Ketones I (2555)
KETONES I
Formulas: See Table 1
MW: Table 1
METHOD: 2555, Issue 1
(1) (2) (3) (4) (5) (6) (7)
CAS: Table 1
PROPERTIES:
Issue 1: 15 March 2003 See Table 3
Acetone: dimethyl ketone, ketone propane, 2-propanone. Methyl ethyl ketone: methyl acetone, 2-butanone, MEK. 2-Pentanone: ethyl acetone, methyl propyl ketone, MPK. Methyl isobutyl ketone: hexone, 4-methyl-2-pentanone, MIBK. 2-Hexanone: methyl n-butyl ketone, methyl butyl ketone, MBK. Di-isobutyl ketone: sym-diisopropyl acetone, 2,6-dimethyl-4-heptanone, isovalerone, valerone, DIBK. Cyclohexanone: anone, cyclohexyl ketone, pimelic ketone.
SAMPLING SAMPLER:
RTECS: Table 1
EVALUATION: PARTIAL
OSHA : See Table 2 NIOSH: See Table 2 ACGIH: See Table 2 SYNONYMS:
2555
SOLID SORBENT TUBE (Anasorb CMS, 150 mg/75 mg)
MEASUREMENT TECHNIQUE:
GAS CHROMATOGRAPHY, FID
ANALYTE:
See Table 1
DESORPTION:
1 mL CS2 for 30 minutes
INJECTION VOLUME:
1 µL
250°C 300°C 40°C (1 min) to 200°C (8°C/min)
FLOW RATE: 0.01 to 0.2 L/min
VOL-MIN: -MAX:
Acetone 0.5 L 3.0 L
SHIPMENT:
Refrigerate samples.
Others 1L 10 L
SAMPLE STABILITY:
All analytes 30 days @ 5°C
TEMPERATURE -INJECTION: -DETECTOR: -COLUMN:
BLANKS:
2 to 10 field blanks per set.
CARRIER GAS:
Helium, 1mL/min
COLUMN:
Capillary, fused silica, 30 m x 0.53-mm ID, 3.00-µm film crossbonded® 35% diphenyl - 65% dimethyl polysiloxane
CALIBRATION:
Standard solutions of analytes in CS 2
RANGE:
See Table 4.
ACCURACY RANGE STUDIED:
Not studied.
BIAS:
Not determined.
OVERALL PRECISION ( Ö r T ):
Not determined.
ACCURACY:
Not determined.
ESTIMATED LOD: See Table 4. PRECISION ( þ r ):
See Table 4.
APPLICABILITY: For three-liter sample, the working range for acetone was 0.378 to 41.4 ppm (0.92 to 100.2 mg/m3 ). For a 10-L sample the working range for methyl ethyl ketone was 0.092 to 10.2 ppm (0.275 to 30.5 mg/m3 ), for 2-pentanone was 0.077 to 8.67 ppm (0.276 to 31.1 mg/m3 ), for methyl isobutyl ketone was 0.066 to 6.83 ppm (0.275 to 28.5 mg/m3 ), for 2hexanone was 0.066 to 7.45 ppm (0.275 to 31.1 mg/m3 ), for diisobutyl ketone was 0.052 to 5.07 ppm (0.308 to 30.1 mg/m3 ), and for cyclohexanone was 0.075 to 9.79 ppm (0.300 to 39.2 mg/m3 ). INTERFERENCES: Any compounds with similar retention times as the analytes of interest. Alternate columns include Rtx-1 and Rtx-5 or equivalent capillary columns. OTHER METHODS: This method was developed as part of an update for NMAM 1300, issue 2 (dated 15 August 1994) [1]. NMAM 1300, issue 2 was based on NIOSH Manual of Analytical Methods, 2nd edition methods S1, S18, S19, S20, S178, and S358. This method includes: lower LOD/LOQ values for each analyte, improved DE recovery results for each analyte (at lower levels), inclusion of methyl ethyl ketone and methyl isobutyl ketone in the method by the use of a different sorbent tube (Anasorb CMS), a 30-day storage stability study, and replacement of the packed column with a Rtx-35 fused silica capillary column.
NIOSH Manual of Analytical Methods (NMAM), Fourth Edition KET ON ES I: MET HO D 255 5, Issue 1, dated 15 M arch 200 3 - Page 2 o f 5 REAGENTS:
EQUIPMENT:
1. 2. 3. 4. 5. 6.
1. Sam pler: glass tube, 7 cm long, 6-mm OD, 4mm ID, flame-sealed ends with plastic caps, containing two sections of Anasorb CMS (150 m g/ 75 m g) separated b y a 2-mm urethane plug. A silylated glass wool plug precede s the front section and a 3-m m urethane foam plug follows the back section. Tu bes are c om m ercially available. 2. Personal sampling pump, 0.01 to 0.2 L/min, connected with flexible tubing. 3. Gas chromatograph equipped with FID, integrator and capillary colum n (page 25 55-1). 4. Autosampler vials, 2-mL, glass, with PTFElined crimp caps. 5. Syringes, 10-µL, 25-µL, and 1-mL. 6. Pipettes, 3-mL and 5-mL. 7. Volumetric flasks, 10-mL. 8. Bagge d refrigera nt, Blue -ice or equ ivalent.
Ca rbon disulfide (G C grade ).* Analytes, reage nt gra de.* Helium, prepurified and filtered. Hydrogen, prepurified and filtered. Air, compressed, purified, filtered. Ca libration s tock solution: Ad d know n am oun ts of analytes to carbon disulfide in 10-m L volum etric flas k.
- See SPECIAL PRECAUTIONS
SPECIAL PRECAUTIONS: Carbon disulfide is toxic, explosive, and a fire hazard (FP = -30°C). W ork with carbon disulfide in a well ventilated hood. Analytes should be handled in a fume hood. Use protective clothing and eyew ear.
SAMPLING: 1. Calibrate each personal sampling pump with a representative sampler in line. 2. Break the ends of the sampling tube imm ediately before sampling. Attach sampling tube to personal sampling pump with flexible tubing. 3. Sa m ple at an accu rately know n flow rate between 0.01 a nd 0.2 L/m in for a total sam ple size of 3 L for acetone and 10 L for all other analytes. 4. Ca p the sam plers with plastic (not rub ber) cap s and pa ck sec urely for shipm ent.
SAMPLE PREPARATION: 5. Place the front and back sorbent sections of the sampler tube in separate vials. Place the glass wool preceding the front section into the vial containing the front sorbent sec tion. Discard the urethane foam plugs. 6. Ad d 1.0 m L of carbon disulfide into each vial. Attach crim p caps to each vial. 7. Allow to stand fo r 30 m inutes with oc cas ional agitation.
CALIBRATION AND QUALITY CONTRO L: 8. Ca librate daily with at least six working s tandards from below the LOD to 10 times the LOQ . If nec ess ary, additional stand ards m ay be a dde d to exten d the calibra tion cu rve. a. Add known amounts of analytes to carbon disulfide solvent in a 10 -m L volum etric flas k and d ilute to the mark. Prepare additional standards by serial dilution in 10-mL volumetric flasks. b. Analyze together with samp les and blanks (steps 11 and 12). c. Prepare c alibration graph (pe ak area vs µg ana lyte). 9. Determine desorption efficiency (DE) at least once for each lot of Anasorb CMS used for sampling in the calibration ranges (step 8). a. Prepare three tubes at each of five levels plus three media blanks.
NIOSH Manual of Analytical Methods (NMAM), Fourth Edition KET ON ES I: MET HO D 255 5, Issue 1, dated 15 M arch 200 3 - Page 3 o f 5 b. Inject a known amount (5 to 25 µL) of DE stock solution directly onto the front sorbent section of each Anasorb CMS tube with a microliter syringe. c. Allow the tub es to air equ ilibrate for several m inutes , then cap the ends of ea ch tube a nd a llow 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 vs µg analyte recovered. 10. Analyze a minimum of three quality control blind spikes and three analyst spikes to ensure that the calibra tion gra ph and D E graph are in control.
MEASUREMENT: 11. Set gas chrom ato graph acc ording to m anufacturer’s recomm endations and to conditions given on page 2555-1. Inje ct a 1-µ L sam ple aliquot m anually using the solvent flush technique or with an autosam pler. NOTE: If peak a rea is above the linear range of the working standard s, dilute w ith solve nt, reanalyze and app ly the app ropriate dilution facto r in the c alculations. 12. Measure peak areas.
CALCULATIONS: 13. De termine the m ass, µg (co rrected for DE ), of analyte 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) sorbent sections. NOTE: 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):
NOTE: :g/L = m g/m 3
EVALUATION OF METHOD: This method development was based upon a prioritized list of problematic gas chromatographic methods identified in a survey of external users of the NIOS H M anu al of Analytical M ethods. M etho d im prov em ents include the use of capillary column chromatography, lower LOD/LOQ values, improved desorption efficiency (DE) at lower quantitative levels, and a storage stability study conducted at 7, 14, and 30 days. The method also incorporate s the use of a n im proved solid sorbent tu be sam pler (A nasorb CM S) res ulting in improved sample recovery and allowing methyl ethyl ketone and methyl isobutyl ketone to be included in the m ethod without loss of sample recovered from the sorbent tube. Table 4 lists the method evaluation data, the LOD/LOQ values, the range of measurements, and the precisions for each analyte. [2] The average D E dete rm ined fo r ac eto ne was 98.2% (RSD = 0.01 9), for m eth yl ethyl ketone was 98.6% (RSD = 0.017), for 2-pentanone was 99.3% (RSD = 0.01 1), for m eth yl isobutyl ketone w as 96.4% (RSD = 0.011), for 2-hexanone was 100.6% (RSD = 0.013), for diisobutyl ketone was 102.4% (RSD = 0.013), and for cycloh exa non e wa s 95 .4% (RS D = 0.015). The average 30-day storage stability recovery for acetone was 100.7% (RSD = 0.017), for methyl ethyl ketone was 101.7% (RSD = 0.018), for 2-pentanone was 10 1.5% (R SD = 0.028), for methyl isobutyl ketone was 103.8% (RSD = 0.018), for 2-hexanone was 101.4% (RSD = 0.029), for diisobutyl ketone was 103.5% (RSD = 0.019), a nd fo r cycloh exa non e wa s 87 .4% (RS D = 0.009).
NIOSH Manual of Analytical Methods (NMAM), Fourth Edition KET ON ES I: MET HO D 255 5, Issue 1, dated 15 M arch 200 3 - Page 4 o f 5 REFERENCES: [1] [2]
NIO SH Ma nua l of Analytical Metho ds, 4 th ed., V. 2, U .S. De pt. o f Health and Hu m an Servic es, Pu bl. (NIO SH ) 94-113 (199 4). Pendergrass SM [1998]. Backup data for Ketones I, NIOSH M ethod 2555, Issue 1. Cincinnati, Oh: Department of Health and Human Services, Public Health Service, Centers for Disease Control and Prevention, National Institute for Occ upational Safety and Health, (unpublished, Februa ry).
METHOD WRITTEN BY: Stephanie M. Pendergrass, NIOSH/DART
TABLE 1. GENERAL INFORMATION Analyte
Fo rm ula
MW
CAS #
RTECS #
Acetone
(CH 3) 2CO
58.1
67-64-1
AL3150000
MEK
CH 3COCH 2CH 3
72.1
78-93-3
EL6475000
2-Pentanone
CH 3CO(CH 2) 2CH 3
86.1
107-87-9
SA7875000
MIBK
CH 3COCH 2CH(CH 3) 2
100 .2
108-10-1
SA9275000
2-Hexanone
CH 3CO(CH 2) 3CH 3
100 .2
591-78-6
MP1400000
Diisobutyl ketone
[(CH 3) 2CHCH 2]2CO
142 .3
108-83-8
MJ5775000
Cyclohexanone
C 6H 10O
98.2
108-94-1
GW 1050000
TABLE 2. ANALYTE EXPOSURE LIMITS Analyte
OSHA PEL (ppm )
NIOSH REL (ppm )
ACGIH TLV (ppm )
1000
250
500
1 pp m = 2.42 m g/m 3
MEK
200
200
200
1 pp m = 3.00 m g/m 3
2-Pentanone
200
150
200
1 pp m = 3.58 m g/m 3
MIBK
100
50
50
1 pp m = 4.17 m g/m 3
2-Hexanone
100
1
5
1 pp m = 4.17 m g/m 3
Diisobutyl ketone
50
25
25
1 pp m = 5.92 m g/m 3
Cyclohexanone
50
25
25 (A3 - unclassified carcinogen)
1 pp m = 4.00 m g/m 3
Acetone
NIOSH Manual of Analytical Methods (NMAM), Fourth Edition
Conversion ppm to m g/m 3 KET ON ES I: MET HO D 255 5, Issue 1, dated 15 M arch 200 3 - Page 5 o f 5
TABLE 3. PHYSICAL PROPERTIES. State
Den sity @ 20 oC (g/mL)
BP ( oC)
Vap or Pre ssu re (@ 20 oC) kPa(mm Hg)
Acetone
liquid
0.7915
56.2
35.5 (266)
MEK
liquid
0.8050
79.6
13.0 (100)
2-Pentanone
liquid
0.8120
101 .7
3.6 (27)
MIBK
liquid
0.8042
115 .8
2.0 (15)
2-Hexanone
liquid
0.8120
127 .2
0.4 (3)
Diisobutyl ketone
liquid
0.8089
168 .2
0.23 (1.7)
Cyclohexanone
liquid
0.9470
156 .7
0.3 (2)
Analyte
TABLE 4. METHOD EVALUATION Analyte
LOD (µg/sample)
LOQ (µg/sample)
Range (µg/sample)
Precision (S r)
Acetone
0.9
2.7
2.7 - 295.0
0.021
Methyl Ethyl Ketone
0.9
2.7
2.7 - 300.0
0.008
2-Pentanone
0.9
2.7
2.7 - 305.0
0.009
Methyl Isobutyl Ketone
0.9
2.7
2.7 - 280.0
0.013
2-Hexanone
0.9
2.7
2.7 - 305.0
0.010
Diisobutyl Ketone
1.0
3.0
3.0 - 295.0
0.010
Cyclohexanone
1.0
3.0
3.0 - 273.0
0.006
NIOSH Manual of Analytical Methods (NMAM), Fourth Edition