This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles

for the
Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.

Designation: D5504 − 20

Standard Test Method for

Determination of Sulfur Compounds in Natural Gas and
Gaseous Fuels by Gas Chromatography and
Chemiluminescence1
This standard is issued under the fixed designation D5504; 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 (´) indicates an editorial change since the last revision or reapproval.

1. Scope Development of International Standards, Guides and Recom-

1.1 This test method is primarily for the determination of mendations issued by the World Trade Organization Technical
speciated volatile sulfur-containing compounds in high meth- Barriers to Trade (TBT) Committee.
ane content gaseous fuels such as natural gas. It has been 2. Referenced Documents
successfully applied to other types of gaseous samples, includ-
ing air, digester, landfill, and refinery fuel gas. The detection 2.1 ASTM Standards:2
range for sulfur compounds, reported as picograms sulfur, is D1072 Test Method for Total Sulfur in Fuel Gases by
0.01 to 1000. This is equivalent to 0.01 to 1000 mg/m3, based Combustion and Barium Chloride Titration
upon the analysis of a 1 cc sample. D1945 Test Method for Analysis of Natural Gas by Gas
Chromatography
1.2 The range of this test method may be extended to higher D3609 Practice for Calibration Techniques Using Perme-
concentration by dilution or by selection of a smaller sample ation Tubes
loop. D4010 Specification for Waterless Hand Cleaner (With-
NOTE 1— Dilution will reduce method precision. drawn 2000)3
1.3 This test method does not purport to identify all sulfur D4150 Terminology Relating to Gaseous Fuels
species in a sample. Only compounds that are eluted through D4468 Test Method for Total Sulfur in Gaseous Fuels by
the selected column under the chromatographic conditions Hydrogenolysis and Rateometric Colorimetry
chosen are determined. The detector response to sulfur is D4884 Test Method for Strength of Sewn or Bonded Seams
equimolar for all sulfur compounds within the scope (1.1) of of Geotextiles
this test method. Thus, unidentified compounds are determined E177 Practice for Use of the Terms Precision and Bias in
with equal precision to that of identified substances. Total ASTM Test Methods
sulfur content is determined from the total of individually E594 Practice for Testing Flame Ionization Detectors Used
quantified components. in Gas or Supercritical Fluid Chromatography
E691 Practice for Conducting an Interlaboratory Study to
1.4 Units—The values stated in SI units are to be regarded Determine the Precision of a Test Method
as standard. The values given in parentheses after SI units are
provided for information only and are not considered standard. 3. Terminology
1.5 This standard does not purport to address all of the 3.1 For definitions of general terms used in D03 Gaseous
safety concerns, if any, associated with its use. It is the Fuels standards, refer to Terminology D4150.
responsibility of the user of this standard to establish appro-
priate safety, health, and environmental practices and deter- 4. Summary of Test Method
mine the applicability of regulatory limitations prior to use. 4.1 The analysis of gaseous sulfur compounds is challeng-
1.6 This international standard was developed in accor- ing due to the reactivity of these substances. They are difficult
dance with internationally recognized principles on standard- to sample and analyze. Ideally, analysis is performed on-site to
ization established in the Decision on Principles for the eliminate sample deterioration as a factor in analysis. Sampling

1 2
This test method is under the jurisdiction of ASTM Committee D03 on Gaseous For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Fuels and is the direct responsibility of Subcommittee D03.06.02 on Analysis of contact ASTM Customer Service at [email protected]. For Annual Book of ASTM
Minor Constituents by Gas Chromatography. Standards volume information, refer to the standard’s Document Summary page on
Current edition approved Nov. 1, 2020. Published December 2020. Originally the ASTM website.
3
approved in 1994. Last previous edition approved in 2012 as D5504 – 12. DOI: The last approved version of this historical standard is referenced on
10.1520/D5504-20. www.astm.org.

Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States

'RZQORDGHG3ULQWHG$FFHVVHGE\XVHU0DUFRDOEHUWR_'DWH7KX'HF
 D5504 − 20
must be performed using non-reactive containers, such as tion of sulfur to satisfy regulatory, production, or distribution
Silcosteel4 lined vessels, Tedlar5 bags with polypropylene requirements. Fuel gases are also used in energy production or
fittings, or the equivalent. Tedlar5 bag samples require protec- are converted to new products using catalysts that are poisoned
tion from light and heat. Laboratory equipment must be inert or by excessive sulfur in the feed gas. Industry frequently requires
passivated to ensure reliable results. measurement of sulfur in these fuel type gases to protect their
4.2 A one cc (mL) sample is injected into a gas chromato- catalyst investments.
graph where it is eluted through a megabore, thick film, methyl 5.4 Analytical Methods—Gas chromatography (GC) is com-
silicone liquid phase, open tubular partitioning column or other monly used in the determination of fixed gas and organic
suitable column, and separated into its individual constituents. composition of natural gas (Test Method D1945). Other
4.3 Sulfur Chemiluminescence Detection—As sulfur com- standard ASTM methods for the analysis of sulfur in fuel gases
pounds elute from the gas chromatographic column, they are include Test Methods D1072 and D4468 for total sulfur and
processed in a flame ionization detector (FID) or a heated Test Methods D4010 and D4884 for hydrogen sulfide.
combustion zone. The products are collected and transferred to
a sulfur chemiluminescence detector (SCD). This technique 6. Apparatus
provides a sensitive, selective, linear response to volatile sulfur
6.1 Chromatograph—Any gas chromatograph of standard
compounds and may be used while collecting hydrocarbon and
manufacture, with hardware necessary for interfacing to a
fixed gas data from a FID.
chemiluminescence detector and containing all features neces-
4.3.1 Detectors in Series With a SCD—A SCD can fre-
sary for the intended application(s) can be used. Chromato-
quently be used in series with other fixed gas and hydrocarbon
graphic parameters must be capable of obtaining retention time
detectors. However, regulatory bodies may question detector
repeatability of 0.05 min (3 s) throughout the scope of this
compatibility and require demonstration of equivalence be-
analysis.
tween a SCD in a multi-detector system and a SCD operated
using a FID or combustion zone. The user is referred to USEPA 6.1.1 Sample Inlet System—A sample inlet system capable
Method 301 for an example of a general equivalence proce- of operating continuously at the maximum column temperature
dure. is used. A split/splitless injection system capable of splitless
4.3.2 Alternative Detectors—This test method is written for operation and split control from 10:1 up to 50:1 may be used
the sulfur chemiluminescent detector, but other sulfur specific with capillary columns, or when interferants are encountered.
detectors can be used, provided they have sufficient sensitivity, An automated gas sampling valve is required for many
respond to all eluted sulfur compounds, do not suffer from applications. The inlet system must be conditioned or con-
interferences, and satisfy quality assurance criteria. Regulatory structed of inert material and evaluated frequently for compat-
agencies may require demonstration of equivalency of alterna- ibility with trace quantities of reactive sulfur compounds.
tive detection systems to the SCD. 6.1.2 Carrier and Detector Gas Control—Constant flow
control of carrier and detector gases is critical for optimum and
5. Significance and Use consistent analytical performance. Control is achieved by use
5.1 Many sources of natural and petroleum gases contain of pressure regulators and fixed flow restrictors. The gas flow
sulfur compounds that are odorous, corrosive, and poisonous to is measured by appropriate means and adjusted. Mass flow
catalysts used in gaseous fuel processing. controllers, capable of maintaining gas flow constant to 61 %
at the flow rates necessary for optimal instrument performance
5.2 Low ppm amounts of sulfur odorants are added to can be used.
natural gas and LP gases for safety purposes. Some odorants
6.1.3 Detector—Sulfur compounds are processed using a
are unstable and react to form compounds having lower odor
flame ionization detector (FID), a heated combustion zone, or
thresholds. Quantitative analysis of these odorized gases en-
a similar device. The products are collected and delivered to a
sures that odorant injection equipment is performing to speci-
sulfur chemiluminescence detector (SCD).
fication.
6.1.3.1 FID—The detector must meet or exceed the speci-
5.3 Although not intended for application to gases other fications in Table 1 of Practice E594 while operating within
than natural gas and related fuels, this test method has been manufacturer’s specifications. The detector must be capable of
successfully applied to fuel type gases, including refinery, operating at the maximum column temperature. The flow path
landfill, cogeneration, and sewage digester gas. Refinery, from the injection system through the column to the FID must
landfill, sewage digester, and other related fuel type gases remain at or above the column temperature throughout the
inherently contain volatile sulfur compounds that are subject to analysis. The FID must allow for the insertion of a SCD
federal, state, or local control. The methane fraction of these sampling probe into the flame without compromising the
fuel type gases is occasionally sold to distributors of natural ability of the FID to detect hydrocarbons. Flow rates of air and
gas. For these reasons, both regulatory agencies and production hydrogen or, alternatively of oxygen and hydrogen, must be
and distribution facilities may require the accurate determina- optimized to produce a hydrogen rich flame or combustion
zone that is capable of combusting hydrocarbons. This is
4
necessary to minimize matrix effects. When performing the
Silcosteel is a trademark of Restek Corporation, 110 Benner Circle, Bellefonte,
PA, 16823. simultaneous detection of hydrocarbons is necessary, a FID
5
Tedlar is a trademark of DuPont. and heated combustion zone can be used in series. Zero air is

'RZQORDGHG3ULQWHG$FFHVVHGE\XVHU0DUFRDOEHUWR_'DWH7KX'HF
 D5504 − 20
necessary when performing the simultaneous determination of TABLE 1 Example Retention Times Using 4 µ Capillary Column
sulfur gases and hydrocarbons. (30 m × 0.32 mm)A
Conditions as in Table 2
6.1.3.2 SCD—The sulfur chemiluminescence detector shall
Compound Ave. RT min Compound Ave. RT min
meet or exceed the following specifications: (1) greater than Methane 1.458 ?S 16.363
105 linearity, (2) less than 5 pg S/s sensitivity, with modern Ethane 1.730 n-Octane 16.423
detectors reaching as low as 0.5 pg S/s, (3) greater than 106 Ethylene 1.733 ?S 16.425
Hydrogen Sulfide 2.053 ?S 16.592
selectivity for sulfur compounds over hydrocarbons, (4) no Propylene 2.550 ?S 16.692
quenching of sulfur compound response, and (5) no interfer- Carbonyl Sulfide 2.586 ?-EtThiophene 16.983
Propane 2.679 ?S 17.183
ence from co-eluting compounds at the usual GC sampling Sulfur Dioxide 2.815 ?S 17.319
volumes. i-Butane 4.422 ?S 17.631
6.1.3.3 Heated Combustion Zone—Sulfur compounds elut- Butene-1 5.263 ?S 17.754
n-Butane 5.578q m&p-Xylene 17.788
ing from the chromatographic column are processed in a heated Methanethiol 5.804 ?S 17.913
hydrogen rich combustion zone or a flame ionization detector t-Butene-2 5.938 ?S 18.063
fitted to the end of the column. Products are transferred under 2,2-DMO3 6.009 ?S 18.139
c-Butene-2 6.409 o-Xylene 18.279
reduced pressure to the reaction chamber of a chemilumines- 3-Me-Butene-1 7.463 n-None 18.448
cence detector. An excess of ozone present in the chamber i-Pentane 8.035 ?S 18.450
reacts with the sulfur combustion product(s) to liberate blue Pentene-1 8.500 ?S 18.567
Ethanethiol 8.583 ?S 18.642
(480 nm) and ultraviolet light (260 nm). 2-Me-Butene-1 8.717 DiEthylDiSulfide 18.767
6.1.3.4 SCD operation is based on the chemiluminescence n-Pentane 8.860 ?S 18.911
Isoprene 8.983 ?S 19.008
(light emission) produced by the reaction of ozone with an t-Pentene-2 9.096 ?S 19.125
unidentified sulfur species produced in a combustion zone, Dimethylsulfide 9.117 ?S 19.292
flame ionization detector, or related device. The chemilumi- o-Pentene-2 9.321 ?S 19.979
2-Me-Butene-2 9.463 2,2,4-TriMeBz 20.227
nescent sulfur species is the subject of on-going research. The Carbon Disulfide 9.617 n-Decane 20.308
appendix describes two chemiluminescence reaction models. 2,2-DMO4 9.898 ?S 20.550
The sulfur combustion product(s) and an excess of ozone are i-Propanethiol 10.222 ?S 21.396
Cyclopentene 10.392 ?S 21.733
drawn into a low pressure (<20 Torr) reaction cell. The ozone 3-MePentadiene 10.525 ?S 21.808
reacts to produce blue light (480 nm), oxygen, and other CP/2,3-DMO4 10.733 n-Undecane 22.033
products. A blue sensitive photomultiplier tube detects the 2-MO5 10.883 ?S 22.208
3-MO5 11.269 ?S 23.046
emitted light, which is then amplified for display or output to t-Butanethiol 11.278 ?S 22.417
a data collection system. Hexene-1 11.392 n-Dodecane 23.631
n-Propanethiol 11.625 Benzothiophene 23.717
6.2 Column—A variety of columns can be used in the n-Hexane 11.720 n-Tridecane 25.134
MethylEthylSulfide 11.779 MeBzThiophene 25.225
determination of sulfur compounds. Typically, a 60 m ×
MeCyC5 12.457 MeBzThiophene 25.328
0.54 mm ID fused silica open tubular column containing a Benzene 13.154 MeBzThiophene 25.433
5 µm film thickness of bonded methyl silicone liquid phase is s-Butanethiol 13.154 MeBzThiophene 25.550
used. The selected column should provide retention and A
The 4 µ column may not have the molecular loading capable of meeting the
resolution characteristics such as listed in Table 2 and illus- detection range as described in the method.

trated in Fig. 1. The column must be inert towards sulfur

compounds. The column must be inert towards sulfur com-
TABLE 2 Typical Gas Chromatographic Operating Parameters
pounds. The column must also demonstrate a sufficiently low
Injector, gas sample loop: 150 °C 0.5 cc
liquid phase bleed at high temperature such that loss of the Injector, splitless: 150 °C 100 % sample to
SCD response is not encountered while operating the column at column
200 °C. Flame ionization detector (FID): 250 °C
H2: 200 cm3/min
6.3 Data Acquisition: Air: 400 cm3/min
Make-up gas (He): 20 cm3/min
6.3.1 Recorder—A 0 to 1 mV range recording potentiometer Or a Heated combustion zone (HCZ): 800 °C
or equivalent, with a full-scale response time of 2 s or less can H2: 100 cm3/min
Air: 40 cm3/min
be used. SCD: output at 0–1 V cell pressure at 6.0 torr
6.3.2 Integrator—An electronic integrating device or com- Column Program: 1.5 min at 30 °C
puter can be used. A dual channel system is necessary for 15.0°/min to 200 °C
hold at 200 °C as required
simultaneous acquisition of both the FID and SCD signals. The Carrier gas (helium): adjust to methane retention time of 1.10 min
device and software must have the following capabilities: 3
Carrier: 11 cm /min
6.3.2.1 Graphic presentation of the chromatogram.
6.3.2.2 Digital display of chromatographic peak areas.
6.3.2.3 Identification of peaks by retention time or relative 7. Reagents and Materials
retention time, or both. NOTE 2—Warning: Sulfur compounds contained in permeation tubes
or compressed gas cylinders may be flammable and harmful or fatal if
6.3.2.4 Calculation and use of response factors. ingested or inhaled. Permeation tubes and compressed gas standards
6.3.2.5 External standard calculation and data presentation. should only be handled in well ventilated locations away from sparks and

'RZQORDGHG3ULQWHG$FFHVVHGE\XVHU0DUFRDOEHUWR_'DWH7KX'HF
 D5504 − 20

Hydrogen sulfide (H2S)

Carbonyl sulfide (COS)
Methyl mercaptan (CH3SH)

7.2.3 The following substances can also be included in a

compressed gas standard.
Ethyl mercaptan (CH3CH2SH)
1-propanethiol (CH3CH2CH2SH)
2-propanethiol (CH3CHSHCH3)
Dimethyl sulfide (CH3SCH3)

7.2.4 The following compounds are not recommended for

inclusion in mixed component standards due to their potential
for promoting degradation.
Carbon disulfide (CS2)
FIG. 1 Standard: Perm Tube Analysis Run Dimethyl disulfide (CH3SSCH3)
Other disulfides

7.2.5 All multicomponent compressed gas standards must

flames. Improper handling of compressed gas cylinders containing air, be re-certified as recommended by the manufacturer or as
nitrogen, or helium can result in explosion. Rapid release of nitrogen or needed to ensure accuracy.
helium can result in asphyxiation. Compressed air supports combustion.
7.2.6 For the analysis of complex samples, such as refinery
7.1 Sulfur Standards—Accurate sulfur standards are re- fuel and related fuel type gases, the SCD system must
quired for sulfur gas quantitation. Permeation and compressed demonstrate the capability of eluting common relatively high
gas standards should be stable, of high purity, and of the molecular weight volatile sulfur compounds including di-n-
highest available accuracy. propyl sulfide (propyl sulfide). A retention time standard for
7.1.1 Permeation Devices—Sulfur standards can consist of demonstrating this capability can be prepared from the com-
permeation tubes, one for each selected sulfur species gravi- pound (ACS Grade) at approximately 160 ppmv concentration
metrically calibrated and certified at a convenient operating by addition of a 1 µL aliquot of the liquid to a 10 L Tedlar bag
temperature. With constant temperature, calibration gases cov- filled with UHP nitrogen or helium.
ering a wide range of concentration can be generated by
varying and accurately measuring the flow rate of diluent gas 7.2.7 Carrier Gas—Helium or nitrogen of high purity. Use
passing over the tubes. These calibration gases are used to of molecular sieves or other suitable agents to remove water,
calibrate the GC/SCD system. oxygen, and hydrocarbons is recommended. Gas pressure must
7.1.1.1 Permeation System Temperature Control— be sufficient to ensure a constant carrier flow rate (see 6.1.2).
Permeation devices are maintained at the calibration tempera- 7.2.8 Hydrogen—High purity hydrogen is required as fuel
ture within 0.1 °C for a flame ionization detector, a heated combustion zone, or a
7.1.1.2 Permeation System Flow Control—The permeation similar device.
flow system measures diluent gas flow over the permeation 7.2.9 Air—High purity air is required as oxidant for a flame
tubes within 62 %. ionization detector, a heated combustion zone, or a similar
7.1.1.3 Permeation tubes are inspected and weighed to the device.
nearest 0.01 mg on at least a monthly basis using a balance 7.2.10 Oxygen—High purity oxygen supply gas to the SCD
calibrated against NIST traceable “S” class weights or the ozone generator may be used for maximum detector sensitivity.
equivalent. Analyte concentration is calculated by weight loss
and dilution gas flow rate as per Practice D3609. These devices 8. Equipment Preparation
are discarded when the liquid contents are reduced to less than
ten (10) percent of the initial volume or when the permeation 8.1 Chromatograph—Place in service in accordance with
surface is unusually discolored or otherwise compromised. the manufacturer’s instructions. Many operating conditions can
be used to perform sulfur gas speciation and quantitation.
7.2 Compressed Gas Standards—Alternatively, blended Typical, minimal performance criteria for chromatographic
gaseous sulfur standards in nitrogen, helium, or methane base conditions are:
gas may be used. Care must be exercised in the use of
8.1.1 The conditions must separate all volatile sulfur com-
compressed gas standards since they can introduce errors in
pounds required for calibration.
measurement due to lack of uniformity in their manufacture or
instability in their storage and use. The protocol for com- 8.1.2 Chromatographic conditions must elute all sulfur
pressed gas standards contained in the appendix can be used to species of interest.
ensure uniformity in compressed gas standard manufacture and 8.1.3 The injection system must transfer, without loss or
provide for traceability to a NIST or NMi reference material. absorption, all sulfur compounds of interest to the GC column
7.2.1 Compressed gas standard regulators must be appropri- without reaction between sulfur species or excessive carryover
ate for the delivery of sulfur gases and attached fittings must be between samples.
passivated or inert to sulfur gases. 8.1.4 The operating conditions presented in Table 1 have
7.2.2 The following sulfur compounds are recommended been successfully used to fulfill the above criteria. Table 1
for inclusion in a compressed gas standard. provides a listing of the retention times of selected sulfur

'RZQORDGHG3ULQWHG$FFHVVHGE\XVHU0DUFRDOEHUWR_'DWH7KX'HF
 D5504 − 20
compounds obtained using the parameters in Table 2. Figs. 2
and 3 illustrate typical analyses of a standard mixture and
natural gas.
8.2 SCD—Place in service in accordance with the manufac-
turer’s instructions. FID, heated combustion zone, and mixed
FID/heated combustion zone interface configurations can be
successfully applied to the analysis of sulfur gases in gaseous
samples. For each of these interface configurations, optimiza-
tion of the oxidant/fuel ratio is critical for ensuring complete
combustion of hydrocarbon components in a sample. A flame
or combustion zone that is too hydrogen rich will result in
incomplete combustion and will produce a methane peak
before elution of H2S (Fig. 4). Matrix interference is occasion- FIG. 3 Natural Gas Analysis-Hydrocarbon Compounds
ally observed when changing sample size. Matrix interference
is also indicated by recoveries less than 90 % or greater than
110 % for samples spiked with calibration gas or samples
diluted with air. When matrix interference is indicated, samples gases. Samples demonstrating high hydrocarbon interference
may be analyzed by dilution or application of other mitigation can frequently be analyzed using this configuration.
efforts provided a spiked sample performed using the mitiga-
tion procedure results in recoveries within 10 % of theoretical 9. Calibration
results. Operational features specific to the interface configu-
ration employed are described in the following. 9.1 Sample Introduction—Using passivated or inert
8.2.1 FID Interface—Placed into service as per the SCD equipment, transfer an aliquot of calibration standard to the GC
manufacturer’s instructions. For this interface, probe place- sample loop. The aliquot must be of sufficient size to com-
ment is critical for optimal sensitivity and reproducibility. pletely flush and fill the sample loop. Generally, a sample size
Response that remains the same or decreases with increasing 10 times the volume of the sample loop and inlet line is
sample size indicates questionable interface efficiency (Figs. 5 sufficient. Inject the sample in the sample loop into the GC
and 6). column and start the chromatographic program. Appropriate
8.2.2 Flameless Interface or Other Heated Combustion analyte concentrations should be selected for calibration.
Zone—Placed into service as per manufacturer’s instructions. 9.2 SCD Calibration—Monthly, or whenever maintenance
The typical flameless/combustion zone interface contains ce- is performed, a three-point calibration curve forced through
ramic tubes in its construction. The performance of these tubes zero and prepared for each analyte of interest is suggested and
is critical to performance of the SCD system. Compromised may be required for certain applications. Linearity confirma-
ceramic tubes are susceptible to matrix effects. Compromised tion is consistent with acceptable SCD performance.
tubes may allow for reproducible duplicate sample analysis but 9.2.1 When needed, linearity can be established according
will fail QA procedures such as matrix dilution and spike to the following procedure. For each concentration of analyte,
analyses. Poorly functioning tubes can also result in severe the standard is analyzed until three (3) consecutive trials yield
instrument drift, loss of equimolar response, and general a maximum range of 5 %. The average area for each point is
response instability. Compromised tubes must be replaced to calculated. A linear regression is performed for each compo-
restore nominal instrument function. nent using the average area. For each calibration point, the
8.2.3 Mixed FID Heated Combustion Zone Systems— determined concentration is calculated from the average areas.
Combining a FID and a heated combustion zone in series can Linearity is confirmed when the determined amount is within
afford the simultaneous detection of hydrocarbons and sulfur 5 % of the actual amount of the analyte.
9.2.2 Establishment of linearity validates use of daily
single-point calibration. When linearity cannot be established,
a daily three-point calibration curve with end points bracketing
anticipated analyte concentrations is suggested.
9.2.3 Typically daily, standards are analyzed until three (3)
consecutive trials yield a maximum range of 5 %.
9.2.4 The SCD is an equimolar detector; therefore, response
factors for all calibration components should be within 5 % of
the response factor for hydrogen sulfide. Failure to satisfy this
criteria indicates either calibration standard degradation or
failure of the SCD heated combustion zone, flame ionization
detector (FID), or related device.
9.2.5 Calculate the relative response factor for each sulfur
compound:
FIG. 2 Natural Gas Analysis-Sulfur Compounds F n 5 ~ C n /A n ! (1)

'RZQORDGHG3ULQWHG$FFHVVHGE\XVHU0DUFRDOEHUWR_'DWH7KX'HF
 D5504 − 20

FIG. 4 Too Rich of a Combustion Flame Will Cause Methane Breakthrough

where: examined for continued sulfur gas stability and acceptable

Fn = response factor of compound, sample carryover characteristics. Passivated or lined vessels
Cn = concentration of the sulfur compound in the mixture, may allow for reliable sample analysis after 24 h. In such
and cases, analysis is recommended within 7 days of collection.
An = peak area of the sulfur compound in the mixture. 10.3 External Calibration—Procedures delineated in 9.2
The response factor (Fn) of each single sulfur compound validate the use of a single-point calibration. At least once a
should be within 5 % of Fn for hydrogen sulfide. Fig. 1 day, analyze the calibration standard and determine standard
provides an example of a typical chromatogram and Table 4 response factors. Typically, standards are analyzed until three
shows the data and calibration report. Table 3 contains infor- (3) consecutive trials yield a maximum range of 5 %.
mation useful for calibration calculations. 10.4 Blank Analysis—Confirmation of a lack of carry-over
or contamination is recommended and may be required for
10. Procedure
certain applications. This is accomplished through analysis of
10.1 Many operating conditions can be used to perform a nitrogen or zero air blank. Observation of excessive amounts
sulfur gas speciation and quantitation. Minimum criteria for of high molecular weight volatile sulfur compounds is typical
acceptable operating conditions are as stated in 8.1. In addition, of injection valve deterioration.
it is advisable and required for regulatory purposes to establish 10.5 Sample Analysis—The analysis of each sample in
the limit of detection (LOD) for a SCD system. duplicate is strongly suggested and may be required for certain
10.2 Sampling and Preparation of Samples—Appropriate applications. Duplicate sample analysis will verify adequate
sampling procedures are critical for meaningful sulfur deter- SCD system conditioning and performance. Duplicate sample
mination and must be tailored to the particular sample source. response for components present at or greater than 1 ppm (v/v)
10.2.1 Samples—Samples are delivered to the laboratory in concentration in either analysis should generally be within ten
Tedlar bags with polypropylene fittings or other inert fittings at (10) percent of the initial analysis to verify acceptable system
atmospheric pressure, protected from heat and light. Samples performance. When the determined amount of any sulfur
normally must be analyzed within 24 h of sampling. component exceeds the calibration range established under
Alternatively, samples are delivered to the laboratory in silica- 9.2.2, a split injection should be used. Alternatively, samples
lined vessels or other passivated/lined vessel demonstrated to may be diluted using UHP nitrogen or zero air as the diluant.
not degrade sulfur gas samples over 24 h. As part of a QA/QC Retention times for peaks in sample chromatogram are com-
program, passivated or lined vessels should periodically be pared to those of peaks in the standard chromatograms to

'RZQORDGHG3ULQWHG$FFHVVHGE\XVHU0DUFRDOEHUWR_'DWH7KX'HF
 D5504 − 20

FIG. 5 Example of Matrix Interference; Changing the Sample Size Should Give a Change in Response

identify sulfur compounds. Compounds for which a standard is 10.6.2 Calibration Standard Reanalysis—A standard is re-
not available are conveniently quantified using the response analyzed after samples every day as part of a QA/QC program.
factor from one of the calibrants. Run the analysis per the All components should be within 10 % of the theoretical
conditions specified in Table 1, or using other conditions amounts based on the original standards. Unacceptable results
satisfying the chromatographic performance criteria in 8.1. typically are indicative of SCD combustion zone failure.
Obtain the chromatographic data via a potentiometric record
(graphic), digital integrator, or computer-based chromato- 11. Calculations
graphic data system. Examine the graphic display or digital
11.1 Determine the chromatographic peak area for compo-
data for any errors (for example, over-range component data).
nents and use the response factors obtained from the calibration
10.6 Quality Assurance—The following quality assurance run to calculate amounts of sulfurs present.
(QA) procedures are suggested and may be required in certain Example:
applications. These QA procedures will identify inaccuracy Assume 1.0 ppmv of dimethyl sulfide, DMS, injected into a
due to a compromised flame ionization detector or heated 1.0 cc sample loop with no split.
combustion zone or other SCD system component. 1 ppmv DMS = 2.54 mg/M3 (Table 3)
10.6.1 Spiked Samples—A spiked sample is analyzed each 2540 pg × 51.61 % S = 1310 picog S/peak
day as part of a QA/QC program. Spikes are prepared by
If area is found to be 15 850 counts—
quantitative addition of a mixed component calibration gas to
response factor picograms (S/peak) is 1310/15 850 = 8.27 ×
a known volume of sample gas. Typically, 20 or 50 mL of a
10−2 (in terms of picograms sulfur per peak) or
mixed component standard is added to a sample to give a final
volume of 100 mL. Acceptable recoveries for components response
−6
factor (ppmv DMS sample) = 1.0/15 850 = 63 ×
present at the greater of 5 ppmv or 5 % of the total volatile 10 (in terms of ppmv of sulfur compound in sample)
sulfur should fall within 10 % of the theoretical amounts to NOTE 3—Since detector response is proportional to weight sulfur, all
verify nominal system performance. Unacceptable recoveries mono sulfur compounds (COS, H2S, DMS, etc.) will have approximately
indicate matrix interference or system malfunction. In many the same response factor for picograms S or ppmv (see 9.2.2).
instances, when unacceptable recoveries are obtained, samples Alternatively, concentration of volatile sulfur compounds is
can be analyzed by dilution or other mitigation efforts. calculated in ppm (v/v) by the following:

'RZQORDGHG3ULQWHG$FFHVVHGE\XVHU0DUFRDOEHUWR_'DWH7KX'HF
 D5504 − 20

FIG. 6 Example of Typical Response Curve with Varying Sample Size

TABLE 3 Sulfur Gas Standard TABLE 4 Calibration Table

(Conversion) SIEVERS 8 PTUBES NEW DET—MEGABORE/20PSIG He 5/6/91
Mg/M3 per SPLITLESS Calibration file: DATA:SVPT.Q Last Update: 24 Jul 91
Compound Mol. Wt. Density BP°C %S 5:37 pm Reference Peak Window: 5.00 % of Retention Time Non-
PPMV
(298 K) Reference Peak Window: 5.00 % of Retention Time Sample Amount:
Hydrogen sulfide (H2S) 34.08 1.1857 — 94.08 1.39 0.000 Uncalibrated Peak RF: 60.00e-6 Multiplier: 1.000
Carbonyl sulfide (COS) 60.08 1.24 — 53.37 2.46 Pk-Type
Methanethiol (MeSH) 48.110 0.8665 6.2 66.65 1.97 Ret Time Ph# Signal Descr Amt PPMV cvl RespFact
Partial Name
Ethanethiol (EtSH) 62.134 0.8391 35.0 51.61 2.54
1.461 1 GC Signal 1 0.9100 1 59.60e-6 1 H2S
Dimethylsulfide (DMS) 62.134 0.8483 37.3 51.61 2.54
1.595 2 GC Signal 1 0.2610 1 36.92e-6 1 COS
Carbon disulfide (CS2) 76.14 — — 84.23 3.11
2.861 3 GC Signal 1 0.3570 1 50.11e-6 1 MTM
2-Propanethiol (iPrSH) 76.160 0.8143 52.6 42.10 3.11
3.529 4 GC Signal 1 0.4150 1 50.28e-6 1 ETM
t-Butanethiol (tBSH) 90.186 0.8002 65.0 35.56 2.62
3.809 5 GC Signal 1 0.4943 1 49.02e-6 1 DMS
1-Propanethiol (nPrSH) 76.160 0.8415 67.0 42.10 3.11
4.185 6 GC Signal 1 0.2289 1 0001001 1 CS2
Methylethylsulfide (MES) 76.160 0.8422 67.0 42.10 3.11
4.481 7 GC Signal 1 0.3904 1 50.04e-6 1 1PM
Thiophene (TP) 84.14 1.07 84.16 38.03 3.44
5.179 8 GC Signal 1 0.6140 1 49.99e-6 1 TBM
s-Butanethiol (s-BuSH) 90.186 0.8299 85.0 35.56 3.69
5.521 9 GC Signal 1 2.600 1 50.00e-6 1 MES
i-Butanethiol (i-BuSH) 90.186 0.8343 88.7 35.56 3.69
6.738 10 GC Signal 1 0.9870 1 49.99e-6 1 SBM
Diethylsulfide (DES) 90.190 0.8362 92.0 35.55 3.69
7.129 11 GC Signal 1 1.225 1 48.81e-6 1 DES
n-Butanethiol (n-BuSH) 90.186 0.8416 98.5 35.56 3.69
7.868 12 GC Signal 1 1.135 1 49.99e-6 1 NBM
Dimethyldisulfide (DMDS) 94.200 1.0625 109.7 68.08 3.85
7.912 13 GC Signal 1 0.07660 1 0.0001000 1 DMDS
Diethyldisulfide (DEDS) 122.252 0.9931 154.0 52.46 5.00
9.017 14 GC Signal 1 1.558 1 49.99e-6 1 THT

pksamp
Analyte concentration, ppm 5 × Std (2)
pkstd

'RZQORDGHG3ULQWHG$FFHVVHGE\XVHU0DUFRDOEHUWR_'DWH7KX'HF
 D5504 − 20
where: “test result” reported represents an individual determination.
analyte concentration = concentration of individual sulfur Each participating laboratory reported five replicate test results
compounds or SO2, for every material. Practice E691 was followed for the design
pksamp = peak area in the sample, and analysis of the data; the details are given in ASTM
pkstd = peak area in the standard, and Research Report RR:D03-1009.6
Std = concentration of analyte in the 13.1.1 Repeatability Limit (r)—Two test results obtained
standard, ppm. within one laboratory shall be judged not equivalent if they
Peak heights can be substituted for peak areas. differ by more than the “r” value for that material; “r” is the
Total volatile sulfur is the sum of all identified and uniden- interval representing the critical difference between two test
tified sulfur compounds. results for the same material, obtained by the same operator
using the same equipment on the same day in the same
11.2 Recoveries for the total volatile sulfur or each compo-
laboratory.
nent in spiked samples are calculated by the following:
13.1.1.1 Repeatability limits are listed in Tables 5-7.
SM
Recovery ~ % ! 5 × 100 (3) 13.1.2 Reproducibility (R)—Two test results shall be judged
~ SA! ~ DF1 ! 1 ~ SS! ~ DF2 ! not equivalent if they differ by more than the “R” value for that
where: material; “R” is the interval representing the critical difference
SM = measure spiked sample concentration in ppm (v/v), between two test results for the same material, obtained by
SA = the average sample concentration from duplicate different operators using different equipment in different labo-
analysis of the sample in ppm (v/v), ratories.
SS = concentration of the analyte used to spike the sample 13.1.2.1 Reproducibility limits are listed in Tables 5-7.
in ppmv, 13.1.3 The above terms (repeatability limit and reproduc-
DF1 = dilution factor for the sample, and ibility limit) are used as specified in Practice E177.
DF2 = dilution factor for the standard. 13.1.4 Any judgment in accordance with statements 13.1.1
Recoveries are only calculated for components in the stan- and 13.1.2 would have an approximate 95 % probability of
dard used to spike the sample. The total recovery for the spike being correct.
is calculated according to the above equation using only
13.2 Using the certified values reported for the concentra-
components in the standard used to perform the spike.
tion of each laboratory’s specific cylinders, the laboratories’
11.3 Recoveries for post sample reanalyzed standards are recoveries were averaged, and the mean of the recoveries is
calculated by the following: reported by level in Tables 5-7.
Calibration Value 2 Measured Value 13.3 The precision statement was determined through sta-
QA\QC Recovery ~ % ! 5 × 100
Calibration Value tistical examination of 270 results, from six laboratories, on
(4) three materials. These three materials were described as the
following:
12. Report Material 1: cylinder of approximately 1 ppm v/v each H2S,
12.1 Report the identification and concentration of each COS, MESH
individual sulfur compound. The sum of all sulfur components Material 2: cylinder of approximately 10 ppm v/v each
detected to the nearest picogram, calculated as sulfur (pg S) H2S, COS, Meoh
can be used to calculate the total sulfur. Alternatively, the Material 3: cylinder of approximately 20 ppm v/v each
results may be reported in ppm (v/v) when required by using H2S, COS, MESH
the alternative calculations contained in 11.1. To judge the equivalency of two test results, it is recom-
mended to choose the concentration closest in characteristics to
13. Precision and Bias the test material.
13.1 Precision—The precision of this test method is based
on an interlaboratory study of Test Method D5504 conducted
in 2008. Results in this study were obtained from six labora- 6
Supporting data have been filed at ASTM International Headquarters and may
tories reporting Hydrogen sulfide, Carbonyl sulfide, and methyl be obtained by requesting Research Report RR:D03-1009. Contact ASTM Customer
mercaptan concentrations on three different materials. Every Service at [email protected].

TABLE 5 Methyl Mercaptan (ppm)

Material AverageA Repeatability Reproducibility Repeatability Reproducibility Avg. %
Standard Standard limit Limit Recovery
Deviation Deviation
x̄ sr sR r R
1 1.48 0.10 0.32 0.29 0.89 78.0%
2 9.17 0.19 2.07 0.52 5.81 99.8%
3 20.37 0.71 2.40 1.98 6.73 96.0%
A
The average of the laboratories’ calculated average.

'RZQORDGHG3ULQWHG$FFHVVHGE\XVHU0DUFRDOEHUWR_'DWH7KX'HF
 D5504 − 20
TABLE 6 Hydrogen Sulfide (ppm)
A
Material Average Repeatability Reproducibility Repeatability Reproducibility Avg. %
Standard Standard limit Limit Recovery
Deviation Deviation
x̄ sr sR r R
1 1.79 0.10 0.60 0.27 1.67 87.4%
2 10.79 0.20 3.78 0.56 10.59 98.5%
3 21 0.50 3.48 1.39 9.76 99.7%
A
The average of the laboratories’ calculated average.

TABLE 7 Carbonyl Sulfide (ppm)

Material AverageA Repeatability Reproducibility Repeatability Reproducibility Avg. %
Standard Standard limit Limit Recovery
Deviation Deviation
x̄ sr sR r R
1 2.36 0.06 0.30 0.16 0.85 116.0%
2 11.37 0.22 1.78 0.60 4.97 99.8%
3 26.88 0.71 3.73 1.97 10.46 117.6%
A
The average of the laboratories’ calculated average.

14. Keywords
14.1 chemiluminescence detection; gas chromatography;
sulfur compounds

APPENDIXES

(Nonmandatory Information)

X1. PROTOCOL FOR COMPRESSED GAS CALIBRATION STANDARDS

This protocol was developed to assist compressed gas sulfur X1.3 The values for individual sulfur components and the
standard users. It can provide calibration gas traceability to a total sulfur amount are calculated according to the formula:
NIST, NMi, or similar standard reference material. This
Sulfur calculated concentration
protocol requires the determination of the speciated and total
sulfur using a NIST or NMi hydrogen sulfide SRM or a NTRM Average area as calculated in step 1
5 × H 2 S Std.Conc.
as the primary reference. This procedure will ensure uniformity Average area as calculated in step 2
in measurement of sulfur content. This protocol was developed (X1.1)
by compressed gas vendors and should be submitted to vendors
when calibration gas is ordered. X1.4 The analysis for total volatile sulfur and individual
components calculated as hydrogen sulfide (X1.1 – X1.3) is
X1.1 A standard is analyzed according to Test Method
performed at least twice, with a minimum 48 h incubation
D5504. The GC temperature program is designed to elute all
period between the two analyses. The difference in percent
sulfur species up to and including di-n-propyl sulfide. A
between the two values, for total volatile sulfur and individual
minimum of three consecutive data points are collected with
components calculated as hydrogen sulfide must be less than
the necessary precision to support the reported analytical
2 %. This is necessary to assure product stability. The reported
accuracy. The necessary precision is achieved with a percent
relative standard deviation (% RSD) calculated from a mini- total and individual sulfur concentrations are the value ob-
mum of three consecutive data points, less than or equal to one tained in the second analysis.
percent. An average area for each component and the total
sulfur area is calculated using all consecutive analyses. X1.5 The values for total volatile sulfur and individual
components are reported on the certificate of analysis as
X1.2 A hydrogen sulfide standard reference material is follows:
analyzed under identical conditions used in the analysis of the
standard. Acceptable hydrogen sulfide reference standards X1.5.1 The values for the total volatile sulfur and individual
include NIST or NMi traceable SRMs or NTRMs. A minimum components from both the first and second analysis in X1.4,
three consecutive data points are collected with the necessary along with the date of analyses.
precision to support the reported analytical accuracy. An X1.5.1.1 The cylinder number, concentration, and NIST or
average area of the hydrogen sulfide is calculated using all NMi SRM/NTRM batch ID from the NIST reference standard
consecutive analysis: used in the standard analysis.

10

'RZQORDGHG3ULQWHG$FFHVVHGE\XVHU0DUFRDOEHUWR_'DWH7KX'HF
 D5504 − 20
X1.5.1.2 The total sulfur reported must include all
components, including any unknowns. The total of the un-
knowns shall also be reported in ppm.

X2. CHEMILUMINESCENCE REACTION MODELS

Gas chromatography with sulfur chemiluminescence detec- using a photomultiplier tube. A vacuum maintains the reaction
tion is a powerful means to separate and measure sulfur cell at or below 10 mm of pressure. This prevents the loss of
compounds in complex samples including natural gas, refinery sulfur monoxide and minimizes loss of response due to
fuel gas, landfill gas, and other gaseous fuels (1-3).7 Two collisional quenching.
mechanisms have been proposed as the basis for SCD opera-
tion. X2.2 Model 2—A second reaction mechanism proposed as
the basis for SCD operation is depicted below (13-15):
X2.1 Model 1—One chemical reaction proposed as the basis
for SCD operation is shown below (4-9); some background R·S1O 2 →SO2 1CO2 1other oxidation products (X2.2)
references on sulfur chemistry and chemiluminescence are also
SO2 1H 2 →H 2 S1other reduced sulfur species
given (10-14):
Sulfur compund1hydrogen products/oxygen combustion→SO H 2 S1other reduced sulfur species1O 3 →SO2 *1H 2 O
1products (X2.1) SO2 *→SO2 1hν
SO1O 3 →SO2 1O 2 1h ν According to this mechanism, sulfur compounds are com-
where: busted to SO2. Sulfur dioxide is reduced in the presence of
excess hydrogen to H2S. Hydrogen sulfide is transferred to a
hν = light energy at 300 nm to 400 nm.
reaction cell. Ozone produced in an ozonator is added to the
According to this mechanism, sulfur monoxide and the other reaction cell where it reacts with hydrogen sulfide to create
combustion products are transferred to a reaction cell. Ozone excited state sulfur dioxide. Relaxation of sulfur dioxide to the
produced in an ozonator is added to the reaction cell where it ground state releases a photon. The emitted light is measured
reacts with sulfur monoxide. The emitted light is measured using a photomultiplier tube. A vacuum maintains the reaction
cell at or below 10 mm of pressure. This minimizes the loss of
7
The boldface numbers in parentheses refer to the list of references at the end of response due to collisional quenching of excited state sulfur
this standard. dioxide.

REFERENCES

(1) Johansen, N. G., “Recent Advances in Improved Sulfur Analysis for (6) Benner, R. L. and Stedman, D. H., “Chemical Mechanism and
Natural Gas and Condensates,” presented at IGT Symposium on Gas Efficiency of the Sulfur Chemiluminescence Detector,” Applied
Quality & Energy Measurement, Chicago, Illinois, June 12-13 1989. Spectroscopy, 48, 848 (1994).
(2) Hines, W. J., “Sulfur Speciation by Capillary Gas Chromatography (7) Burrow, P.L and Birks, J.W., “Flow Tube Kinetics Investigation of the
and Sulfur Chemiluminescence Detection-GPA Sulfur Research Mechanism of Detection in the Sulfur Chemiluminescence Detector,”
Project,” Proceedings of the Seventy-Second GPA Annual Anal. Chem. 69, 1299 (1997).
Convention, 50-54 1990 and “Report on GPA Analytical Methods to (8) Shearer, R. L., “Development of Flameless Sulfur Chemilumines-
Measure Sulfur in LP-Gas,” Proceedings of the Seventy-Second GPA cence Detection: Application to Gas Chromatography,” Anal. Chem.
Annual Convention, 91-96 1990. 64, 2192 (1992).
(3) Dominguez, R. and Wadley, M. W., “G. C. Detection of Volatile (9) Shearer, R. L., Chapter 2, “Flameless Sulfur Chemiluminescence
Sulfur Compounds: An Evaluation of Sulfur Chemiluminescence Detection,” Ed.: Sievers, R. E., Selective Detectors Vol. 131 in
Detectors,” South Coast Air Quality Management District, Technical Chemical Analysis: A Series of Monographs on Analytical Chemistry
Services Division Report, March 1990, and Dominguez, R. and Choa, and Its Applications; John Wiley & Sons, Inc, New York, 1995.
C. B., "The Gas Chromatographic Detection of Volatile Sulfur (10) Halstead, C. J. and Thrush, B. A., “Chemiluminescent Reactions of
Compounds in Gas Chromatography using Electrolytic Conductivity, SO,” Photochem. Photobiol. 4, 1007 (1965).
Sulfur Chemiluminescence and Flame Photometric Detection," South (11) Akimoto, H., Finlayson, B. J., and Pitts, J. N., “Chemiluminescent
Coast Air Quality Management District, Technical Services Division Reactions of Ozone with Hydrogen Sulphide, Methyl Mercaptan,
Report, October 1991. Dimethyl Sulphide and Sulphur Monoxide,” Chem. Phys. Lett. 12,
(4) Benner, R. L. and Stedman, D. H., “Universal Sulfur Detection by 199 (1971).
Chemiluminescence,” Anal. Chem. 61, 1268 (1989). (12) DeMore, W. B., Sander, S. P., Golden, D. M., Hampson, R. F.,
(5) Martin, H. R. and Glinski, R. J., “Chemiluminescence from Sulfur Kurylo, M. J., Howard, C. J., Ravishankara, A. R., Kolb, C. E. and
Compounds in Novel Flame and Discharge Systems: Proof of Sulfur Molina, M. J., “Chemical Kinetics and Photochemical Data for Use
Dioxide as the Emitter in the New Sulfur Chemiluminescence in Stratospheric Modeling,” NASA Evaluation No. 11, Nation Tech-
Detector,” Applied Spectroscopy, 46, 948 (1992). nical Information Service, Springfield, VA, 1994.

11

'RZQORDGHG3ULQWHG$FFHVVHGE\XVHU0DUFRDOEHUWR_'DWH7KX'HF
 D5504 − 20
(13) Cadle, R.D., and Ledford, M., “The Reaction of Ozone With Company, New York, 1968.
Hydrogen Sulfide,” Air and Wat. Pollut. Int. J., Vol. 10, pp. 25-30, (15) Yan, X., “Detection by Ozone-induced Chemiluminescence in
Permagon Press, Great Britain, 1966. Chromatography,” Journal of Chromatography A, 842, 267-308
(14) Nickless, G., “Inorganic Sulphur Chemistry,” Elsevier Publishing (1999).

ASTM International takes no position respecting the validity of any patent rights asserted in connection with any item mentioned
in this standard. Users of this standard are expressly advised that determination of the validity of any such patent rights, and the risk
of infringement of such rights, are entirely their own responsibility.

This standard is subject to revision at any time by the responsible technical committee and must be reviewed every five years and
if not revised, either reapproved or withdrawn. Your comments are invited either for revision of this standard or for additional standards
and should be addressed to ASTM International Headquarters. Your comments will receive careful consideration at a meeting of the
responsible technical committee, which you may attend. If you feel that your comments have not received a fair hearing you should
make your views known to the ASTM Committee on Standards, at the address shown below.

This standard is copyrighted by ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959,
United States. Individual reprints (single or multiple copies) of this standard may be obtained by contacting ASTM at the above
address or at 610-832-9585 (phone), 610-832-9555 (fax), or [email protected] (e-mail); or through the ASTM website
(www.astm.org). Permission rights to photocopy the standard may also be secured from the Copyright Clearance Center, 222
Rosewood Drive, Danvers, MA 01923, Tel: (978) 646-2600; http://www.copyright.com/

12

'RZQORDGHG3ULQWHG$FFHVVHGE\XVHU0DUFRDOEHUWR_'DWH7KX'HF