per sample
METHOD

ACCURACY: 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: EQUIPMENT:

1. Eluent: Carbon disulfide* (chromatographic 1. Sampler: glass tube, 7 cm long, 6-mm OD,
grade) with 1% (v/v) methanol 4-mm ID, flame-sealed ends, containing two
(chromatographic grade). sections of 20/40 mesh activated (600 °C)
2. Analytes, reagent grade. coconut shell charcoal (front = 100 mg; back
3. Nitrogen, prepurified. = 50 mg) separated by a 2-mm urethane foam
4. Hydrogen, dry. plug. A silylated glass wool plug precedes the
5. Air, filtered. 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
* See SPECIAL PRECAUTIONS. 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. Calibrate each personal sampling pump with a representative sampler in line.

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

SAMPLE PREPARATION:

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

CALIBRATION AND QUALITY CONTROL:

8. 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).
9. Determine desorption efficiency (DE) at least once for each batch of charcoal used for sampling
in the calibration range (step 8). Prepare three tubes at each of five levels plus three media
blanks.

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.
10. Analyze three quality control blind spikes and three analyst spikes to insure that the calibration
graph and DE graph are in control.

MEASUREMENT:

11. Set gas chromatograph according to manufacturer's recommendations and to conditions given
on page 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.
12. Measure peak area.

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.
14. Calculate concentration, C, of analyte in the air volume sampled, V (L):

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
Range Overall
Method (mg per Range Precision Bias Accuracy
Compound [1,2] sample) DE 2- Sr (mg/m 3) (L) ŜrT (%) (±%)

Camphor S10 0.02 to 0.40 0.97 0.018 6 to 25 >48 0.074 0.9 10.5

Mesityl oxide S12 0.10 to 3.0 0.81 0.014 45 to 210 >48 0.071 7.0 22.8

5-Methyl-3-heptanone S13 0.15 to 4.0 0.90 0.014 60 to 270 >36 0.10 13.1 31.0

Methyl-(n-amyl)-ketone S15 0.5 to 10.0 0.82 0.012 200 to 925 >36 0.066 4.9 15.0

Ethyl butyl ketone S16 0.25 to 7.0 0.94 0.022 100 to 460 >24 0.086 -3.1 26.3
1
5% breakthrough, 0.2 L/min at high end of concentration range in dry air.
2
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) ACGIH
CAS Formula TLV mg/m 3/ppm
RTECS (M.W.) OSHA NIOSH STEL @NTP

Camphor C10H16O 2 2 2 6.22 ;d2

d9
im
9Ll/.o
g
0s@ C;° 52
(CAS #76-22-2) (152.24) 3 ;C4°M
P2
V
0
8aP
14k7
.1
0
.0
RTECS EX1225000 mmm H
;m
g/g0741

Mesityl oxide CH 3COCH=C(CH 3)2; C 6H10O 25 10 15 4.01 ;dP

Biu
9q
21
;Ci°P
V1l .aP
1k
(4-methyl-3-penten-2-one) (98.15) 25 8(m L2;2/8d
)ggH
.0
(CAS #141-79-7)
RTECS SB4200000

5-Methyl-3-heptanone CH 3CH 2COCH 2CH(CH 3)- 25 25 25 5.00 ;dP

Biu9q51
;C
i°P
V
72
laP.k0
(Ethyl amyl ketone) CH 2CH 3; C 8H16O -- 2(m L2;2/8d
)ggH
.0
(CAS #541-85-5) (122.22)
RTECS MJ7350000

Methyl-(n-amyl)-ketone CH 3CO(CH 2)4CH 3; C 7H14O 100 100 50 4.67 ;dP

Biu1q51;C
i°P
V
7l2aP.k0
(2-Heptanone) (114.19) 2(m L0;2/8d
)ggH
.0
(CAS #110-43-0)
RTECS MJ5075000

Ethyl butyl ketone CH 3CH 2CO(CH 2)3CH 3; C 7H14O 50 50 50 4.67 ;dP

Biu8
q41
;C
i°P
V
35
laP.k0
(3-heptanone) (114.19) 4(m L8;1/8d
)ggH
.0
(CAS #106-35-4)
RTECS MJ5250000

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

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