ACETONITRILE 1606

CH3CN MW: 41.06 CAS: 75-05-8 RTECS: AL7700000

METHOD: 1606, Issue 3 EVALUATION: FULL Issue 1: 15 February 1984

Issue 3: 15 January 1998

OSHA : 40 ppm PROPERTIES: liquid; d 0.783 g/mL @ 20 C; BP 82 C;

NIOSH: 20 ppm VP 12 kPa ( 89 mm Hg) @ 25 C, explosive
ACGIH: 40 ppm; STEL 60 ppm range 4.4 to 16% v/v in air
(1 ppm = 1.68 mg/m3 @ NTP)

SYNONYMS: methyl cyanide, cyanomethane, ACN.

SAMPLING MEASUREMENT

SAMPLER: SOLID SORBENT TUBE TECHNIQUE: GAS CHROMATOGRAPHY, FID

(coconut shell charcoal, 400/200 mg)
ANALYTE: acetonitrile

FLOW RATE: 0.01 to 0.2 L/min DESORPTION: 2 mL methylene chloride/methanol (85:15);

ultrasonic bath for 45 minutes.
VOL-MIN: 1 L @ 40 ppm
-MAX: 25 L INJECTION
VOLUME: 1 µL

SHIPMENT: keep cold; pack securely for shipment. TEMPERATURE-INJECTION: 250 C

-DETECTOR: 300 C
SAMPLE -COLUMN: 35 C, hold 4 min; 12 C/min to
STABILITY: at least 30 days at 5 C 150 C

BLANKS: 2 to 10 field blanks per set CARRIER GAS: He, 2.4 mL/min

COLUMN: capillary, fused silica, 30 m x 0.32-mm ID, 1-

ACCURACY µm film, crossbonded PEG, Stabilwax® or
equivalent
RANGE STUDIED: 39.2 to 275 mg/m3 [1]
CALIBRATION: solutions of acetonitrile in methylene
BIAS: 4.0% chloride/methanol (85:15)

OVERALL PRECISION ( ): 0.071 [1,2] RANGE: 2.6 to 2000 µg per sample [1, 2]
rT

ACCURACY: ± 16.4% ESTIMATED LOD: 0.8 µg per sample [1]

PRECISION ( r): 0.015

APPLICABILITY: The working range is 0.06 to 7.4 ppm (0.1 to 12.5 mg/m3) for a 25-L air sample [1]. Large (400 mg/200 mg) charcoal
tubes are required for analyte collection, since breakthrough volume is lower with smaller charcoal tubes [2]. Analyte capacity of the large
charcoal tubes has not been determined under conditions of high relative humidity [3].

INTERFERENCES: Samples containing greater than 15% methanol or other alcohols.

OTHER METHODS:This method revises NMAM 1606 (dated 8/15/94) and is based on Method S165 [4]. In this method, a capillary GC
column has replaced the original packed column. Improvements include but are not limited to the following: new and less hazardous
desorption solvent, smaller volume of desorption solvent required, improved desorption efficiency (DE), and lower LOD/LOQ. A storage
stability study was completed and was found acceptable at 98.5% after 30 days at 5 C.

NIOSH Manual of Analytical Methods (NMAM), Fourth Edition

 ACETONITRILE: METHOD 1606, Issue 3, dated 15 January 1998 - Page 2 of 3

REAGENTS: EQUIPMENT:

1. Acetonitrile (ACN), reagent grade (99.9+%)*. 1. Sampler: glass tube, 10 cm, 6-mm ID, flame-
2. Methylene chloride, HPLC grade*. sealed ends with plastic caps, containing two
3. Methanol, HPLC grade*. sections of 20/40 mesh activated coconut shell
4. Helium, purified. charcoal (front = 400 mg, back = 200 mg),
5. Hydrogen, purified. separated by a 3-mm section of polyurethane
6. Air, prefiltered and purified. foam. A silanized glass wool plug precedes the
front section and a 3-mm polyurethane plug
follows the back section. Tubes are
* See SPECIAL PRECAUTIONS commercially available (SKC # 226-09,
Supelco ORBO-32, or equivalent).
2. Personal sampling pump, 0.01 to 0.2 L/min,
with flexible tubing.
3. Gas chromatograph, flame ionization detector
(FID), integrator, and Stabilwax® fused silica
capillary column, or equivalent (page 1606-1).
4. Vials, glass, 4-mL, PTFE-lined screw caps.
5. Syringes, 10-µL to 1-mL.
6. Volumetric flasks, 10-mL.
7. Pipets, various sizes.
8. Refrigerant packs.

SPECIAL PRECAUTIONS: Acetonitrile is toxic and flammable. Methylene chloride is a potential

carcinogen. Methanol is moderately toxic and flammable. Perform all work in a chemical hood and wear
appropriate protective equipment.

SAMPLING:

1. Calibrate each personal sampling pump with a representative sample tube in line.
2. Break open the ends of the sample tube immediately prior to sampling. Attach sample tube 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 both ends of the sample tubes with plastic caps and pack securely for shipment. Ship with
refrigerant packs to keep samples cold.

SAMPLE PREPARATION:

5. Place the initial glass wool plug and front sorbent section of the sample tube in a 4-mL glass screw cap
vial. Place the back sorbent section of the sample tube in separate 4-mL vial. Discard the
polyurethane foam plugs.
6. Add 2.0 mL of methylene chloride/methanol (85:15) to each 4-mL vial and cap securely.
7. Place each vial in an ultrasonic bath for 45 minutes.
8. Transfer 1.0-mL aliquots of each sample to autosampler vials and analyze (steps 11 and 12).

CALIBRATION AND QUALITY CONTROL:

9. Calibrate daily with at least six working calibration standards over the range of interest.
a. Add known amounts of calibration stock solution (prepare in concentration range of samples;
1 µL ACN = 78.3 µg) to methylene chloride/methanol (85:15) 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. µg acetonitrile).
10. Determine the desorption efficiency (DE) atleast once for each batch of charcoal used for sampling

NIOSH Manual of Analytical Methods (NMAM), Fourth Edition

 ACETONITRILE: METHOD 1606, Issue 3, dated 15 January 1998 - Page 3 of 3

in the calibration range (step 9). Prepare three tubes at each of five levels plus three media blanks.
a. Remove the back sorbent section of the sampler.
b. Inject a known amount of calibration stock solution directly onto the front sorbent section of each
charcoal tube.
c. Allow the tubes to air equilibrate for several minutes, then cap the ends of the tubes and allow to
stand overnight.
d. Desorb (steps 5 through 8) and analyze together with standards and blanks (steps 11 and 12).
e. Prepare a graph of DE vs. µg acetonitrile recovered.

MEASUREMENT:

11. Set gas chromatograph according to manufacturer’s recommendations and to conditions given on page
1606-1. Inject a 1-µL sample aliquot manually using the solvent flush technique or with an
autosampler. NOTE: If peak area is above the linear range of the working standards, dilute with
methylene chloride/methanol (85:15), reanalyze and apply the appropriate
dilution factor in the calculations.
12. Measure peak areas.

CALCULATIONS:

13. Determine the mass, µg (corrected for DE), for acetonitrile found in the sample front (W
f) and back (Wb)
sorbent sections, and in the average media blank front (B f) and back (Bb) sorbent sections.
NOTE: If Wb > Wf/10, report breakthrough and possible sample loss.
14. Calculate concentration, C, of acetonitrile in the air volume sampled, V (L):

Wf Wb Bf Bb
C , mg/m 3
V

NOTE: µg/L mg/m3

EVALUATION OF METHOD:

This method development was based upon NMAM user requests to update and improve problematic gas
chromatography methods. After determining that a methylene chloride/methanol (85:15) solution was the
best desorption solvent (improved DE recovery and less hazardous than benzene), the desorption efficiency
was determined for acetonitrile at 5 levels ranging from 39 µg to 275 µg. The average DE for acetonitrile was
determined to be 1.019. The LOD was determined to be 0.8µg per sample. The precision, as determined
from the pooled relative standard deviation (Sr), was determined to be 0.015 [1]. Acetonitrile storage stability
at 0.25 x REL and 5 C, was acceptable after 30 days with an average recovery of 98.5%.

REFERENCES:

[1] Pendergrass SM [1997]. Acetonitrile Backup Data Report, unpublished data, NIOSH/DPSE.
[2] NIOSH [1977]. Documentation of the NIOSH Validation Tests, S165, U.S. Department of Health,
Education, and Welfare (NIOSH) Publ. No. 77-185.
[3] NIOSH [1981]. Health Hazard Evaluation Report, HHE 81-359-1058.
[4] NIOSH [1977]. Acetonitrile: Method S165. In: Taylor, DG, ed. NIOSH Manual of Analytical Methods,
2nd ed., V. 3, U.S. Department of Health, Education, and Welfare (NIOSH) Publication No. 77-157C.

METHOD WRITTEN BY: Stephanie M. Pendergrass, NIOSH/DPSE

NIOSH Manual of Analytical Methods (NMAM), Fourth Edition