Designation: D 2913 – 96 (Reapproved 2007)

Standard Test Method for

Mercaptan Content of the Atmosphere1
This standard is issued under the fixed designation D 2913; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (e) indicates an editorial change since the last revision or reapproval.

1. Scope D 2914 Test Methods for Sulfur Dioxide Content of the

1.1 This test method covers measurement of the concentra- Atmosphere (West-Gaeke Method)
tion of mercaptans (organic thiols) in the atmosphere at D 3195 Practice for Rotameter Calibration
concentrations below 100 parts per billion (ppb(v) = 195 D 3249 Practice for General Ambient Air Analyzer Proce-
µg/m3). For concentrations above 100 ppb(v) level, the sam- dures
pling period can be reduced or the liquid volume increased D 3609 Practice for Calibration Techniques Using Perme-
either before or after aspirating. The minimum detectable ation Tubes
amount of methyl mercaptan is 0.04 µg/mL (1)2 in a final liquid D 3631 Test Methods for Measuring Surface Atmospheric
volume of 25 mL. When sampling air at the maximum Pressure
recommended rate of 2 L/min for 2 h, the minimum detectable E 1 Specification for ASTM Liquid-in-Glass Thermometers
mercaptan concentration is 1.0 ppb(v) (1.95 µg methyl 3. Terminology
mercaptan/m3 at 101.3 kPa (760 mm Hg) and 25°C). This test
method determines total mercaptans and does not differentiate 3.1 Definitions—For definitions of terms used in this test
among individual mercaptans, although it is most sensitive to method, refer to Terminology D 1356.
the lower molecular weight alkanethiols. 4. Summary of Test Method
1.2 The values stated in SI units are to be regarded as the
standard. 4.1 This test method is intended for obtaining an integrated
1.3 This standard does not purport to address all of the sample over a selected time span (such as 2 h) either manually
safety concerns, if any, associated with its use. It is the or in an automatic sequential sampler using 10 mL of absorp-
responsibility of the user of this standard to establish appro- tion liquid in a bubbler.
priate safety and health practices and determine the applica- 4.2 The absorption liquid is delivered to the laboratory for
bility of regulatory limitations prior to use. Specific precau- colorimetric analysis by reaction between the collected mer-
tionary statements are given in 8.7, 8.8, and Section 9. captan and N,N-dimethyl-p-phenylenediamine.

2. Referenced Documents 5. Significance and Use

2.1 ASTM Standards: 3 5.1 Mercaptans are odorous substances offensive at low
D 1193 Specification for Reagent Water concentrations and toxic at higher levels. They are emitted
D 1356 Terminology Relating to Sampling and Analysis of from geothermal sources, industrial processes, and food pro-
Atmospheres cessing facilities.
D 1357 Practice for Planning the Sampling of the Ambient 6. Interferences
Atmosphere
D 1914 Practice for Conversion Units and Factors Relating 6.1 The N,N-dimethyl-p-phenylenediamine reaction is also
to Sampling and Analysis of Atmospheres suitable for the determination of other sulfur-containing com-
pounds including hydrogen sulfide and dimethyl disulfide (2).
The potential for interference from these latter compounds is
1
This test method is under the jurisdiction of ASTM Committee D22 on Air especially important, since all of these compounds commonly
Quality and is the direct responsibility of Subcommittee D22.03 on Ambient coexist in certain industrial emissions. Appropriate selection of
Atmospheres and Source Emissions. the color formation conditions and measurements of absor-
Current edition approved April 1, 2007. Published May 2007. Originally
approved in 1970. Last previous edition approved in 2001 as D 2913 - 96(2001)e1. bance at the specified wavelength will eliminate the potential
2
The boldface numbers in parentheses refer to the list of references at the end of interference from hydrogen sulfide.
this test method.
3
6.2 Hydrogen sulfide, if present in the sampled air, may
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at [email protected]. For Annual Book of ASTM
cause a turbidity in the sample absorbing solution. This
Standards volume information, refer to the standard’s Document Summary page on precipitate must be filtered before proceeding with the analysis.
the ASTM website. One study showed that 100 µg of H2S gave a mercaptan color

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 D 2913 – 96 (2007)
equivalent to 1.5 to 2.0 µg of mercaptan (3). Another study 7.1.11 The arrangements of the component parts of sam-
reported no absorption at 500 nm in the presence of 150 µg of pling is shown in Fig. 1a, Test Methods D 2914.
hydrogen sulfide (4, 5). 7.2 Calibration Apparatus—A means of generating dy-
6.3 Approximately equimolar response is obtained from the namic standard atmospheres using a permeation device. Dilu-
hydrolysis products of dimethyl disulfide, the molar extinction tion air and excess dilution flow must be filtered through
coefficient for the amine-mercaptan reaction product being activated charcoal to prevent recirculating small quantities of
4.4 3 103, and the amine-dimethyl disulfide reaction product mercaptans. See Practice D 3609 for details.
being 5.16 3 103 (5). The interference due to dimethyl disul- 7.3 Colorimeter or Spectrophotometer, (at 500 nm)—Use
fide has been experimentally determined. Dimethyl disulfide 2.5- or 5.0-cm path length to obtain adequate sensitivity.
concentrations of 0.6 ppm(v) and 1.0 ppm(v) given an equiva-
lent response as 0.4 ppm(v) and 0.8 ppm(v), respectively, of 8. Reagents and Materials
methyl mercaptan.4 8.1 Purity of Reagents—Reagent grade chemicals shall be
6.4 Sulfur dioxide up to 250 µg does not influence the color used in all tests. All reagents shall conform to the specifications
development even when sampling a test atmosphere containing of the Committee on Analytical Reagents of the American
300 ppm(v) of SO2. Chemical Society, where such specifications are available.5
6.5 Nitrogen dioxide does not interfere up to 700 µg of NO2 Other grades may be used, provided it is first ascertained that
when sampling a test atmosphere containing 6 ppm. Higher the reagent is of sufficiently high purity to permit its use
concentrations of NO2 caused a positive interference when without lessening the accuracy of the determination.
mercaptans were present, but no interference in the absence of 8.2 Purity of Water—Unless otherwise indicated, references
mercaptans. Such elevated NO2 concentrations are unrealistic to water shall mean referee reagent water conforming to
and would not be encountered in the ambient air except in the Specification D 1193.
vicinity of an accidental spillage. 8.3 Solutions should be refrigerated when not in use.
6.6 The supply of mercuric acetate must be free of mercu- 8.4 Amine-Hydrochloric Acid Solution, Stock—Dissolve 5.0
rous ion. If mercurous ion is present, turbidity will result when g of N,N-dimethyl-p-phenylenediamine hydrochloride (p-
the chloride ion-containing reagents are added in the last step aminodimethylaniline hydrochloride) in 1 L of concentrated
of the analytical procedure. hydrochloric acid (HCL). Refrigerate and protect from light.
This solution is stable for at least 6 months.
7. Apparatus 8.5 Reissner Solution—Dissolve 67.6 g of ferric chloride
7.1 Sampling Apparatus: hexahydrate (FeCl3·6H2O) in distilled water, dilute to 500 mL,
7.1.1 Absorber—Midget bubbler with coarse porosity frit. and mix with 500 mL of nitric acid (HNO3) solution containing
7.1.2 Air Sample Probe—TFE-fluorocarbon, polypropy- 72 mL of boiled concentrated nitric acid (sp gr 1.42). This
lene, or glass tube with a polypropylene or glass funnel at the solution is stable.
end. 8.6 Color-Developing Reagent—Mix 3 volumes of amine
7.1.3 Moisture Trap-Glass, or polypropylene tube with a solution and 1 volume of Reissner solution. Prepare this
two port closure. The entrance port of the closure is fitted with solution freshly for each set of determinations.
tubing that extends to the bottom of the trap. The unit is loosely 8.7 Absorbing Solution—Dissolve 50 g of mercuric acetate
packed with 16-mesh activated charcoal to prevent moisture Hg (CH3COO)2 in 400 mL of distilled water and add 25 mL of
entrainment. The charcoal should be changed weekly. glacial acetic acid (CH3COOH). Dilute to 1 L. The mercuric
7.1.4 Filter—Membrane, of 0.8 to 2.0 µm porosity. acetate must be free of mercurous salts to prevent precipitation
7.1.5 Pump—Capable of maintaining a vacuum greater than of mercurous chloride during color development. Reagent
70 kPA (0.7 atm) at the specified flowrate. grade mercuric acetate sometimes contains mercurous mer-
7.1.6 Flow Control Device—A needle valve capable of cury. Determine the acceptability of each new bottle of
maintaining a constant flow rate (62 %). Protect the needle mercuric acetate by adding 3 mL of concentrated hydrochloric
valve from particulate matter and moisture entrainment. acid to 3 mL of the 5 % mercuric acetate. If the solution
7.1.7 Flow meter, having a range of 0 to 2.5 L/min. becomes cloudy, the mercuric acetate is not acceptable.
7.1.8 Thermometers—ASTM Thermometer 33C, meeting (Warning—The absorbing solution and mercury salts are very
the requirements of Specification E 1, will be suitable for most poisonous. Avoid contact with the skin and especially with the
applications of this test method. eyes. Avoid generating or breathing dust. Wash hands after use.
7.1.9 Barograph or Barometer—Capable of measuring at- Keep away from food. Do not ingest.)
mospheric pressure to 60.5 kPa (4 Torr), meeting the require- 8.8 Lead Methyl Mercaptide—Bubble tank methyl mercap-
ments of Test Methods D 3631. tan gas (CH3SH) into 10 % lead acetate solution
7.1.10 Stopwatch or timer, accurate to 61 s/24 h. Pb(CH3COO)2 in an adequate fume hood (1). Collect the

4 5
Supporting data giving the results of a laboratory examination of this method Reagent Chemicals, American Chemical Society Specifications, American
by the National Council of the Paper Industry for Air and Stream Improvement Chemical Society, Washington, DC. For suggestions on the testing of reagents not
(NCASI) are available in special report No. 80-07, “A Laboratory Examination of listed by the American Chemical Society, see Analar Standards for Laboratory
the Use of the ASTM/APHA. Spectrophotometric Method for the Measurement of Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
Methyl Mercaptan in Kraft Mill Workspace Atmospheres,” May 1980, NCASI, 260 and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
Madison Ave., New York, NY 10016. MD.

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 D 2913 – 96 (2007)
yellow crystals by vacuum filtration, wash with distilled water, 11.1.1 The pressure drop of the flow meter must be main-
and dry overnight in a vacuum oven at 45°C. Store crystals in tained the same during sampling as during calibration.
a vacuum-sealed container in the dark. One mole of this 11.2 Standard Atmospheres—See Practice D 3609 for
mercaptide is equivalent to two moles of a mercaptan. Lead preparation of standard atmospheres using the calibration
mercaptide may be purchased from commercial sources, if apparatus and the permeation device.
desired.6 (Warning—Methyl mercaptan gas is extremely 11.2.1 Calibrate the components of the calibration apparatus
toxic. At high levels of exposure, the human olfactory sense and the permeation device in accordance with Practice D 3609
may become insensitive to its presence.) before and after use.
8.9 Concentrated, Standard Lead Mercaptide Solution— 11.3 Calibration Curve:
Weigh out 156.6 mg of the crystalline lead mercaptide and 11.3.1 Sample five standard atmospheres in accordance with
make up to 100 mL with the 5 % mercuric acetate absorbing Section 12.1. The mercaptan content of the standard atmo-
solution. This solution contains the equivalent of 500 µg of spheres shall be such that the intensities of the color of the
methyl mercaptan/mL. resultant analyzed solutions shall be evenly spaced over the
8.10 Diluted Mercaptan Solution, Standard—Dilute 2 mL dynamic range of the analytic procedure. One of the five
of the concentrated standard solution to 100 mL with the 5 % standard atmospheres shall be a blank, generated by removing
mercuric acetate absorbing solution. This solution contains the or bypassing the permeation device.
equivalent of 10 µg CH3SH/mL. 11.3.2 Analyze the solutions according to 12.2.
8.11 Methyl Mercaptan Permeation Device, with a perme- 11.3.3 Prepare a calibration curve of total mass of mercap-
ation rate appropriate to the dilution flow and concentrations tan collected versus absorbance of developed color, using the
expected.7 For example, see table below. least squares method.
Concentrations Permeation Rate Required 11.4 Spot checks or audit samples are prepared by analyzing
the diluted standard Mercaptan solutions prepared in 8.10. A
10 ppb(v) @ 2 L/min 40 ng/min
100 ppm(v) @ 1 L/min 200 ng/min minimum of two audit samples shall be analyzed for each ten
atmospheric samples.
9. Safety Precautions 11.4.1 Pipet appropriate aliquots of the diluted standard lead
9.1 Mercury—The absorbing solution contains mercury mercaptide into a series of 25-mL volumetric flasks, diluting
salts. Precautions for its use are described in 8.7. each to 15 mL with 5 % mercuric acetate absorbing solution
9.2 Disposal procedures are described in Annex A3, Test and developing the color in the same manner as the samples. A
Methods D 2914. reference blank is prepared in the same manner with the
9.3 Compressed Gas Cylinders. exception that no lead mercaptide is added. Determine the
9.3.1 Compressed gas cylinders may be used in this test absorbance at 500 nm against the mercaptan-free reference
method for preparation of reagents or standard atmospheres. blank.
Precautions on methyl mercaptan cylinders are described in
8.8. 12. Procedure
9.3.2 General safety precautions for handling and storing 12.1 Collection of Sample—Collect the sample by bubbling
compressed gas cylinders are described in Practice D 3249. the air through 10 mL of absorbing solution in a bubbler at a
10. Sampling measured rate between 0.6 to 2.0 L/min for a selected period up
to 2-h duration.
10.1 Sampling procedures are described for 2–h sampling
12.2 Analysis—Quantitatively transfer the sample from the
periods. Different sampling rates and sampling times may be
bubbler to a 25-mL volumetric flask and dilute to approxi-
selected to suit specific requirements, but sample volume and
mately 22 mL with distilled water that has been used to rinse
flow rates must be adjusted to maintain linearity between
the frit and bubbler flask. Add 2 mL of freshly prepared color
absorbance and concentration over the dynamic range of the
developing reagent, dilute to volume with distilled water, and
colorimetric procedure.
mix well. Prepare a reference blank in the same manner using
10.2 Measure the temperature of the atmosphere being
15 mL of unaspirated 5 % mercuric acetate and 2 mL of
sampled before and after sampling.
color-developing reagent diluted to 25 mL. After 30 min,
10.3 Measure the atmospheric pressure during sampling, in
measure the absorbance at 500 nm with a spectrophotometer
accordance with Test Methods D 3631.
against the mercaptan-free reference blank.
11. Calibration and Standardization
11.1 Sampling Equipment—Calibrate the flow meter before 13. Calculation
and after use in accordance with Practice D 3195. 13.1 Calculate the volume of the atmosphere sampled at
standard conditions of 25°C and 101.3 kPa (1 atm) as follows:
6
The sole source of supply of lead mercaptide known to the committee at this P 298.15
Vr 5 Q 3 t 3 101.3 3 T (1)
time is Eastman Chemical Company, P.O. Box 431, Kingsport, TN 37662. If you are
aware of alternative suppliers, please provide this information to ASTM Interna-
tional Headquarters. Your comments will receive careful consideration at a meeting where:
of the responsible technical committee,1 which you may attend. Vr = Volume of air at standard conditions, L,
7
Methyl mercaptan permeation tube is available from Metronics Associates Inc.,
Q = average flow, L/min,
Santa Clara, CA, or PolyScience Corp., Evanston, IL.

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 D 2913 – 96 (2007)

t = sampling time, min, 1000 = conversion factor, L/m.

P = average atmospheric pressure, kPa, 13.3 See Practice D 1914 for a method to convert µm/m3 to
T = average temperature of air sample, K, ppm(v).
101.3 = pressure of standard atmosphere, kPa, and
298.15 = temperature of standard atmosphere, K. 14. Precision and Bias
13.2 Calculate the concentration of total mercaptan in the 14.1 The relative standard deviation for four mercaptans for
atmosphere as follows: methyl to hexyl mercaptan ranged from 0.0 to 2.6 % (1). The
Mercaptan, µg/m3 5 A 3 1000/Vr (2) relative standard deviation increased with increasing molecular
weight of the mercaptans.
where:
A = mass of mercaptan read from calibration curve, µg, 15. Keywords
and 15.1 ambient atmospheres; analysis; mercaptans; sampling

REFERENCES

(1) Moore, H., Helwig, H. L., and Graul, R. J., Journal of Industrial (4) Adams, D. F., “Analysis of Malodorous Sulfur-Containing Gases,”
Hygiene, Vol 21, 1960, p. 466. paper presented at the Ninth Methods Conference on Air Pollution and
(2) Marbach, E. P., and Doty, D. M., Journal of Agriculture and Food Industrial Hygiene Studies, Pasadena, CA, February 1968.
Chemistry, Vol 4, 1956, p. 881. (5) Bamesberger, W. L., and Adams, D. F., unpublished information, 1968.
(3) O’Keefe, A. E., and Ortman, G. C., Analytical Chemistry, Vol 38,
1966, p. 750.

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