NIOSH Manual of Analytical Methods (NMAM), Fifth Edition

NIOSH Manual of Analytical Methods (NMAM) 5th Edition 

BACKUP DATA REPORT

NIOSH Method No. 6001

Title: Arsine 

Analyte: Arsine

Author/developer: Developed under contract 

Date: 1976

Note: Method 6001 is a combination of two older, previously published 

methods: S229 and P&CAM 265. Therefore, the backup data report is a

combination of the two methods’ reports. The backup data report for

method S229 is a regular written report. The backup data report for

P&CAM 265, however, is in the form of a published journal article.

The written report for S229 follows, the journal article for P&CAM can be 

seen here as a pdf.

Disclaimer: Mention of any company or product does not constitute endorsement by the National 

Institute for Occupational Safety and Health, Centers for Disease Control and Prevention. In addition, 

citations to websites external to NIOSH do not constitute NIOSH endorsement of the sponsoring 

organizations or their programs or products. Furthermore, NIOSH is not responsible for the content of 

these websites. All web addresses referenced in this document were accessible as of the publication 

date. 
NIOSH Manual of Analytical Methods (NMAM), Fifth Edition

Backup Data Report

Method S229

Substance: Arsine 

OSHA Standard: 0.2 mg/m3

 

Chemical Used: Arsine in Nitrogen (14 ppm), Linde Specialty Gases

Procedure

The general procedure used is described in NIOSH Method 6001. The collection method has been 

adapted from P&CAM 127. The charcoal used was Lot 105 activated coconut charcoal supplied by SKC, 

Inc., Pittsburgh, PA. Desorption efficiency tests have not been carried out because the low 

concentration of the arsine source would require that large volumes of gas (200-800 ml) had to be 

injected directly into the charcoal tube. The arsine vapor samples were collected using the sample 

collection equipment described in the Butyl Acetate S47 Backup Data Report. The samples were 

desorbed in 10.0 ml of 0.01 M nitric acid with ultrasonic agitation for 10-15 minutes. The samples were 

then allowed to stand for one hour with occasional shaking. Tests indicate that this desorption period is 

sufficient for adequate desorption.

The samples were analyzed in a Perkin-Elmer Atomic Absorption Spectrophotometer, Model 503, 

equipped with a heated graphite atomizer, HGA Model 2100, and a Deuterium Background Corrector. A 

Hewlett Packard Recorder, Model 17501A was used. The source was an Electrodeless Discharge Lamp 

powered by a Perkin-Elmer EDL power supply. The arsenic absorption line at 193.7 nm was used for the 

assay.

With the aid of an Eppendorff automatic pipettor with disposable plastic tips, duplicate 50 microliter 

aliquots of the desorbed sample solutions were injected directly into selected graphite tubes. Argon 

was used as the inert gas stream flowing through the furnace. The furnace conditions were as follows:

Table 6001-1. Furnace conditions

Sample cycle Time in seconds Temperature (°C)

Sample drying 40 150

Sample charring 20 250

Sample atomization 10 2200

Peak areas of the absorption peaks, as determined using the Perkin-Elmer 503 integrator accessory, 

were used to determine the quantity of arsenic present in the sample. The analyses were carried out 

such that the samples were carefully alternated with standards of about the same response as the 

sample in order to minimize errors due to observed instrument response variations. 

Discussion

The development of an analytical and sampling method for arsine was initiated by testing the arsine 

evolution method using the Perkin-Elmer Arsine Generator and sodium borohydride as reducing agent; 

the atomic absorption was measured at 193.7 nm. The reproducibility of calibration standards was 
studied from 0.1 to 1.0 μg of arsenic; poor precision was observed with a relative standard deviation of 

15.6% over that concentration range. The precision was also tested for the 18-sample analytical set 

over a fourfold concentration interval by adding 0.2, 0.4, and 0.8 μg of arsenic as sodium arsenate into 

the generator. As shown in Table 6001-2, the observed poor precision does not favor the use of this 

method; the relative standard deviation was 9.7%.

Table 6001-2. Reproducibility of Calibration Standards (Arsine by arsine evolution using Perkin-Elmer 

arsine generator with AA at 193.7 nm)

μg added μg found Mean Std dev CV

0.2 0.21

0.2 0.17

0.2 0.24

0.2 0.23

0.2 0.22

0.2 0.20 0.21 0.025 0.118

0.4 0.42

0.4 0.40

0.4 0.34

0.4 0.44

0.4 0.40

0.4 0.42 0.40 0.034 0.086

0.8 0.84

0.8 0.73

0.8 0.79

0.8 0.74

0.8 0.82

0.8 0.67 0.77 0.063 0.082

The alternative approach studied is the heated graphite atomizer (HGA) method for the analytical 

measurement of arsine; the absorbance at 193.7 nm was used. Initial analytical studies were done by

considering both silver nitrate/impingers and charcoal tubes as viable routes for collection.

The HGA studies were initiated by testing the effect of silver nitrate concentration on the analytical

scheme. It was observed that high concentrations of silver nitrate interferes with the assay because of 

the dense smoke formed during the ignition process, but a 0.01 M solution of silver nitrate was

acceptable. Six analytical samples were prepared by adding 2 μg of arsenic (as sodium arsenate) into 10

ml of 0.01 M silver nitrate. This concentration is equivalent to a 10-liter sample at the OSHA standard 

level. Duplicate 50 μl aliquots of these six samples were analyzed by the HGA method. The data 

summarized in Table 6001-3 indicate that poor precision was obtained when peak height measurements

were used, but the precision was improved considerably when some form of peak area measurement

was used. The relative standard deviation was 0.293 for peak height determined concentrations but

dropped to 0.033 when the planimeter-integrated areas were used.

NIOSH Manual of Analytical Methods (NMAM), Fifth Edition
NIOSH Manual of Analytical Methods (NMAM), Fifth Edition

Table 6001-3. Reproducibility of Calibration Standards (Arsine as arsenic by HGA; in 0.01M AgNO3; peak 

height vs peak area.) 

μg added μg found (peak height) μg found (peak area)1

2.0 2.06 1.99

2.0 3.58 2.03

2.0 2.04 2.03

2.0 3.62 2.09

2.0 1.98 1.90

2.0 2.54 2.01

Mean 2.64 2.01

Std dev 0.77 0.066

CV1 0.293 0.033

1. Peak area determined by planimeter integration of areas of absorption peak. Recorder chart speed

was run at fast mode i.e., 1”/sec.

Subsequent studies were done using the Model 503 integrator accessory in the 10-second integration 

mode; the peak width of the absorption peaks was 3-5 seconds. Five calibration solutions containing 6-

44 μg As/10 ml (3-22 ng/50 μL) were analyzed repetitively six times and the observed relative standard 

deviation over this concentration interval was 2.7%

To test the precision of the method, eighteen samples were prepared by spiking 10 ml of 0.01 M silver 

nitrate with sodium arsenate containing arsenic equivalent to that present in a 10-liter sample at 0.5, 1, 

and 2X OSHA standard for arsine. The data summarized in Table 6001-4 show an average recovery of 

99.5% with average CV1=0.065, indicating that the HGA method is acceptable.
NIOSH Manual of Analytical Methods (NMAM), Fifth Edition

Table 6001-4. Arsine* (10 mL 0.01 M silver nitrate)

μg added μg found Recovery Mean Std dev CV1

1.0 1.14 1.14

1.0 1.84 1.84**

1.0 0.90 0.90

1.0 1.00 1.00

1.0 0.92 0.92

1.0 0.96 0.96 0.984 0.095 0.097

2.0 1.96 0.98

2.0 1.80 0.90

2.0 2.06 1.03

2.0 2.02 1.01

2.0 1.98 0.99

2.0 1.94 0.97 0.980 0.045 0.046

4.0 3.92 0.980

4.0 3.98 0.995

4.0 3.84 0.960

4.0 4.26 1.065

4.0 4.32 1.080

4.0 4.16 1.040 1.020 0.049 0.048

�C��V�

1 = 0.0651; C���V�

A+�D��E� = 0.0705

*Samples spiked with sodium arsenate containing arsenic equivalent to 10 liters at 0.5, 1 and 2X OSHA 

standard for arsine.

**These values excluded from statistical analysis 

In order to determine the most suitable collection media, a "quick-screening" process was set up using a 

single stage, six outlet miniature generator to test a series of alternative collection media for arsine. The 

experimental results summarized in Table 6001-5 indicated that 0.1 M silver nitrate and charcoal could 

both be acceptable. 

Table 6001-5. Comparison of various collection media for Arsine (test conc: 0.324 mg/m3) 

Collection media Flowrate (L/min) % Recovery

0.01 M AgNO3/0.01 M HNO3 1.5 18

0.10 M AgNO3/0.01 M HNO3 1-1.5 75

0.1 M AgNO3 1-1.5 91

3% hydrogen peroxide 1 10

Charcoal 1 50 (front); 18 (backup)

Charcoal 0.2 93 (front); 0 (backup)

Further studies were conducted to evaluate both silver nitrate and charcoal for collection. The

recommended method is collection on charcoal and desorption with 0.01 M nitric acid; the

experimental data with silver nitrate is also presented, to indicate that the overall recovery with this 

method is low.
NIOSH Manual of Analytical Methods (NMAM), Fifth Edition

The collection efficiency in 10 ml of 0.1 M silver nitrate is 91%, as shown in Table 6001-6 for a 110-liter

sample. The solutions were diluted to 100 ml with 0.01 M nitric acid prior to analysis to decrease the 

silver nitrate concentration to 0.01 M. 

Table 6001-6. Collection efficiency of Arsine (0.1M siliver nitrate/impingers; sample size of 110 L)

μg found (1st impinger) μg found (2nd impinger) Total Collection efficiency

35.0 3.9 38.9 0.900

33.5 3.8 37.3 0.898

33.9 3.3 37.2 0.911

34.7 3.0 37.7 0.920

34.9 2.6 37.5 0.931

33.9 3.1 37.0 0.916

Avg collection efficiency=0.913; CV=0.014

Two sets of 18 samples were collected- one set was analyzed immediately while the other set was 

stored for six days. The experimental results tabulated in Tables 6001-7 and 6001-8 show an average 

recovery of 89% for the fresh samples and 86% for the stored samples with an average precision of 

0.066 and 0.038 respectively. All data have been corrected for a desorption efficiency of 0.91. 

Table 6001-7 Sampling and Analysis (0.1M Silver Nitrate/Impingers, stored for 0 days) 

μg 

found

Corrected 

μg found

Liters 

found

mg/m3

found

mg/m3

taken

Recovery Mean Std dev CV2

7.80 8.57 111.3 0.0770 0.095

8.63 9.48 109.5 0.0866 0.095

9.05 9.95 109.5 0.0909 0.095

9.46 10.40 111.1 0.0936 0.095

8.53 9.37 110.4 0.0849 0.095

8.22 9.03 109.9 0.0822 0.095 90.4 0.0859 0.0060 0.696

16.43 18.05 110.6 0.1632 0.201

18.62 20.46 111.2 0.1840 0.201

18.30 20.11 112.6 0.1786 0.201

21.22 23.32 111.5 0.2091 0.201

16.95 18.63 111.5 0.1671 0.201

18.30 20.11 110.6 0.1818 0.201 89.9 0.1806 0.0162 0.0898

36.4 40.0 109.1 0.367 0.415

34.8 38.2 108.8 0.351 0.415

35.3 38.8 110.3 0.352 0.415

36.1 39.7 110.8 0.358 0.415

36.3 39.9 110.7 0.360 0.415

35.2 38.7 109.5 0.353 0.415 86.0 0.357 0.0061 0.0171
NIOSH Manual of Analytical Methods (NMAM), Fifth Edition

Table 6001-8 Sampling and Analysis (0.1M Silver Nitrate/Impingers, stored for 6 days)

μg found Corrected 

μg found

Liters 

found

mg/m3

found

mg/m3

taken

Recovery Mean Std dev CV2

7.86 8.64 111.4 0.0776 0.098

7.92 8.70 109.7 0.0793 0.098

7.80 8.57 109.7 0.0781 0.098

7.68 8.44 111.2 0.0759 0.098

8.69 9.55 110.6 0.0863 0.098

8.36 9.19 110.1 0.0835 0.098 81.7 0.0801 0.0040 0.0495

18.11 19.90 110.8 0.1796 0.204

18.18 19.98 111.3 0.1795 0.204

17.46 19.19 112.8 0.1701 0.204

18.75 20.60 111.6 0.1846 0.204

18.06 19.85 111.6 0.1779 0.204

16.83 18.49 110.8 0.1669 0.204 86.5 0.1764 0.0066 0.0375

28.5* 31.3* 109.3 0.286* 0.415

37.0 40.7 108.9 0.374 0.415

37.2 40.9 110.5 0.370 0.415

37.2 40.9 110.9 0.369 0.415

38.3 42.1 110.8 0.380 0.415

36.2 39.8 109.7 0.363 0.415 89.4 0.371 0.0063 0.0169

*These values excluded from statistical analysis

Generation

The test atmosphere samples at 0.5, 1 and 2X OSHA standard were generated by delivering arsine from 

a gas cylinder via a needle valve into the vapor generation equipment described in the Butyl Acetate S47 

Backup Data Report. The arsine source is a mixture of arsine in nitrogen with a manufacturer's reported 

concentration of 14 ppm. The arsine content of the tank was independently calibrated by using the 

silver diethyldithiocarbamate/pyridine method described in P&CAM 140 and also by collection in 0.1 M 

silver nitrate and analysis by HGA. In both cases, known volumes of arsine from the gas cylinder were 

collected directly into either of the two collection media referred to above; the volume of arsine gas 

collected was determined by water displacement. The determined arsine concentration of the gas 

cylinder by the silver diethyldithiocarbamate method and by the silver nitrate/HCA method was 16.5 

ppm and 15.8 ppm respectively. The generator concentration was calculated on the basis of the silver 

nitrate/HCA assay because this method appeared to be more reliable than the silver

diethyldithiocarbamate method. The latter method required the preparation of a calibration curve by 

generating arsine by the action of metallic zinc on trivalent arsenic and absorbing the arsine formed in 

the pyridine-silver diethyldithiocarbamate. The conversion of arsenic to arsine may not be complete 

and this introduces a bias in the assay of the arsine tank concentration.

Test atmosphere samples at a concentration two times the OSHA standard level were generated by 

delivering 40.8 mg/min (818 ml/min of 15.8 ppm arsine in nitrogen, at 27.6°C and 761 mm Hg) of arsine 

from a gas cylinder into a dry air stream flowing at a rate of 0.1011 m3

/min. The three sample lines were 

maintained at dilution ratios of 0.233, 0.479 and 1.000 to produce the 0.5, 1 and 2X OSHA standard test 

levels. All six samples at the three test levels were collected simultaneously at 0.22 L/min for 45 
NIOSH Manual of Analytical Methods (NMAM), Fifth Edition

minutes (10 liters). The data are summarized in Table 6001-9. The samples were stored for 6 days 

before desorption and analysis. 

Table 6001-9. Sampling and Analysis (lot 105 charcoal, sample stored 6 days)

Test 

level

μg 

Found

Liters 

found

mg/m3

found

mg/m3 

taken

Recovery Mean Std dev CV2

0.5S 0.865 10.16 0.0851 0.0941

0.5S 0.832 10.25 0.0812 0.0941

0.5S 0.857 10.20 0.0840 0.0941

0.5S 0.859 10.43 0.0824 0.0941

0.5S 0.859 10.02 0.0857 0.0941

0.5S 0.809 10.16 0.0796 0.0941 88.2 0.830 0.00236 0.0284

1S 1.957 10.25 0.1909 0.1935

1S 1.907 10.20 0.1870 0.1935

1S 1.917 10.43 0.1838 0.1935

1S 1.857 10.25 0.1812 0.1935

1S 1.936 10.25 0.1889 0.1935

1S 1.956 10.25 0.1908 0.1935 96.7 0.1871 0.00393 0.0210

2S 4.16 10.16 0.409 0.404

2S 3.99 10.25 0.389 0.404

2S 4.07 10.66 0.382 0.404

2S 4.05 10.25 0.395 0.404

2S 3.94 10.25 0.384 0.404

2S 3.93 10.20 0.385 0.404 96.8 0.391 0.0101 0.0258

Breakthrough

The collection efficiency on charcoal was determined based on the analysis of the front and backup 

sections of the charcoal tubes for sampling periods of 45-240 minutes at 0.22 liters per minute. Data 

are summarized in Table 6001-10. 

The first section of the charcoal tube was found to hold at least 0.022 mg of arsine when a test 

atmosphere containing 0.405 mg/m3 of arsine in air was sampled at 0.227 L/min for 240 minutes; i.e., at 

that time the concentration of analyte in the effluent was less than 5% of that in the influent.
NIOSH Manual of Analytical Methods (NMAM), Fifth Edition

Table 6001-10. Collection efficiency* of arsine (lot 105 charcoal, 0.22 L/min, 0.405 mg/m3

) 

Sample size (L) Arsine found 

front 

Arsine found 

backup

Total arsine 

found

% front

10.16 4.16 0.01 4.17 99.8

10.25 3.99 0.00 3.99 100

10.66 4.07 0.00 4.07 100

10.25 4.05 0.00 4.05 100

10.25 3.94 0.00 3.94 100

10.20 3.93 0.00 3.93 100

27.01 10.58 0.01 10.59 99.9

27.25 11.70 0.01 11.71 99.9

42.5 16.66 0.01 16.67 99.9

40.9 17.06 0.00 17.06 100.0

54.5 21.01 0.00 21.01 100.0

54.3 22.57 0.00 22.57 100.0

Overall collection efficiency=99.96%

*all values have not been corrected for desorption efficiency

Precision and Accuracy 

The statistical procedures used are described in Reference 1. 

C���V�

2 = 0.0253 C���V�T = 0.056

The average recovery of the generated samples over all levels was 93.9%.

Because the desorption efficiency was not determined as explained in the procedure section, the results 

should be corrected by this average recovery to reflect the undetermined desorption efficiency factor. 

The NIOSH Method 6001, however, was written with the usual protocol of determining desorption

efficiency for the concentration range studied. The DE experiments can be done using a more 

concentrated arsine source, such as 15% in nitrogen. With a 15% arsine source, only 20-80 microliters of 

gas are needed to cover the 0.5, 1, and 2X OSHA standard and no complications are anticipated in 

directly injecting these small sample volumes into the charcoal tubes.
NIOSH Manual of Analytical Methods (NMAM), Fifth Edition

References

1. Stanford Research Institute [1976]. Documentation of NIOSH Validation Tests. Menlo Park, CA:

Stanford Research Institute, NIOSH Contract No. CDC-99-74-45.