Ketones II (2553)
KETONES II FORMULAS: TABLE 1
MW: TABLE 1
METHOD: 2553, Issue 1
CAS: TABLE 1
EVALUATION: PARTIAL
PROPERTIES:
OSHA : Table 1 NIOSH: Table 1 ACGIH: Table 1
COMPOUNDS/ SYNONYMS:
2553
(1) 2-Heptanone: Methyl-n-amyl ketone (2) 3-Heptanone: Ethyl butyl ketone (3) Mesityl oxide: 4-Methyl-3-penten-2-one
SOLID SORBENT TUBE (Anasorb CMS, 150/75 mg) [1]
FLOW RATE:
0.01 to 0.2 L/min
VOL-MIN: -MAX:
1L 25 L
SHIPMENT:
Routine
SAMPLE STABILITY:
30 days @ 5°C [1]
BLANKS:
10% of samples ACCURACY
RANGE STUDIED:
Not Determined.
BIAS:
Not Determined.
OVERALL PRECISION ( Ö r T ):
Not Determined.
ACCURACY:
Not Determined.
Issue 1: 15 March 2003
Table 1
(4) 5-Methyl-3-heptanone: Ethyl amyl ketone (5) Camphor: 2-Camphanone, Gum Camphor
SAMPLING SAMPLER:
RTECS: TABLE 1
MEASUREMENT TECHNIQUE:
GAS CHROMATOGRAPHY, FID
ANALYTE:
Table 1
DESORPTION:
1 mL of 2% isopropanol in CS 2 with agitation [1]
INJECTION VOLUME:
1 µL
TEMPERATURE -INJECTION: -DETECTOR: -COLUMN:
225°C [1] 300°C [1] 55°C (3 min hold) to 190°C (8°C/min) [1]
CARRIER GAS:
Helium (4.8 mL/min) [1]
COLUMN:
Capillary, fused silica, 30-m x 0.32-mm ID; 1.00 µm film crossbond trifluoropropylmethyl polysiloxane or equivalent [1]
CALIBRATION:
Solutions of analytes in desorption solvent
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 3heptanone 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-3heptanone 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.
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 2 o f 4 REAGENTS:
EQUIPMENT:
1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11.
1. Sam pler: glass tube, 7 cm long, 6-mm OD, 4mm ID, flame-sealed ends, containing two sec tions o f Anaso rb C MS (front = 150 m g; back = 75 mg) separated by a 2-mm urethane plug. A silylated glass wool plug precedes the front section and a 3-mm urethane plug follows the back se ction. Tubes are com m ercially available (S KC # 226-12 1). 2. Personal sa m pling pum p, 0.01 to 0.2 L/m in, with flexible connecting tubing. 3. Gas chromatograph, FID, integrator, and Rtx200 fused silica capillary column. 4. GC autosam pler vials, 2-m L glass, with PTF Elined crimp caps. 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.
2-Hep tanone, reagen t grade (98% ). 3-Hep tanone, reagen t grade (98% ). Mes ityl oxide, reagent grade (98% ). 5-Methyl-3-heptanone , reagent grade (97% ). Cam phor, reagent grade (99% ). Ca rbon disulfide, low b enze ne g rade .* Iso propanol. Helium, prepurified and filtered. Hydrogen, prepurified and filtered. Air, compressed and filtered. Desorption solvent: 2% isopropanol in carbon disulfide (v/v). 12. DE s tock solution: Add kn own am ount of analyte to desorption solvent in 10-m L volumetric flask.
- 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. 2. 3. 4.
Calibrate each personal sampling pump with a representative sampler in line. Break the ends of the sampler imm ediately prior to sampling. Attach sampler to personal sampling pump with flexible tubing. 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. Ca p the sam plers and pac k secu rely for shipm ent.
SAMPLE PREPARATION: 5. 6. 7.
Place the front (include the initial glass wool plug) and back sorbent sections of the sampler in separate vials. Discard the foam plugs. Add 1.0 mL of the 2% isopropanol/carbon disulfide desorption solvent to each vial. Securely attach crim p caps to each vial. Allow to desorb for 30 m inutes with oc cas ional agitation.
CALIBRATION AND QUALITY CONTRO L: 8.
9.
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). 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 KET ON ES II: MET HO D 255 3, Issue 1, dated 15 M arch 200 3 - Page 3 o f 4
10.
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. 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.
12.
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. Measure peak areas.
CALCULATIONS: 13.
14.
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. 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] [2]
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. 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]
[4]
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. 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/ (Synonyms) CAS # RTECS
Fo rm ula (M .W .)
mg/m 3= 1 ppm
Expo sure Lim its NIOSH REL (ppm)
OSHA PEL (ppm)
ACGIH TLV (ppm)
@ NTP
Properties
Methyl-n-amyl-ketone (2-Heptanone) (CAS # 110-43-0) RTECS MJ5075000
C7 H1 4 O (114.19)
100
100
50
4.67
liquid; d 0.820 g/mL; BP 151 o C; VP 0.27 kPa (2 mm Hg)
Ethyl butyl ketone (3-Heptanone) (CAS # 106-35-4) RTECS MJ5250000
C7 H1 4 O (114.19)
50
50
50
4.67
liquid; d 0.818 g/mL; BP 148 o C; VP 0.53 kPa (4 mm Hg)
Mesityl oxide (4-methyl-3-penten-2-one) (CAS # 141-79-7) RTECS SB4200000
C6 H1 0 O (98.15)
10
25
15
4.01
liquid; d 0.822 g/mL; BP 129 o C; VP 1.1 kPa (8 mm Hg)
5-Methyl-3-heptanone (Ethyl amyl ketone) (CAS # 541-85-5) RTECS MJ7350000
C8 H1 6 O (128.21)
25
25
25
5.00
liquid; d 0.822 g/mL; BP 159 o C; VP 0.27 kPa (2 mm Hg)
Camphor (CAS # 76-22-2) RTECS EX1225000
C1 0 H1 6 O (152.24)
2
2
2
6.22
solid; spec. gr. 0.992 @ 25 o C; MP 174 o C; 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 (µg)
Precision (S r)
Range (µg)
DE (Avg)
Storag e Stability (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