Industrial Hygiene

NIOSH Manual of Analytical Methods (NMAM), Fourth Edition

KETONES II 2553

FORMULAS: TABLE 1 MW: TABLE 1 CAS: TABLE 1 RTECS: TABLE 1

METHOD: 2553, Issue 1 EVALUATION: PARTIAL Issue 1: 15 March 2003

OSHA : Table 1 NIOSH: Table 1 ACGIH: Table 1

PROPERTIES: Table 1

COMPOUNDS/ (1) 2-Heptanone: Methyl-n-amyl ketone (4) 5-Methyl-3-heptanone: Ethyl amyl ketone SYNONYMS: (2) 3-Heptanone: Ethyl butyl ketone (5) Camphor: 2-Camphanone, Gum Camphor

(3) Mesityl oxide: 4-Methyl-3-penten-2-one

SAMPLING MEASUREMENT

SAMPLER: SOLID SORBENT TUBE (Anasorb CMS, 150/75 mg) [1]

FLOW RATE: 0.01 to 0.2 L/min

VOL-MIN: 1 L -MAX: 25 L

SHIPMENT: Routine

SAMPLE STABILITY: 30 days @ 5°C [1]

BLANKS: 10% of samples

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: 225°C [1] -DETECTOR: 300°C [1] -COLUMN: 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 trifluoro- propylmethyl 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]

ACCURACY

RANGE STUDIED: Not Determined.

BIAS: Not Determined.

OVERALL PRECISION (Ör T): Not Determined.

ACCURACY: Not Determined.

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 3- heptanone 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-3- heptanone 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 2n d 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.

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NIOSH Manual of Analytical Methods (NMAM), Fourth Edition

REAGENTS:

1. 2-Hep tanone, reagen t grade (98% ).

2. 3-Hep tanone, reagen t grade (98% ).

3. Mes ityl oxide, reagent grade (98% ).

4. 5-Methyl-3-heptanone , reagent grade (97% ).

5. Cam phor, reagent grade (99% ).

6. Ca rbon disulfid e, low b enze ne g rade .*

7. Iso prop an ol.

8. Helium, prepurified and filtered.

9. Hydrogen, prepurified and filtered.

10. Air, compressed and filtered.

11. 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

E Q U IP M E N T :

1. Sam pler: glass tube, 7 cm long, 6-mm OD, 4-

mm ID, flame-sealed ends, containing two

sec tions o f An aso rb C MS (fron t = 15 0 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 erc ially available (S KC # 22 6-12 1).

2. Pe rso nal sa m pling p um p, 0.0 1 to 0 .2 L/m in,

with flexible connecting tubing.

3. Gas chromatograph, FID, integrator, and Rtx-

200 fused silica capillary column.

4. GC autosam pler vials, 2-m L glass, with PTF E-

lined 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.

SPECIAL PRECAUTIONS: Ca rbon disulfid e is tox ic and a fire/e xplo sion haza rd (flas h po int = -30 °C) .

Isop ropa nol is flam m able . All work sho uld be perf orm ed in a ven tilated fu m e ho od.

S AM P L IN G :

1. Calibrate each personal sampling pump with a representative sampler in line.

2. Break the ends of the sampler imm ediately prior to sampling. Attach sampler to personal sampling

pump with flexible tubing.

3. 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.

4. Ca p the sam plers and pac k s ecu rely for s hipm ent.

SAMPLE PREPARATION:

5. Place the front (include the initial glass wool plug) and back sorbent sections of the sampler in

separate vials. Discard the foam plugs.

6. Add 1.0 mL of the 2% isopropanol/carbon disulfide desorption solvent to each vial. Securely attach

crim p c ap s to ea ch vial.

7. Allow to de sor b for 30 m inutes with oc cas iona l agitation .

CALIBRATION AND QUALITY CONTRO L:

8. Ca librate d aily with at leas t six wo rkin g sta nda rds to co ver th e an alytical ran ge. If n ece 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

an d d ilute to th e m ark. Mix w ell.

b. Analyze together with samp les and blanks (steps 11 and 12).

c. Prepare c alibration graph (pe ak area versus µg analyte).

9. Determine desorption efficiency (DE) at least once for each lot of Anasorb CMS used for sampling in

the c alibration rang e (ste p 8).

a. Prepare three tubes at each of five levels plus three media blanks.

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NIOSH Manual of Analytical Methods (NMAM), Fourth Edition

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 ov ernig ht.

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.

10. Analyze three quality control blind spikes and three analyst spikes to ensure that the calibration

grap h a nd DE gra ph are in c on tro l.

M E A SU R E M E N T :

11. 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 a rea is abo ve the linear ra nge of the wor king stan dard s, dilute w ith solve nt,

reanalyze and apply the appropriate dilution factor in the calculations.

12. Measure peak areas.

CALCULATIONS:

13. 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 (Bb) sor ben t sec tions.

NO TE: 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):

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

13 01 . The averag e D E rec ov ery wa s im prov ed for all ana lytes at le ve ls lo we r than tho se 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] Pe nde rgra ss S M [1 999 ]. Keto nes II Me thod De velop m ent B ack up D ata R epo rt, unp ublish ed d ata,

N IO S H /D A R T .

[2] NIOS H [1994]. Ketones II: Method 1301. In: Eller PM , Cassinelli ME, eds. NIOS H M anual of

An alytical M etho ds, 4 th

ed. C incinn ati, OH : Na tional Ins titute for O ccu pation al Sa fety an d H ealth,

DHHS (NIOSH) Publication No. 94-113.

KET ON ES II: MET HO D 255 3, Issue 1, dated 15 M arch 200 3 - Page 4 o f 4

NIOSH Manual of Analytical Methods (NMAM), Fourth Edition

[3] NIO SH [197 7]. M etho ds S 10, S 12, S 13, S 15, a nd S 16. N IOS H M anu al of A nalytical 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.

[4] NIO SH [197 7]. 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

T AB L E 1 . G E NE R AL IN F O RM A T IO N

Compound/

(Synonyms)

CAS #

RTECS

Fo rm ula

(M .W .)

Expo sure Lim its m g/m 3 =

1 ppm

@ NTP

Properties

NIOSH REL (ppm)

OSHA PEL (ppm)

ACGIH TLV (ppm)

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

C 7 H

1 4 O

(114.19) 100 100 50 4.67 liquid; d 0.820 g/mL;

BP 151 oC; VP 0.27 kPa (2 mm Hg)

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

C 7 H

1 4 O

(114.19) 50 50 50 4.67 liquid; d 0.818 g/mL;

BP 148 oC; VP 0.53 kPa (4 mm Hg)

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

C6H1 0O (98.15)

10 25 15 4.01 liquid; d 0.822 g/mL; BP 129 oC; VP 1.1 kPa (8 mm Hg)

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

C8H1 6O (128.21)

25 25 25 5.00 liquid; d 0.822 g/mL; BP 159 oC; VP 0.27 kPa (2 mm Hg)

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

C 1 0

H 1 6

O (152.24)

2 2 2 6.22 solid; spec. gr. 0.992 @ 25 oC; MP 174 oC; 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.

T A BL E 2. AN AL Y T IC AL R E SU L T S [1]

Analyte L O D

(µg)

Precision

(Sr)

Range

(µg)

DE (Avg) Storag e Stability

(at 5 o C 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