Ketones I (1300)
KETONES I
TABLE 1
MW: TABLE 1
METHOD: 1300, Issue 2
1300
CAS: TABLE 1
EVALUATION: FULL
OSHA/NIOSH/ACGIH: Table 1
COMPOUNDS: (SYNONYMS: Table 1)
Issue 1: 15 May 1989 Issue 2: 15 August 1994
PROPERTIES: Table 1
acetone cyclohexanone diisobutyl ketone
2-hexanone methyl isobutyl ketone 2-pentanone
SAMPLING SAMPLER:
RTECS: TABLE 1
MEASUREMENT
SOLID SORBENT TUBE (coconut shell charcoal, 100 mg/50 mg)
FLOW RATE:
0.01 to 0.2 L/min
VOL-MIN: -MAX:
acetone 0.5 L 3L
SHIPMENT:
MIBK must be refrigerated [1]
SAMPLE STABILITY:
unknown
FIELD BLANKS:
2 to 10 field blanks per set
others 1L 10 L
TECHNIQUE:
GAS CHROMATOGRAPHY, FID
ANALYTE:
compounds above
DESORPTION:
1 mL CS 2; stand 30 min
INJECTION VOLUME:
5 µL
TEMPERATURE-INJECTOR: -DETECTOR: -COLUMN:
250 °C 300 °C 50 °C to 170 °C @ 10°/min
CARRIER GAS:
N 2 or He, 30 mL/min
COLUMN:
glass (3.5 m x 6-mm ID), packed with 10% SP2100 0.1% Carbowax 1500 on Chromosorb WHP
ACCURACY CALIBRATION: ˆ rT), RANGE STUDIED, BIAS, OVERALL PRECISION (S and ACCURACY
standard solutions of analyte in CS 2
RANGE:
0.06 to 10 mg per sample [2]
see EVALUATION OF METHOD
ESTIMATED LOD: 0.02 mg per sample PRECISION (Sr):
see EVALUATION OF METHOD
APPLICABILITY: This is intended as a general method for the ketones listed above. If only certain compounds are of interest, the instrumental conditions can be changed to maximize instrument response for these compounds.
INTERFERENCES: None reported. Alternate columns, e.g., 10% SP-2100 or DB-1 fused silica capillary, can be used.
OTHER METHODS: This method combines and replaces Methods S1, S18, S19 and S20 [3], S178 and S358 [4], and 1300 (dated 2/15/84).
NIOSH Manual of Analytical Methods (NMAM), Fourth Edition, 8/15/94 KETONES I: METHOD 1300, Issue 2, dated 15 August 1994 - Page 2 of 5 REAGENTS: 1. 2. 3. 4. 5.
EQUIPMENT:
Carbon disulfide (CS 2) GC grade.* Analytes, reagent grade. Nitrogen, prepurified. Hydrogen, dry. Air, filtered, dry.
See SPECIAL PRECAUTIONS.
1. Sampler: glass tube, 7 cm long, 6-mm OD, 4mm ID, flame-sealed ends with plastic caps, containing two sections of 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 at 1 L/min must be less than 3.4 kPa. Tubes are commercially available. 2. Personal sampling pump, 0.01 to 0.2 L/min, with flexible connecting tubing. 3. Gas chromatograph equipped with FID, integrator and column (page 1300-1). 4. Vials, 2-mL, glass, PTFE-lined crimp caps. 5. Syringe, 10-µL, readable to 0.1 µL. 6. Pipet, TD, 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); work with it only in a 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 0.5 to 3 L for acetone or 1 to 10 L for the other analytes. Cap the samplers 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 CS 2 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 six working standards over the range 0.02 to 10 mg analyte per sample. a. Add known amounts of analyte to CS 2 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 lot of charcoal used for sampling in the calibration range (step 8). Prepare three tubes at each of five levels plus three media blanks. a. Remove and discard back sorbent section of a media blank sampler. b. Inject a known amount of analyte or of a standard solution of analyte in CS 2 directly onto NIOSH Manual of Analytical Methods (NMAM), Fourth Edition, 8/15/94 KETONES I: METHOD 1300, Issue 2, dated 15 August 1994 - Page 3 of 5
10.
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.
MEASUREMENT: 11.
12.
Set gas chromatograph according to manufacturer's recommendations and to conditions given on page 1300-1. 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.
CALCULATIONS: 13.
14.
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):
EVALUATION OF METHOD: The methods on which this method was based were validated under NIOSH Contract CDC-99-74-45 [5]. Desorption efficiency was checked by spiking known amounts of the compounds (either neat or in solutions with CS 2) on coconut shell charcoal. Samples were generated for acetone, cyclohexanone, 2-pentanone, and methyl isobutyl ketone by heating a quantity of the liquid to just below its boiling point in a 3-necked, 500-mL round bottom flask. The compound was carried through a fixed-temperature condenser to the concentrations. Samples were generated for diisobutyl ketone and 2-hexanone using a syringe pump which delivered the compounds to a heated glass-lined inlet which was swept with nitrogen, carrying the vapor to the mixing chamber. Low-level desorption efficiency checks showed the DEs to be 70% and 76% for 0.024 and 0.096 mg/sample respectively for cyclohexanone and 87% for 0.052 mg/sample of MIBK [2]. Results of the evaluation experiments are given below.
NIOSH Manual of Analytical Methods (NMAM), Fourth Edition, 8/15/94 KETONES I: METHOD 1300, Issue 2, dated 15 August 1994 - Page 4 of 5
Compound
Method [2-5]
Acetone
S1, 127
Cyclohexanone
S19
Diisobutyl ketone
Range, mg/m 3 Overall Precision (SˆrT)
Breakthrough 1 (L)
Measurement Range, mg/sample (Sr) DE 2
1200 to 4500 (0.082)
4.3
2.4 to 14.2 (0.024)
0.86
98 to 392 (0.062)
65
3.8 to 18.0 (0.025)
0.82
S358
145 to 582 (0.070)
44
1.8 to 7.0 (0.032)
0.97
2-Hexanone
S178
188 to 790 (0.053)
>45
1.5 to 8.1 (0.018)
0.81
MIBK
S18
208 to 836 (0.064)
17
2.1 to 8.3 (0.008)
0.91
2-Pentanone
S20
395 to 1570 19 3.5 to 14.0 0.90 (0.063) (0.011) ____________________________________________________________________________________ ____ 1 5% breakthrough, 0.2 L/min at high end of concentration range in dry air. 2 Averaged over mass range shown.
REFERENCES: [1] UBTL Report, Sequence #5528-J (NIOSH, unpublished, Oct. 2, 1986). [2] Williams, Karen, Desorption Efficiency Determination for Cyclohexanone and Methyl Isobutyl Ketone, NIOSH/MRSB, Unpublished (1986). [3] NIOSH Manual of Analytical Methods, 2nd. ed., V. 2, S1, S18, S19 and S20, U.S. Department of Health, Education, and Welfare, Publ. (NIOSH) 77-157-B (1977). [4] Ibid, V. 3, S178 and S358, U.S. Department of Health, Education, and Welfare, Publ. (NIOSH) 77-157-C (1977). [5] Documentation of the NIOSH Validation Tests, U.S. Department of Health, Education, and Welfare, Publ. (NIOSH) 77-185 (1977), available as Stock No. PB 274-248 from NTIS, Springfield, VA 22161. [6] NIOSH Manual of Analytical Methods, 2nd. ed., V. 1, P&CAM 127, U.S. Department of Health, Education, and Welfare, Publ. (NIOSH) 77-157-A (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 I: METHOD 1300, Issue 2, dated 15 August 1994 - Page 5 of 5 Table 1. General Information Exposure Limits, ppm OSHA NIOSH ACGIH
mg/m 3/ ppm @ NTP
Compound (Synonyms)
Formula (M.W.)
Acetone 2-Propanone; (CAS #67-64-1) RTECS AL3150000
CH 3COCH 3 (58.08)
liquid; BP 56 °C; 750; STEL 1000 d 0.791 g/mL; 250: Group III Pesticide VP 35.5 kPa (266 mm Hg) 750; STEL 1000
2.37
Cyclohexanone Cyclohexyl ketone (CAS #108-94-1) RTECS GW1050000
C 6H 10O (98.15)
liquid; BP 155 °C; d 0.947 g/mL; VP 0.3 kPa (2 mm Hg)
4.01
Diisobutyl ketone (2.6,-dimethyl4-heptanone; CAS #108-83-8) RTECS MJ5775000
((CH 3)2CHCH 2)2CO liquid; BP 169 °C; 25 (142.24) d 0.847 g/mL; 25; Group II Pesticide VP 0.23 kPa (1.7 mm Hg) 25
2-Hexanone (methyl n-butyl ketone; MBK; CAS #591-78-6) RTECS MP1400000
CH 3(CH 2)3COCH 3 (100.16)
Methyl isobutyl ketone (MIBK; hexone; isopropyl acetone; 4-methyl2-pentanone; CAS #108-10-1) RTECS SA9275000
(CH 3)2CHCH 2COCH 3 (100.16)
Properties*
liquid; BP 127 °C; d 0.812 g/mL; VP 0.4 kPa (3 mm Hg)
25 (skin) 25 (skin); Group III Pesticide 25 (skin)
100
5.82
4.09
1 5
liquid; BP 117 °C; 50; STEL 75 d 0.800 g/mL; 50; STEL 75 VP 2.0 kPa (15 mm Hg) 50; STEL 75
4.09
2-Pentanone CH 3CH 2CH 2COCH 3 liquid; BP 100 °C; 200; STEL 250 3.52 (methyl propyl ketone: (86.13) d 0.812 g/mL; 150 CAS #107-87-9) VP 3.6 kPa (27 mm Hg) 200; STEL 250 RTECS SA 7875000 _________________________________________________________________________________________________________ ___
- Density @ 25 °C; VP @ 20 °C.
NIOSH Manual of Analytical Methods (NMAM), Fourth Edition, 8/15/94