Designation: D 4810 – 06

Standard Test Method for

Hydrogen Sulfide in Natural Gas Using Length-of-Stain
Detector Tubes1
This standard is issued under the fixed designation D 4810; 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 converted to ppm (by volume) hydrogen sulfide (H2S), by

1.1 This test method covers a procedure for a rapid and comparison to a calibration scale supplied by the manufacturer
simple field determination of hydrogen sulfide in natural gas for each box of detection tubes (higher range tubes have units
pipelines. Available detector tubes provide a total measuring of percent by volume). The system is direct reading, easily
range of 0.5 ppm by volume up to 40 % by volume, although portable, and completely suited to making rapid spot checks for
the majority of applications will be on the lower end of this hydrogen sulfide under field conditions.
range (that is, under 120 ppm). 4. Significance and Use
1.2 Typically, sulfur dioxide and mercaptans may cause
positive interferences. In some cases, nitrogen dioxide can 4.1 The measurement of hydrogen sulfide in natural gas is
cause a negative interference. Most detector tubes will have a important because of the gas quality specifications, the corro-
“precleanse” layer designed to remove certain interferences up sive nature of H2S on pipeline materials, and the effects of H2S
to some maximum interferent level. Consult manufacturers’ on utilization equipment.
instructions for specific interference information. 4.2 This test method provides inexpensive field screening of
1.3 The values stated in SI units are to be regarded as the hydrogen sulfide. The system design is such that it may be used
standard. by nontechnical personnel with a minimum of proper training.
1.4 This standard does not purport to address all of the 5. Apparatus
safety concerns, if any, associated with its use. It is the
responsibility of the user of this standard to establish appro- 5.1 Length-of-Stain Detector Tube and Calibration
priate safety and health practices and determine the applica- Scale—A sealed glass tube with breakoff tips sized to fit the
bility of regulatory limitations prior to use. tube holder of the pump. The reagent layer inside the tube,
typically a silica gel substrate coated with the active chemicals,
2. Referenced Documents must be specific for hydrogen sulfide and must produce a
2.1 Gas Processors Association Standard: distinct color change when exposed to a sample of gas
No. 2377-86 Test for Hydrogen Sulfide in Natural Gas containing hydrogen sulfide. Any substances known to inter-
Using Length of Stain Tubes2 fere must be listed in the instructions accompanying the tubes.
A calibration scale should be marked directly on the tube or
3. Summary of Test Method other markings which provide for easy interpretation of hydro-
3.1 The sample is drawn through a detector tube filled with gen sulfide content from a separate calibration scale supplied
a specially prepared chemical. Any hydrogen sulfide present in with the tubes. The calibration scale shall correlate hydrogen
the sampling reacts with the chemical to produce a color sulfide concentration to the length of the color stain. Shelf life
change or stain. The length of the stain produced in the detector of the detector tubes must be a minimum of two years from
tube, when exposed to a measured volume of sample, is date of manufacture when stored according to manufacturers’
directly proportional to the amount of hydrogen sulfide present recommendations.
in the sample. A hand-operated piston or bellows-type pump is 5.2 Detector Tube Pump—A hand-operated pump of a
used to draw a measured volume of sample through the tube at piston or bellows type. It must be capable of drawing 100 cm3
a controlled rate of flow. The length of stain produced is per stroke of sample through the detector tube with a volume
tolerance of 65 cm3.3 It must be specifically designed for use
with detector tubes.
1
This test method is under the jurisdiction of ASTM Committee D03 on Gaseous
Fuels and is the direct responsibility of Subcommittee D03.05 on Determination of
NOTE 1—A detector tube and pump together form a unit and must be
Special Constituents of Gaseous Fuels.
Current edition approved June 1, 2006. Published June 2006. Originally
approved in 1988. Last previous edition approved in 1999 as D 4810 - 98 (1999).
2 3
Available from Gas Processors Association, 1812 First National Bank Bldg., Direct Reading Colorimetric Indicator Tubes Manual, 1st ed., American
Tulsa, OK 74103. Industrial Hygiene Association, Akron, OH 44311, 1976.

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D 4810 – 06
used as such. Each manufacturer calibrates detector tubes to match the 6. Procedure
flow characteristics of their specific pump. Crossing brands of pumps and
tubes is not permitted, as considerable loss of system accuracy is likely to 6.1 Select a sampling point that will provide access to a
occur.3 (Note that at least one manufacturer allows extended samples up representative sample of the gas to be tested (for example,
to 100 pumpstrokes to obtain lower detection levels. This may be source valve on the main line). The sample point should be on
automated for screening purposes by drawing the sample from an inert top of the pipeline and equipped with a stainless steel sample
collapsable container by vacuum displacement. The sample flow rate probe extending into the middle third of the pipeline. Open the
should be maintained within 65 % of the manufacturer’s specified flow
source valve momentarily to clear the valve and connecting
rate. Accuracy losses are apt to occur in such special applications, and
such a system is recommended only for screening purposes. Consult nipple of foreign materials.
manufacturers regarding limitations.) 6.2 Install needle valve (or pressure regulator) at the source
valve outlet. Connect sampling chamber using the shortest
5.3 Gas Sampling Chamber—Any container that provides length of flexible tubing possible (Fig. 1). Avoid using tubing
for access of the detector tube into a uniform flow of sample that reacts with or absorbs H2S, such as copper or natural
gas at atmospheric pressure and isolates the sample from the rubber. Use materials such as TFE-fluorocarbon, vinyl, poly-
surrounding atmosphere. A stainless steel needle valve (or ethylene, or stainless steel.
pressure regulator) is placed between the source valve and the
6.3 Open source valve. Open needle valve enough to obtain
sampling chamber for the purpose of throttling the sample
positive flow of gas through chamber, in accordance with 5.3.
flow. Flow rate should approximate one to two volume changes
Purge the container for at least 3 min (Fig. 1).
per minute or, at minimum, provide positive exit gas flow
throughout the detector tube sampling period. NOTE 4—If a collection bag is used instead of a sampling chamber,
follow 6.1 and 6.2, substituting the bag for the chamber. Follow 6.3,
NOTE 2—A suitable sampling chamber may be devised from a poly-
disconnecting the bag when filled. Deflate the bag to provide a purge, and
ethylene wash bottle of nominal 500-mL (16-oz) or 1-L (32-oz) size. The
fill a second time to provide a sample. The bag must be flattened
wash bottle’s internal delivery tube provides for delivery of the sample gas
completely before each filling (Note 3).
to the bottom of the bottle. A 12.5-mm (1⁄2-in.) hole cut in the bottle’s cap
provides access for the detector tube and vent for the purge gas (Fig. 1). 6.4 Before each series of measurements, test the pump for
(An alternate flow-through sampler may be fashioned using a 1-gal leaks by operating it with an unbroken tube in place. Consult
Ziploc-type food storage bag. The flexible line enters one corner of the
the manufacturer’s instructions for leak check procedure de-
bag’s open end and extends to the bottom of the bag. The opposite corner
of the open end is used for tube access and sample vent. The remainder of tails and for maintenance instruction, if leaks are detected. The
the bag’s top is sealed shut. The basic procedure for the sampler in Fig. 1 leak check typically takes 1 min.
applies.) 6.5 Select a detector tube with the range that best encom-
NOTE 3—An alternate sampling container is a collection bag made of a passes the expected H2S concentration. Reading accuracy is
material suitable for the collection of natural gas (for example, Mylar). improved when the stain length extends into the upper half of
The sampling bag should have a minimum capacity of 2 L. the calibration scale. Consult manufacturer’s guidelines for
using multiple strokes to achieve a lower range on a given tube.
6.6 Break off the tube tips and insert the tube into the pump,
observing the flow direction indication on the tube. Place the

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detector tube into the sampling chamber through the access
hole, so that the tube inlet is near the chamber center (Fig. 1).
NOTE 5—Detector tubes have temperature limits of 0 to 40°C (32 to
104°F), and sample gases must remain in that range throughout the test.
Cooling probes are available for sample temperatures exceeding 40°C.
6.7 Operate the pump to draw the measured sample volume
through the detector tube. Observe tube instructions when
applying multiple strokes. Assure that a positive flow is
maintained throughout the sample duration at the sampling
chamber gas exit vent. Observe tube instructions for proper
sampling time per pump stroke. The tube inlet must remain in
position inside the sampling chamber until the sample is
completed. Many detector tube pumps will have stroke finish
indicators that eliminate the need to time the sample.
NOTE 6—If a collection bag is used, the sample is drawn from the bag
via a flexible tubing connection. Do not squeeze the bag during sampling.
Allow the bag to collapse under pump vacuum, so that the pump’s flow
characteristics are not altered.
6.8 Remove the tube from the pump and immediately read
the H2S concentration from the tube’s calibration scale or from
the charts provided in the box of tubes. Read the tube at the
FIG. 1 Apparatus Schematic maximum point of the stain. If “channeling” has occurred

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D 4810 – 06
(nonuniform stain length), read the maximum and minimum 8. Precision and Bias
stain lengths and average the two readings. 8.1 The accuracy of detector tube systems is generally
considered to be 625 %. This value is based on programs
NOTE 7—If the calibration scale is not printed directly on the detector
tube, be sure that any separate calibration chart is the proper match for the conducted by the National Institute of Occupational Safety and
tube in use. Health (NIOSH) in certifying detector tubes for low-level
contaminants in air, adapted to worker exposure monitoring.4
6.9 If the number of strokes used differs from the number of NIOSH tested tubes at 1⁄2 , 1, 2, and 5 times the threshold limit
strokes specified for the calibration scale, correct the reading, value (TLV) requiring 625 % accuracy at the three higher

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as below: levels and 635 % at the 1⁄2 TLV level.5 (For example, H2S with
specified strokes a TLV of 10 ppm was tested at levels of 5, 10, 20, and 50 ppm.)
ppm ~corrected! 5 ppm ~reading! 3 actual strokes (1)
The higher tolerance allowed at the low level was due to the
loss of accuracy for shorter stain lengths.3 NIOSH discontin-
6.10 Record the reading immediately, along with the gas
ued this program in 1983, and it was picked up by the Safety
temperature and the barometric pressure. Observe any tem-
Equipment Institute (SEI) in 1986.
perature corrections supplied in the tube instructions. Altitude
8.1.1 The Gas Processors Association Standard No. 2377
corrections become significant at elevations above 2000 ft.
for natural gas testing via H2S detector tubes summarizes
Correct for barometric pressure, as below:
detector tube accuracy testing in natural gas in which all
760 mm Hg reported results are within 623 %.
ppm ~corrected! 5 ppm ~reading! 3 barometric pressure in mm Hg
8.2 Repeatability—Duplicate results by the same operator,
(2)
under the same test conditions, should produce results within
NOTE 8—Although the amount of chemicals contained in detector tubes 610 % between 3- and 120-ppm H2S and 65 % between 0.05
is very small, the tubes should not be disposed of carelessly. A general and 5 % H2S (see GPA No. 2377). Repeatability is optimized
disposal method includes soaking the opened tubes in water before tube when all tests using a single brand are conducted with detector
disposal. The water should be pH neutralized before its disposal. tubes of the same lot number.
7. Quality Assurance 9. Keywords
9.1 gaseous fuels; natural gas
7.1 Detector tubes from each batch or lot of tubes should be
tested to conform the published accuracy, (generally 6 25 %).
4
7.2 The tubes should continue to meet the published accu- Septon, J. C. and Wilczek, T., “Evaluation of Hydrogen Sulfide Detector
Tubes,” App. Ind. Hyg., Vol. 1, No. 4, 11/86.
racy until the expiration date, if the tubes are shipped and 5
“NIOSH Certification Requirements for Gas Detector Tube Units,” NIOSH
stored per manufacturer instructions. /TC/A-012, 7/78.

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