Trends in Analytical Chemistry 64 (2015) 4252

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Trends in Analytical Chemistry

j o u r n a l h o m e p a g e : w w w. e l s e v i e r. c o m / l o c a t e / t r a c

Sampling of gaseous sulfur-containing compounds at low

concentrations with a review of best-practice methods for
biogas and natural gas applications
Andrew S. Brown a,*, Adriaan M.H. van der Veen b, Karine Arrhenius c, Arul Murugan a,
Lucy P. Culleton a, Paul R. Ziel b, Jianrong Li b
a

Analytical Science Division, National Physical Laboratory (NPL), Teddington, Middlesex TW11 0LW, United Kingdom
VSL, Thijsseweg 11, Delft 2629 JA, Netherlands
c
SP Technical Research Institute of Sweden, Box 857, Bors SE-501 15, Sweden
b

A R T I C L E

I N F O

Keywords:
Biogas
Gas analysis
Hydrogen sulde
Natural gas
Passivated sampling cylinder
Sampling
Stability
Standard gas mixture
Sulfur-containing compound
Trace level

A B S T R A C T

The accurate quantication of low-concentration sulfur-containing compounds is essential for the biogas
and natural gas industries. We review literature data for the stability of these compounds in standard
gas mixtures when sampled in cylinders with different passivations, sample bags, sorbent tubes, solidphase microextraction and glass sampling bulbs, and we present new data obtained at our three National
Measurement Institutes. We show that losses of sulfur-containing compounds are minimized when using
passivated sampling cylinders, and the most suitable sorbent material for sampling these compounds is
Tenax TA. We also discuss methods for transferring gas from sample vessels to analyzers and give recommendations for the selection of regulators (and other pressure-reducing devices) and transfer lines.
Further, we propose approaches that could be taken to reduce or correct for losses in order to provide
more accurate measurements of sulfur-containing compounds.
2014 Elsevier B.V. All rights reserved.

Contents
1.
2.

3.

4.

Introduction ...........................................................................................................................................................................................................................................................
Low-concentration sulfur-containing compounds in biogases ............................................................................................................................................................
2.1.
Typical compounds and concentrations ........................................................................................................................................................................................
2.2.
Specications for transmission in European natural gas networks .....................................................................................................................................
2.3.
Reactivity of sulfur-containing compounds ..................................................................................................................................................................................
2.4.
Analytical techniques ...........................................................................................................................................................................................................................
Sample vessels and sorbent tubes .................................................................................................................................................................................................................
3.1.
Introduction .............................................................................................................................................................................................................................................
3.2.
Cylinders ...................................................................................................................................................................................................................................................
3.3.
Sample bags .............................................................................................................................................................................................................................................
3.4.
Sorbent tubes ..........................................................................................................................................................................................................................................
3.5.
SPME ..........................................................................................................................................................................................................................................................
3.6.
Glass sampling bulbs ............................................................................................................................................................................................................................
Transferring gas from sample vessels to analyzers .................................................................................................................................................................................
4.1.
Introduction .............................................................................................................................................................................................................................................
4.2.
Regulators and other pressure-reduction devices ......................................................................................................................................................................
4.3.
Transfer lines ...........................................................................................................................................................................................................................................

43
43
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43
44
44
44
44
44
47
48
49
50
50
50
50
50

Abbreviations: CEN, European Committee for Standardization; EASEE-gas, The European Association for the Streamlining of Energy Exchange in Gas; GC, Gas chromatograph(y); ISO, International Organization for Standardization; MS, Mass spectroscopy; OFCEAS, Optical feedback cavity enhanced absorption spectroscopy; PEEK, Polyether
ether ketone; PDMS, Polydimethylsiloxane; PTFE, Polytetrauoroethylene; PVC, Poly(vinyl chloride); RH, Relative humidity; SPME, Solid-phase microextraction; TC, Technical Committee; VOC, Volatile organic compound.
* Corresponding author. Tel.: +44 20 8943 6831; Fax: +44 20 8614 0448.
E-mail address: andrew.brown@npl.co.uk (A.S. Brown).
http://dx.doi.org/10.1016/j.trac.2014.08.012
0165-9936/ 2014 Elsevier B.V. All rights reserved.

A.S. Brown et al./Trends in Analytical Chemistry 64 (2015) 4252

5.

43

Conclusions ............................................................................................................................................................................................................................................................ 51
Acknowledgements ............................................................................................................................................................................................................................................. 51
References .............................................................................................................................................................................................................................................................. 51

1. Introduction
The accurate quantication of low concentrations1 of sulfurcontaining compounds2 in gases is essential to ensure compliance
with legislation in a number of industrial and environmental sectors,
such as the natural gas industry and monitoring the quality of
ambient air. These measurements are hugely challenging due to the
reactivity of these compounds and their propensity to adsorb to the
internal surfaces of sample vessels and transfer lines.
In the natural gas industry, measurements of sulfur-containing
compounds are required to ensure that the gas injected into transmission networks conforms to national limits for concentrations of
these compounds. These limits are set to ensure that the levels of
these compounds are not suciently high to cause damage to
the transmission pipelines and equipment or to pose a health risk
[1]. However, some sulfur-containing compounds are added to
natural gas as odorants [2] to enable leaks of natural gas to be
detected by the public. The dosing of such odorants is also subject
to regulatory requirements that require underpinning by accurate
measurements.
The biogas industry also has an urgent need for the traceable
and accurate analysis of sulfur-containing compounds. The continued decline of European natural gas resources is leading to
diversication of the gas supply as promoted by European Directives [3,4] and European Commission (EC) targets that, for example,
specify that 20% of EC energy consumption should come from renewable sources by 2020 [5]. As a direct result of these drivers, the
European biogas industry has increased dramatically over recent
years by the start of 2012, more than 10 Mtoe (megatons of oil
equivalent) of biogas was produced in the European Union [6]. Two
key uses for biogas (as biomethane) are for injection into natural
gas networks, and for vehicle fuel.
Depending on its production source and the stage of the upgrading process, biogas can contain a number of sulfur-containing
compounds that have the capability to corrode processing equipment and gas pipelines, and to inhibit the performance of vehicle
catalysts. The most common sulfur-containing compound found in
biogas is typically hydrogen sulde, but other sulfur-containing compounds (similar to those found in or added to natural gas) may also
be present. This is discussed further in the sub-section 2.1.
CEN (The European Committee for Standardization) Technical
Committee 408 (Natural gas and biomethane for use in transport
and biomethane for injection in the natural gas grid) is currently
working in response to the ECs Mandate M/475 [7] to develop
specications for the permissible levels of a range of compounds
in biomethane, including some sulfur-containing compounds.
When fully developed and introduced into legislation, the robust

1
The term concentration is used in this article only in a generic sense. When
discussing experimental data or work published in other studies, the terms amount
fraction (units of mol mol1 or sub-multiples thereof), volume fraction (m3 m3, L
L1 or sub-multiples thereof) and mass concentration (kg m3 or sub-multiples
thereof) are used as appropriate. In the cases when an article in the literature has
used non-specic units of ppm (parts-per-million) or ppb (parts-per-billion), it is
assumed that the author is referring to volume fraction.
2
The term sulfur-containing compounds is used in this article to refer to those
sulfur-containing compounds typically found in biogas or used to odorise natural
gas articially. These include hydrogen sulde, carbonyl sulde, carbon disulde,
carbon dioxide, organic suldes, organic disuldes, thiols and tetrahydrothiophene.
See Table 2(a) for full details of the compounds studied in this work.

enforcement of this specication will critically depend upon the

availability of traceable and accurate methods of analysis.
This article, which is the rst review of its type, aims to outline
the challenges of performing accurate analysis of low concentrations of sulfur-containing compounds, focusing on the issues around
sampling of these compounds. As a key barrier to the accurate measurement of these compounds is the selection of appropriate
sampling media, the main focus of the article is to review the literature in order to examine the suitability of various types of storage
media, such as cylinders, sample bags, sorbent tubes and solidphase microextraction (SPME). We summarize the stability of sulfurcontaining compounds from gas standards of known composition
in these storage media, and we present new data obtained at our
three National Measurement Institutes. We then discuss bestpractice methods for transferring gases from sample vessels to
analyzers, and present literature data on the losses of sulfurcontaining compounds with different transfer lines.
This article focuses solely on data obtained using synthetic gas
standards of known composition [8] rather than real biogas samples
in order to allow quantitative assessment of the performance of sampling media and the extent of transfer losses. Synthetic gas standards
have known compositions and their stability can be determined from
a priori knowledge of identical mixtures. The use of synthetic gas
standards to test storage and to transfer losses of sulfur-containing
compounds therefore elucidates the performance of the sampling
media under ideal conditions. Samples of real biogas cannot exhibit
greater stability than synthetic gas standards, so the use of gas standards is very much a best case test of performance.
2. Low-concentration sulfur-containing compounds
in biogases
2.1. Typical compounds and concentrations
The concentrations of sulfur-containing compounds in biogas can
vary substantially depending on the source of the gas, but mass concentrations of hydrogen sulde as high as 7000 mg m3 are possible
[9]. However, typically, hydrogen-sulde mass concentrations
are < 600 mg m 3 for biogas produced by anaerobic digestion
and < 100 mg m3 for biogas from landll [10]. Biogas is usually desulfurized whilst still in the bioreactor in order to avoid damage to
downstream processing equipment.
Aside from hydrogen sulde, a range of other sulfur-containing
compounds are present in biogas, most usually as volatile, lowmolecular-weight compounds. For example, a study measuring
sulfur-containing compounds in biogas from a plant in Linkping,
Sweden [11], found that the biogas before upgrading contained hydrogen sulde (at a volume fraction of up to 32.4 L L1), carbonyl
sulde (up to 1.2 L L1), methanethiol (up to 0.75 L L1), dimethyl sulde (up to 9.2 L L1), carbon disulde (up to 0.02 L L1),
2-propanethiol (up to 0.05 L L1), ethyl methyl sulde (up to 1.2 L
L1), diethyl sulde (up to 0.58 L L1) and dimethyl disulde (up
to 1.0 L L1).
2.2. Specications for transmission in European natural
gas networks
In order to ensure the safety and the integrity of gas-transmission
networks, national specications for gas quality exist. In addition
to specifying the permissible ranges for physical properties, such

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A.S. Brown et al./Trends in Analytical Chemistry 64 (2015) 4252

as caloric value, Wobbe index and hydrocarbon dew point, these

specications set maximum levels for a range of sulfur-containing
compounds. The maximum mass concentrations permissible in
selected European countries [12] are shown in Table 1.
The specication for biomethane for injection into natural gas
networks being developed by CEN TC408 [13] had not, as of November 2014, specied maximum concentrations for sulfurcontaining compounds, but it is expected to use the same values
as a European standard for natural gas quality being developed by
CEN TC234 Working Group 11. The latest draft version of this natural
gas quality standard [14] sets limits of 20 mg m3 for total sulfurcontaining compounds, 5 mg m3 (as sulfur) for the sum of hydrogen
sulde and carbonyl sulde, and 6 mg m3 (as sulfur) for thiols. These
values are very similar to those previously given in the proposed
EASEE-gas (the European Association for the Streamlining of Energy
Exchange in Gas) specication for cross-border transport of natural
gas within Europe [15], the only difference being that the EASEEgas document set a limit of 30 mg m3 (rather than 20 mg m3) for
total sulfur-containing compounds.
2.3. Reactivity of sulfur-containing compounds
As the sulfur-containing compounds found in biogas (and other
energy gases) are reactive, one of the key measurement challenges is ensuring that the sample injected into the analyzer contains
the same levels of these compounds as the sample taken from the
gas stream. The relative losses of sulfur-containing compounds
through adsorption onto, or reactions with, surfaces typically increase with decreasing amount fraction.
When preparing gas standards, reactions between components and surfaces can largely be avoided by using passivated
materials for gas cylinders, reducers and pipework, and by the careful
selection of high-purity gases and liquids. However, this option is
not available when measuring sulfur-containing compounds in
biogas, where the compounds may react with water or oxygen. Two
example reactions are:

2H2S(g) + 3O2(g) 2H2O(l) + 2SO2(g)

(1)

COS(g) + H2O(l) H2S(g) + CO2(g)

(2)

Experimental evidence for the reaction in Equation (2) is shown

in Fig. 1, which shows the measured amount fraction (over a period
of more than 10 months) of carbonyl sulde and hydrogen sulde
in a gas standard originally containing 10 mol mol1 of both compounds in methane. The decrease in the measured amount fraction

Table 1
Maximum mass concentrations of sulfur-containing compounds specied in European gas transmission network. An asterisk (*) indicates the specication is for the
sum of hydrogen sulde and carbonyl sulde; a dash (-) indicates that no specication exists.
Country

Austria
Belgium
France
Germany
Italy
Netherlands
Poland
Spain
Sweden
Switzerland
United Kingdom

Maximum mass concentration / mg m3

Total sulfur-containing compounds

Hydrogen sulde

Thiols

100
150
30
30
150
45
40
50
23
10
50

5
5*
5*
5
6.6
5
7
15 *
10
5
5

15
15
6
6
15.5
16
17
-

Fig. 1. Measured amount fractions of hydrogen sulde (lled orange squares), carbonyl sulde (lled purple triangles) and the sum of the two compounds (open red
circles) in a gas standard originally containing 10 mol mol1 of both compounds
in methane. The data are plotted relative to the original (gravimetric) amount fraction of each compound in the gas standard. The relative expanded uncertainty of
each measurement is ~3%.

of carbonyl sulde can be seen to correlate clearly with an increase in the measured amount fraction of hydrogen sulde.
2.4. Analytical techniques
A range of analytical techniques are available for the measurement of sulfur-containing compounds. These are well documented
in the literature and a detailed discussion of the these is out of scope
of this article. However, by far the most commonly-used technique is gas chromatography (GC), which was employed in all of
the studies reviewed in this article using a number of different GC
detection methods: mass spectrometry (MS), ame-ionization detection, atomic emission detection, sulfur chemiluminescence
detection, and pulsed ame photometric detection.
3. Sample vessels and sorbent tubes
3.1. Introduction
The three most common ways in which biogas are sampled are:
into cylinders, into sample bags and onto sorbent tubes. Cylinders
can be internally passivated to prevent losses of sulfur-containing
compounds but are typically expensive to purchase and to transport. Sample bags are a lower cost solution, but are generally
constructed from polymeric materials that are likely to result in losses
of reactive compounds. Sorbent tubes are less straightforward to
employ in the eld and require careful selection of the sorbent material, but are easy to transport. We now examine each of these three
storage media in turn, followed by a brief discussion of two other
sampling media that are often used for sulfur-containing compounds in other matrices (such as ambient air): SPME and glass
sampling bulbs. The published work reviewed in this section is
summarized in Table 2.
3.2. Cylinders
ISO 11114-1 [39], which provides guidance on the safe selection of cylinder materials, species that both aluminum and steel
cylinders are suitable for the storage of hydrogen sulde and
other sulfur-containing compounds, but emphasizes that these
compounds may be corrosive in the presence of water. However,

A.S. Brown et al./Trends in Analytical Chemistry 64 (2015) 4252

45

Table 2
Summary of the studies discussed in this article. The Table is separated into six sections to group together the studies by the type sampling media investigated, which are
(in order) cylinders, sample bags, sorbent tubes, solid-phase microextraction, glass sampling bulbs and transfer lines
Ref.
[16]

Sampling media / transfer line

Fused silica lined 1.4 L canisters

[17]
[18]

SilcoCan canisters
Silcosteel sample cylinders

This article, Fig. 2

This article, Fig. 3

10 L aluminum cylinders with BOC Spectraseal

passivation
5 L aluminum cylinders with Scott Aculife IV,
BOC Spectraseal or Air Liquide AlphaTech
passivation

[19]

Tedlar bags and polyester bags

[20]

Tedlar bags and polyester aluminum bags

[18]

[22]

(Standard) Tedlar bags and black/clear layered

Tedlar bags
Tedlar bags, black layered Tedlar bags, Teon
bags, FlexFoil bags and Nalophan bags
Tedlar bags and polyester aluminum bags

[23]
This article, Fig. 4

Tedlar bags and polyester aluminum bags

FlexFoil bags and FlexFilm bags

[24]

[26]

Tenax TA / Carboxen 1000 dual-bed sorbent

tubes
Sorbent materials: Silica gel and/or molecular
sieves, Carbosieve SIII, Tenax TA, molecular
sieves + Tenax TA, Carbotrap 100 / 150 / 200 /
300 / 301 / 400, Carboxen 569
As [25]

[27]
[28]

[21]

[25]

[29]

[30]

H2S, COS, SO2, CS2, Me2S, Me2S2, MeSH (all at 10 L

1

H2S, COS, CS2 Me2S, MeSH (all at 10 L L )

Me2S, EtMeS, Et2S, MeSH, EtSH, 1-PrSH, 2-PrSH,
1-BuSH, 2-BuSH (all at 1 mg m3)
H2S (0.5 mol mol1 to 200 mol mol1)

Nitrogen and
moist air
Synthetic air
Nitrogen
Methane

H2S (5 mol mol1, 50 mol mol1, 123 mol mol1,

203 mol mol1 and 301 mol mol1)

Synthetic
biogas

H2S, Me2S, Me2S2, MeSH (all at 100 nL L1, 200 nL L1

and 300 nL L1)
H2S, SO2, CS2, Me2S, Me2S2, MeSH (all at 1 nL L1, 10 nL
L1, 100 nL L1, 1 L L1 and 10 L L1)
Me2S, EtMeS, Et2S, MeSH, EtSH, 1-PrSH, 2-PrSH,
1-BuSH, 2-BuSH, (all at 1 mg m3)
H2S, COS, SO2, Me2S, MeSH, EtSH (all at 50 nL L1)

Nitrogen

Duration of stability tests

up to 4 days
up to 10 days
up to 14 days
Up to 39
months
25 months

Nitrogen
Nitrogen

up to 14 days

Nitrogen and
outdoor air
Nitrogen

up to 80 hours

Nitrogen
Methane

3 days
10 days

H2S, COS, CS2, Me2S, MeSH, EtSH (all at 20 nL L1)

Nitrogen

24 hours

H2S (40 L L1)

Air

N/A (recovery
tests only)

COS (40 L L1)

Air

As [25]

MeSH (26.9 L L1)

Air

Tenax TA (alone, or with carbonized molecular

sieve or Carbograph 5TD) and silica gel sorbent
tubes
PDMS, Carbotap 300 and Tenax sorbents

MeSH (124 L L1)

Air

N/A (recovery
tests only)
N/A (recovery
tests only)
4 days

THT, 1-PrSH, 2-PrSH, 2-Me-2-PrSH,1-PenSH, 1-HexSH,

2-TEtOH, Me-3TP, 2-EtTEtOH (3002,250 g L1 in a
liquid solution)
H2S, COS, MeSH, Me2S, CS2, 2-PrSH, EtMeS, Et2S, Me2S2
(402,000 g m3)
Me2S2 (1 g m3 and 50 g m3)

N/A (recovery
tests only)

Air
Air

N/A (recovery
tests only)
-

Me2S, EtMeS, 1-BuSH, 1-Me-1-PrSH, THT, 2,5-DMT (all

at approximately 4 mg m3)

Air

16 days

MeSH (13 L L1), Me2S (17 L L1), 2-PrSH (5 L L1),

2-BuSH (5 L L1)
MeSH, Me2S, 2-PrSH, 2-BuSH (all at 15 L L1)

Air

50 hours

Air

N/A (recovery
tests only)
-

This article, Fig. 5

[32]

Carboxen-PDMS

[33]
[34]

Naon membrane driers and polphenylene

wool
Carboxen-PDMS

[30]

PDMS-Carboxen

[35]

Glass sampling bulbs

[36]

PTFE and stainless steel sampling lines

[37]

Silcosteel-treated stainless steel, stainless

steel, silicone, PTFE, Tygon and copper tubing
Silicon, PTFE and PVC tubing

[38]

Matrix gas
L1)

N/A (recovery
tests only)
3 days

Tenax TA, Carboxen 569 and molecular sieve

5A sorbents
Tenax TA, Tenax GR, Chromosorb 102,
Carbotrap C, Carbopack B, Anasorb 727,
Anasorb 747 and Potrasil C / n-octane sorbents
Tenax TA sorbent tubes

[31]

Compound(s) tested

H2S, COS, CS2, Me2S, EtMeS, Et2S, Me2S2, MeSH, 2-PrSH

(all at 100 L L1)
H2S, COS, SO2, Me2S, Me2S2, MeSH (all at 1 nL L1)
H2S (5 L L1 and 10 L L1)

H2S, COS, MeSH, Me2S, CS2, 2-PrSH, EtMeS, THT, Et2S,

Me2S2 (all at 0.5 nL L1)
H2S, COS, MeSH, Me2S, CS2, 2-PrSH, EtMeS, Et2S, Me2S2
(402,000 g m3)

Nitrogen

20 hours

Air

N/A (recovery
tests only

H2S, CS2 COS (all at 40 L L1), Me2S (33 L L1), MeSH

(27 L L1)

Nitrogen

5 days

H2S, CS2, Me2S Me2S2, MeSH (all at 10 nL L1, 50 nL

L1and 2 L L1)
H2S, Me2S, Me2S2, MeSH (all at 10 nL L1)

Nitrogen

Nitrogen

Not known

Me2S (2.3 L L1), MeSH (3.7 L L1), EtSH (2.4 L L1),

1-PrSH (2.5 L L1), 2-PrSH (2.4 L L1), 1-BuSH (2.4 L
L1), 2-BuSH (2.4 L L1)

The compounds are: 1-BuSH, 1-butanethiol; 2-BuSH, 2-butanethiol; COS, Carbonyl sulde; CS2, Carbon disulde; 2,5-DMT, 2,5-dimethylthiophene; EtMeS, Ethyl methyl sulde;
Et2S, Diethyl sulde; EtSH, Ethanethiol; 2-EtTEtOH, 2-ethylthioethanol; H2S, Hydrogen sulde; 1-HexSH, 1-hexanethiol; Me2S, Dimethyl sulde; Me2S2, Dimethyl disulde;
MeSH, Methanethiol; 1-Me-1-PrSH, 1-methyl-1-propanethiol; 2-Me-2-PrSH, 2-methyl-2-propanethiol; Me-3TP, Methyl-3-thiopropanoate; 1-PenSH, 1-pentanethiol; 1-PrSH,
1-propanethiol; 2-PrSH, 2-propanethiol; SO2, Sulfur dioxide; THT, Tetrahydrothiophene; 2-TEtOH, 2-thioethanol.

it should be noted that the ISO 11114 series of standards focuses

on only the safety aspects of compatibility and does not consider
whether the gas mixtures within the cylinders will remain stable
over time.

The ISO 11141 series of standards also gives information about

which materials are suitable for use as cylinder valves. For example,
ISO 11114-1, which covers metallic valve materials, allows the use
of carbon steels, stainless steel and aluminum (but not brass or other

46

A.S. Brown et al./Trends in Analytical Chemistry 64 (2015) 4252

copper alloys) for cylinder valves for hydrogen sulde. ISO 11114-2
[40] covers non-metallic valve materials that are more likely to be
used on sample bags (see sub-section 3.3) than cylinders.
When preparing gas standards, cylinders are usually treated by
one or both of two approaches:

reducing the internal surface area of the cylinder (e.g., by

polishing); or,
passivation (e.g., by coating or chemically treating).

Examples of commercially-available cylinder-passivation processes are Spectraseal (BOC), Experis (Air Products) and Aculife (Scott
Speciality Gases).
The storage of sulfur-containing compounds at nmol mol1
amount fractions is signicantly more problematic than at higher
mol mol1 levels, although passivation technologies for these mixtures exist (e.g., commercially-available Sulnert or Silcosteel
treatments).
Data on the stability of sulfur-containing compounds in cylinders and canisters are available in the literature. Trabue et al. [16]
investigated the storage of 10 L L1 of hydrogen sulde, carbonyl
sulde, methanethiol, dimethyl sulde, carbon disulde and dimethyl disulde in a matrix of dried air in fused-silica lined canisters.
Recoveries of these compounds of ~90% were recorded after a period
of four days. Introduction of moisture into the canisters led to
signicantly reduced recoveries of 60% after only 4 h.
Khan et al. [17] evaluated the losses of sulfur-containing compounds on commercially-available (SilcoCan) canisters. Tests using
a mixture of 10 nL L 1 of hydrogen sulde, carbonyl sulde,
methanethiol, dimethyl sulde and carbon disulde in air showed
that when using a six-year-old (old generation) canister, more than
50% of the hydrogen sulde and methanethiol was lost after a period
of only one day. The use of a one-year-old (new generation)
canister yielded much better results more than 97% of all the sulfurcontaining compounds were recovered after three days and, even
after seven days, the measured recoveries were more than 85%
for hydrogen sulde and methanethiol and more than 96% for
carbonyl sulde, dimethyl sulde and carbon disulde.
Sulyok et al. [18] examined the suitability of standard Tedlar bags,
black/clear layered Tedlar bags and Silcosteel-treated cylinders
for storage of a gas standard containing 1 mg m 3 of each of
methanethiol, ethanethiol, dimethyl sulde, ethyl methyl sulde,
2-propanethiol, 1-propanethiol, 2-butanethiol, diethyl sulde and
1-butanethiol in nitrogen. The compounds appeared to be stable in
the Silcosteel-treated cylinders, but recoveries of >100% were often
observed, leading the authors to comment that these recoveries required further investigation. The results from the tests in sample
bags are discussed in sub-section 3.3.
The stability of gravimetrically-prepared gas standards of hydrogen sulde in methane has been studied at NPL. Fig. 2 shows
results from a range of mixtures with amount fractions of hydrogen sulde of 0.5100 mol mol1 with ages from a few days up to
39 months. The data, which were obtained using a GC with a sulfur
chemiluminescence detector (GC-SCD) and Sulnert-treated transfer lines, show that that these mixtures are in general stable (within
the uncertainty of the measurement) over this timescale, the only
signicant exception being the point at t = 730 days, a 1.51 mol mol1
hydrogen-sulde mixtures that gave a measured amount fraction
2.65% less than the gravimetric value. The hydrogen sulde in this
mixture has clearly exhibited some decay or losses to the cylinder
walls, likely to be due to an issue with the passivation of that particular cylinder. However, this single data point notwithstanding,
these results show excellent stability of hydrogen-sulde mixtures of challengingly low amount fractions in passivated cylinders.
Fig. 3 shows new data obtained at VSL from a set of more complex
gravimetrically-prepared synthetic biogas gas standards contain-

Fig. 2. Stability data from a range of gravimetrically-prepared mixtures of hydrogen sulde in methane. The mixtures are shown in three sets by amount fraction:
0.54 mol mol 1 (orange circles), 511 mol mol 1 (red triangles) and 20
100 mol mol1 (brown diamonds). The error bars represent the relative expanded
uncertainty of each measurement.

ing hydrogen sulde (which is expected to be the most reactive

sulfur-containing compound present in biogas) at nominal amount
fractions of 5300 mol mol1 and oxygen at amount fractions of
100700 mol mol1. The mixtures were prepared in accordance with
ISO 6142 [41] in 5-L aluminum cylinders with one of three passivation technologies:

Scott Aculife IV (for the mixture containing nominally 300 mol

mol1 hydrogen sulde);
BOC Spectraseal (200 mol mol1 and 125 mol mol1 hydrogen sulde); and,
Air Liquide AlphaTech (50 mol mol1 and 5 mol mol1 hydrogen sulde).

Fig. 3. Stability data from gravimetrically-prepared synthetic biogas mixtures containing hydrogen sulde at amount fractions of 5.03 mol mol1 (red diamonds),
50.2 mol mol1, 125.3 mol mol1 (green triangles), 202.9 mol mol1 (blue squares)
and 300.6 mol mol1 (purple crosses). For each mixture, the measured hydrogensulde amount fractions are plotted relative to the gravimetric amount fraction, which
is represented by the dashed line. The relative expanded uncertainty of each measurement is ~1.5%; the dotted lines indicate the upper and lower ranges of this
uncertainty from the dashed line.

A.S. Brown et al./Trends in Analytical Chemistry 64 (2015) 4252

The data were obtained using a GC with an atomic emission

detector (GC-AED) and Sulnert-treated transfer lines.
Although it might be expected that hydrogen sulde would react
with the oxygen (as shown in Equation (1)), the hydrogen sulde in
these synthetic biogas gas standards shows good stability over a period
of almost two years, even at an amount fraction of 5 mol mol1.
All measurements show no signicant difference to the gravimetric value within their uncertainty (1.5% relative). The stability of the
hydrogen sulde is comparable to that of hydrogen sulde in gas
standards in the absence of oxygen (Fig. 2). These data therefore
demonstrated that, with appropriate passivation, even thermodynamically favorable reactions can be suppressed to an extent that
these gas mixtures are stable for signicant periods of time.
The new studies therefore revealed that use of an appropriate
cylinder is a crucial contributory factor to the stability of sulfurcontaining compounds even hydrogen sulde at low mol mol1
amount fractions can be stable in cylinders for at least three years
in a matrix of methane, and for at least two years in a matrix of
synthetic biogas (which contains oxygen). Sulfur-containing compounds have been shown to be generally less stable in commerciallyavailable sample cylinders than in the passivated cylinders used at
National Measurement Institutes. However, careful selection of the
most suitable sample cylinders can signicantly reduce losses of
these compounds to levels likely to be acceptable for eld testing
applications, provided that samples are analyzed within a few days.
The presence of water has a dramatic effect on the stability of sulfurcontaining compounds, which is a signicant issue because of the
presence of water in most samples of real biogas.

3.3. Sample bags

Specially designed bags are often used to sample biogases, with
the type of bag employed being dependent on the compound being
measured. Although sample bags are low cost and easy to deploy
in the eld, they are not ideally suited for sampling of sulfurcontaining compounds as losses of these compounds are highly likely
due to absorption into the internal surfaces of the bag, which are
typically not passivated. Other effects that may lead to a change of
the concentration of a gas in a sample bag are permeation through
the walls of the bag or reactions with other gases.
A wide variety of materials used to manufacture sample gas bags
exist [42], e.g.:

polyvinyl uoride (trade name: Tedlar);

polyethyleneterephthalate (trade name Nalophan);
polytetrauoroethylene (PTFE, trade name: Teon);
polyester aluminum;
polyethyleneterephtalate-nylon-aluminum; and,
polyvinylidene diuoride.

Bags constructed from other proprietary materials (e.g., FlexFoil

and FlexFilm) are also available. Specic types of sample bags (e.g.,
black-layered Tedlar) have also been developed to sample lightsensitive compounds. These bags contain carbon black, which may
absorb some compounds, so they are typically constructed with a
layer of clear Tedlar on the inside of the bag, so that the gas does
not come in contact with the carbon black. As is the case with cylinders, the selection of a suitable valve is also critical, and valves
constructed of non-metallic materials are more likely to be used with
sample bags than with cylinders.
The challenges around the accurate measurement of sulfurcontaining compounds in gas samples are well reported in the
literature [43]. A number of detailed studies on the use of bags to
sample low-concentration sulfur-containing compounds in gas standards have been published.

47

Kim [19] evaluated the recovery of 100 nL L1, 200 nL L1 and 300 nL
L 1 of four compounds (hydrogen sulde, methanethiol,
dimethyl sulde and dimethyl disulde) in nitrogen in Tedlar bags
and polyester bags. These mixtures were generated by diluting a
gas standard using sample bags and compared with the results obtained via syringe dilution of the same gas standard. Tedlar bags
were shown to give a mean recovery for all compounds of 87%
(ranging from 82% for methanethiol up to 91% for dimethyl disulde), while polyester bags had a lower mean recovery of 77% (ranging
from 73% for hydrogen sulde up to 83% for dimethyl disulde).
Tests of Tedlar and polyester aluminum bags for the storage of
sulfur-containing compounds for up to three days were performed by Jo et al. [20] for ve different volume fractions (1
10 L L1) of hydrogen sulde, methanethiol, carbon disulde,
dimethyl sulde, dimethyl disulde and sulfur dioxide in nitrogen. The results showed that the stability of the sulfur-containing
compounds depended on the initial volume fraction (more rapid
losses were observed from samples of the highest volume fractions), bag materials (sulfur dioxide showed signicant losses in the
Tedlar bag even after one day) and the type of compounds (sulfur
dioxide was signicant less stable that the other sulfur-containing
compounds).
The study of Rosenberg et al. [18] discussed in sub-section 3.2
also examined the stability of the same gas mixture (1 mg m3 of
nine sulfur-containing compounds) in standard Tedlar bags and
black/clear layered Tedlar bags. In the black/clear layered Tedlar bags,
losses of methanethiol of up to 10% were observed after two days,
whereas in the standard Tedlar bags losses of this magnitude were
not observed until after one week. The heavier thiol compounds were
found to be more stable, with 2-propyl mercaptan exhibiting very
good stability for the one week duration of the study.
Mochalski et al. [21] investigated the use of ve types of sample
bags (transparent Tedlar, black layered Tedlar, PTFE, FlexFoil and
Nalophan), the last of these being custom made by the authors. Commercial gas standards were used to produce a test gas containing
~50 nL L1 of the following six sulfur-containing compounds in nitrogen or air: hydrogen sulde, methanethiol, ethanethiol, carbonyl
sulde, dimethyl sulde and carbon disulde. The work showed that
the recoveries of the compounds from FlexFoil bags were (with the
exception of hydrogen sulde) ~ 100% after 6 h and ~90% after 24 h.
The recoveries from transparent Tedlar bags were found to be nearly
equivalent to those from FlexFoil bags for short storage periods,
whilst the lowest recoveries were consistently reported for Nalophan
and PTFE bags recoveries from PTFE bags being typically only 30%
after 24 h and 10% after 48 h.
Nielsen et al. [22] found no losses from 100 L L1 of nine sulfurcontaining compounds (hydrogen sulde, carbonyl sulde,
methanethiol, dimethyl sulde, carbon sulde, propanethiol, ethyl
methyl sulde, diethyl sulde and dimethyl disulde) in nitrogen after
storage in Tedlar bags for 20 h. During the course of these experiments, the relative humidity (RH) within the bag was found to increase
from that of dry nitrogen (less than 3% RH) to ambient levels (~30%
RH), indicating that moisture from the ambient air had permeated
into the bag. The results obtained for the sulfur-containing compounds are generally consistent to those of the other studies discussed
in this section so much that they appear to demonstrate good stability in Tedlar bags for time periods of one day or less.
Finally, Kim et al. [23] performed a study of the performance
of polyester aluminum bags and Tedlar bags using a mixture of
1 nL L1 of hydrogen sulde, methanethiol, dimethyl sulde, dimethyl disulde, sulfur dioxide and carbon disulde in nitrogen.
Slightly greater losses were exhibited in the polyester aluminum
bags with the recoveries of the lightest sulfur-containing compounds (hydrogen sulde and methanethiol) immediately after
sampling being 88% for the Tedlar bags and 85% for the polyester
aluminum bags.

48

A.S. Brown et al./Trends in Analytical Chemistry 64 (2015) 4252

In new work carried out at SP Technical Research Institute of

Sweden, the stability of gas standards of 4.99 mol mol1 and
9.95 mol mol1 hydrogen sulde in methane was tested in FlexFoil
and FlexFilm bags. The gas was sampled into the bags using a 20cm length of PTFE tubing and the hydrogen-sulde amount fraction
in the bag was measured using optical feedback cavity enhanced
absorption spectroscopy (OFCEAS) by directly connecting the valve
of the bag to the analyzer at a ow rate of 25 mL min1. Fig. 4 shows
the results of the tests with the data shown at day zero being measurements taken immediately after sampling.
The results from the 9.95 mol mol1 gas standard show that the
FlexFilm bag was not suitable for storing hydrogen sulde even for
one day, while the loss of hydrogen sulde when the gas was stored
the FlexFoil bag was found not to exceed 10% even after one week
of storage. However, with both bags, immediate losses of ~16% were
observed even when the analysis was performed directly after the
lling of the bag, indicating that some of the hydrogen sulde is
likely to have adsorbed on the internal walls of the bags.
The results from the 4.99 0.10 mol mol1 gas standard show
that the relative losses of hydrogen sulde are greater at this lower
amount fraction. It is also interesting to note that the absolute
amount fraction of hydrogen sulde lost when sampling the gas from
the cylinder (i.e., the gravimetric value minus the value after zero
days) is approximately the same (1.5 mol mol1) for both gas mixtures. This is a result of the approximately the same amount (number
of molecules) of hydrogen sulde being adsorbed onto the internal surfaces of the each sample bag, which have approximately the
same surface area. The initial losses from the mixture are therefore independent of its initial amount fraction.
The results from the tests with sample bags discussed in this
section indicate that signicant losses of sulfur-containing compounds occur when transferring a gas standard into a sample bag.
This is likely to be due to losses on the untreated internal surfaces
of the bags. The stability of the compounds after these initial losses
varies with the type of compound and amount fraction, but, in
general, Tedlar bags have been shown to be suitable for the shortterm storage of sulfur-containing compounds (although analysis
should still be performed as soon as is practicable after sampling).

Fig. 4. Measured amount fractions of a 9.95 mol mol1 hydrogen sulde in methane
gas standard after storage in sampling bags of FlexFoil (lled red diamonds) and
FlexFilm (open red diamonds), and the measured amount fractions of a 4.99 mol
mol1 hydrogen sulde in methane gas standard after storage in a FlexFoil sampling bag (lled blue circles). The dashed lines represent the amount fraction of
the mixtures in cylinders (before sampling into the sample bags). The relative
expanded uncertainty of each measurement is ~5%.

3.4. Sorbent tubes

A third method for sampling gas mixtures containing lowconcentration sulfur-containing compounds is to use sorbent tubes.
Tenax TA is the most common sorbent for the quantitative adsorption of volatile organic compounds (VOCs) and is suitable for
compounds with boiling points of 70320C, meaning that it can
be used for the analysis of a number of sulfur-containing compounds including various thiols, suldes and thiophenes, and
dimethyl disulde. A wide range of other sorbent materials are available [44]. Analysis of the compounds adsorbed on sorbent tubes can
be performed by a number of methods, but is most commonly
carried out by thermal desorption-GC-MS. The thermal desorption is typically performed in two steps:
(1) the tubes are rst heated to transfer the compounds to a cold
trap for cryo-focusing; and,
(2) the trap is then rapidly heated, releasing the trapped compounds for injection into the GC-MS.
A study by Mochalski et al. [24] investigated the measurement
of a gas standard of 20 nL L1 of ve sulfur-containing compounds
(methanethiol, ethanethiol, dimethyl sulde, carbonyl sulde and
carbon disulde) in nitrogen. The recovery of these compounds from
a dual-bed sorbent tube containing Tenax TA and Carboxen 1000
was found to be 9899% for all compounds if analysis took place
immediately after sampling, although signicant losses of the compounds were found if the tubes were stored for 24 h recoveries
then varied from ~12% (for methanethiol) to ~88% (for carbon disulde). It is therefore recommended that analysis is performed as
soon as possible after sampling.
In the rst of three studies published by Devai and DeLaune [25],
the recovery of hydrogen sulde from a range of different sorbents was investigated. A volume of 0.4 mL of a gas mixture
containing 40.0 L L1 hydrogen sulde (and four other sulfurcontaining compounds) was sampled. The best recoveries were
obtained from silica gel plus molecular sieve (79.1%), and silica gel
(78.7%). Three other sorbents (molecular sieve, molecular sieve plus
silica gel, and molecular sieve plus Tenax TA) recovered ~40% of the
hydrogen sulde, with negligible recoveries reported for the other
sorbents. A similar study [26] using carbonyl sulde (at a mass of
carbonyl sulde equivalent to 9 ng of sulfur sampled from a gas
mixture containing 40.0 L L1 of carbonyl sulde), showed that that
best recovery value (99.7%) was obtained using Carbotrap 301. Other
very high recoveries were obtained from silica gel and molecular
sieve (90.4%) and silica gel alone (90.3%), with three sorbents
(Carbotap 100, Carbotap 150 and Tenax TA) trapping negligible
amounts of carbonyl sulde. For the third compound studied,
methanethiol [27] (at a mass of methanethiol equivalent to 6.57 ng
of sulfur sampled from a gas mixture containing 26.9 L L1 of
methanethiol), the best two performing tubes were silica gel and
molecular sieve (99.2% recovery) and silica gel alone (96.4%), with
negligible recoveries reported for Carbotrap 150, Carbotrap 400 and
Carboxen 569.
Andersen et al. [28] performed storage tests on inert coated
stainless-steel sorbent tubes packed with Tenax TA (35/60) and carbonized molecular sieve (60/80) using a methanethiol volume
fraction of 124 nL L1 (diluted from a gas standard of 4.97 L L1 nitrogen). For the short-term recovery tests, a total mass of 0.63
0.71 g of methanethiol was sampled onto the tubes. When the tubes
were stored at 0C, recoveries were ~100% for storage times up to
5 h; however, for tubes stored at room temperature, the recovery
after 5 h was only 20%. Longer-term storage studies were performed on these and two other types of tubes (inert coated stainlesssteel sorbent tubes packed with Tenax TA, and stainless-steel tubes
packed with silica gel). For all three types of tube, recoveries of above

A.S. Brown et al./Trends in Analytical Chemistry 64 (2015) 4252

60% were reported when stored in a freezer for up to 100 h, although almost all methanethiol was lost when the tubes were stored
at room temperature.
A study by Baltussen et al. [29] compared the performance of
three sorbents [i.e., polydimethylsiloxane (PDMS), Carbotap 300
and Tenax] for sampling nine sulfur-containing compounds in a
liquid mixture at mass concentrations of 3002250 g L1. 1 L
of the mixture was used to perform the tests. Recoveries of
tetrahydrothiophene, 1-pentanethiol, 1-hexanethiol, 2-thioethanol,
methyl-3-thiopropanoate and 2-ethylthioethanol were all ~100%
on the PDMS sorbent. For the other three compounds studied (2propanethiol, 2-methyl-2-propanethiol and 1-propanethiol)
recoveries on PDMS were reported as 2%, 14% and 25%, respectively. Higher recoveries for all of these three compounds were reported
on the Tenax tubes and for the rst two of these compounds on
the Carbotrap tubes.
Lestremau et al. [30] studied the behavior of nine sulfurcontaining compounds at 402000 g m3 in air on three different
sorbents (i.e., Tenax TA, Carboxen 569 and molecular sieve 5A). Losses
of methanethiol were observed on all three sorbents. On Tenax TA,
some methanethiol was found to convert to dimethyl disulde
the measured GC-MS dimethyl disulde peak area was ~10% that
of the methanethiol peak. A similar reaction occurred on molecular sieve 5A (where the measured dimethyl disulde peak area was
25% of that of the methanethiol peak area). However, on Carboxen
569, all of the thiols and hydrogen sulde were found to have converted into SO2, but the authors noted that Carboxen 569 is not
normally employed for sampling sulfur-containing compounds.
Sunesson et al. [31] investigated the recovery and the storage
stability of a number of microbially-produced organic compounds
(including one sulfur-containing compound dimethyl disulde)
on eight different sorbents. Recovery tests were rst performed using
a gas from a test chamber containing 50 g m3 of dimethyl disulde in air with an RH of 85%. High recoveries were reported from
Tenax TA (103%), Anasorb 727 (90%) and Tenax GR (89%). Four sorbents (i.e., Tenax TA, Tenax GR, Carbotarp C and Chromosorb 102)
were then selected for further recovery tests at two dimethyl disulde mass concentrations (1 g m3 and 50 g m3) each at two
RHs (20% and 85%). It was found that recoveries from Tenax TA and
Tenax GR sorbents were effectively independent of concentration
and RH. For Chromosrob 102, the recovery of 1 g m3 of dimethyl
disulde at 85% RH was only 37%, approximately half of that from
the same sorbent at all other conditions. The recoveries from
Carbotrap C were in all but one instance < 2%. The results of storage
stability tests of 1 g m3 of dimethyl disulde at 85% RH were also
reported after storage in a freezer for two weeks. No decay was observed for dimethyl disulde on the two Tenax sorbents, but
recoveries of <2% were reported for both Chromosrob 102 and
Carbotrap C after storage under these conditions.
In work that is presented here for the rst time, a solution of six
sulfur-containing compounds (ethyl methyl sulde, 1-methyl-1propanethiol, 1-butanethiol, dimethyl disulde, tetrahydrothiophene
and 2,5-dimethylthiophene) at ~5 mg mL1 in diethyl ether was prepared and 2 L of this solution was introduced in a Tedlar bag containing
2.5 L of air. The resulting mass concentration of each sulfur-containing
compound in air was ~4 mg m3. 100 mL of the gas from the Tedlar bag
was then transferred into each of 10 Tenax TA sorbent tubes. Two of
these tubes were then analyzed after each of the following time periods
(days): 1, 2, 7, 10 and 13, with the average recoveries calculated from
these experiments shown in Fig. 5. Recoveries were found to be more
than 90% for all sulfur-containing compounds even after a period of
13 days. Little variation was observed in the decay rates of the compounds studied, but decay was not unexpected considering the
non-volatile nature of the compounds.
The studies discussed above encompass a wide range of sorbent
materials, compounds and concentrations, and it is clear that careful

49

Fig. 5. Measured recovery of six sulfur-containing compounds sampled onto Tenax

TA after periods of time of up to 16 days. The symbols represent: ethyl methyl sulde
(orange diamonds), 1-methyl-1-propanethiol (red crosses), 1-butanethiol (dark blue
triangles), dimethyl disulde (green circles), tetrahydrothiophene (light blue squares)
and 2,5-dimethylthiophene (purple crosses). The black dashed line indicates the expected (100%) recovery. The upper and lower ranges of the relative expanded
uncertainty of each measurement (~15%) are indicated by the dotted lines.

selection of the sorbent material used is essential very large variations in recoveries were reported for the different sorbent materials
investigated. In general, Tenax TA appears to be a suitable choice
of sorbent for all but the lowest-molecular-weight sulfur-containing
compounds. Appropriate storage of the sorbent tubes after sampling is also critical, with the observed losses of methethiol being
signicantly lower for tubes stored at 0C than for those stored at
room temperature.
3.5. SPME
SPME can be used for the extraction of analytes from different
matrices (including gases), and has a similar advantage to sorbent
tubes in that it performs sampling and pre-concentration in a single
step. SPME can be coupled directly to a range of analytical instrumentation, such as GC, and its use in the analysis of sulfur-containing
has been studied in detail [45].
Haberhauer-Troyer et al. [32], investigated the performance of
Carboxen-PDMS SPME for the analysis of a dynamically-generated
gas standards in air of 13 nL L1 methanethiol, 17 nL L1 dimethyl
sulde, 5 nL L1 2-propanethiol and 5 nL L1 2-butanethiol. Recoveries of all four compounds (at 9C) were shown to be ~100% after
30 min, but signicant losses were observed after 29 h and 50 h
the recoveries were highest for methanethiol (57% after 50 h) and
lowest for 2-propanethiol (10% after 50 h). Losses of the compounds were reduced at lower temperatures the recoveries of
methanethiol and 2-propanethiol after 50 h at 23C were 100% and
65%, respectively.
In a related study [33], the same authors investigated the behavior of the same four compounds (at volume fractions of 15 nL
L1) on two types of Naon membrane driers and polyphenylene
wool (an ozone scrubbing material). No signicant losses of any
compound were observed (with either drier) for gases with RH
of 50%, but losses of up to 30% were reported for the thiols for
gases with higher RH. Higher recoveries were reported for dimethyl sulde, where no losses were reported, even when using a
gas with 92% RH.

50

A.S. Brown et al./Trends in Analytical Chemistry 64 (2015) 4252

Using Carboxen-PDMS SPME, Neilsen et al. [34] studied the behavior of nine sulfur-containing compounds at 0.5 nL L1 in nitrogen.
An extraction temperature of 15C was used and recoveries between
100% (for 2-propanethiol) and 11% (for diethyl sulde) were reported. In general, the losses were higher for the sulfur-containing
compounds with the highest boiling points; other low recoveries
were reported for dimethyl disulde (18%) and ethyl methyl sulde
(41%).
The study of Lestremau et al. discussed above [30] also investigated the performance of the sulfur-containing compounds on
PDMS-Carboxen SPME. Signicant degradation of some of the compounds was observed, particularly methanethiol (to form dimethyl
disulde) and 2-propanethiol (to form diisopropyl disulde). As
with the studies on sorbent tubes in the same paper, quantication of these losses was performed by the measurement of relative
peak area in the worst example of degradation, the measured
GC-MS peak area of dimethyl disulde was 60% of the peak area
of methanethiol.
Although only a small number of studies have been published
using ways to sample low concentrations of sulfur-containing compounds, the results indicate that signicant losses of the more volatile
compounds do occur. We therefore recommend the use of passivated cylinders or Tenax TA sorbent tubes for these compounds.
However, SPME may be a suitable candidate for sampling heaviermolecular-weight sulfur-containing compounds.
3.6. Glass sampling bulbs
Although rarely used for sampling biogas and natural gas, glass
sampling bulbs are sometimes employed for ambient air sampling. Davai et al. [35] performed a study of the stability of a gas
mixture containing ~40 L L1 carbon disulde, carbonyl sulde
and hydrogen sulde, 33 L L1 dimethyl sulde and 27 L L1
methanethiol in nitrogen in a 125-mL glass sampling bulb. All compounds reported minimal losses of less than 5% after 24 h. No further
losses of hydrogen sulde and carbonyl sulde were observed for
periods up to ve days, but losses of 1550% were reported for the
other three compounds over this period. Tests with the same compounds in air revealed losses of ~5% and 12% for hydrogen sulde
and carbonyl sulde, respectively, over ve days; and, the results
from the other compounds were similar to those in nitrogen.
The most striking result was from tests in moist air, where losses
of hydrogen sulde of 95% after only 24 h were revealed. The authors
concluded that, at the concentrations studied, glass sampling bulbs
can be used to collect dried air samples if there are measured within
3 h, but the vessels are not appropriate for use with moist gases.
4. Transferring gas from sample vessels to analyzers
4.1. Introduction
Accurate, reliable transfer of gas is a crucial part of performing
accurate analysis, as any changes to the gas composition before
reaching the analyzer will affect the results obtained. This applies
to both on-line and off-line analysis, but this section focuses on transferring gas from a sample vessel into an off-line instrument, such
as a GC.
As sulfur-containing compounds have the propensity to absorb
to surfaces [46], it is essential that suitable pressure-regulation
devices and lines are used when transferring gas to an analyzer. A
general consideration is that the total internal volume of the regulators and pipework used should be kept to a minimum as the
internal surfaces of pipework and dead volumes (internal volumes
that are out of the ow path) within transfer lines can cause losses
of sulfur-containing compounds.

When introducing a gas into an analyzer, the system must be

fully purged in order to remove air, water, other contaminants or
traces of the previous gas. The normal procedure for purging an analyzer is to use a number of ll and empty cycles [47], although
this depends on the gas being of sucient pressure, which may not
always be the case with samples of biogas, particularly those in
sample bags. An alternative method is to evacuate the transfer lines
using a vacuum pump, but this may not be possible in all cases, particularly with gases, such as biogas, that are hazardous and/or
ammable.

4.2. Regulators and other pressure-reduction devices

A pressure regulator or pressure-reducing device is usually required in order to transfer a gas into an analyzer. When analyzing
sulfur-containing compounds, it is essential to ensure that the material of the device is suitably passivated and that the dead volume
of the device is suciently low. Pressure-regulating devices containing permeable materials should be avoided, as they could allow
a diffusion pathway between the sample and atmosphere.
Although some commercially-available pressure regulators are
available with internal volumes of only a few cubic centimeters, a
preferred approach is to use a device, such as a needle valve [46],
or another ow-restricting device connected directly into the cylinder valve. However, extreme care must then be taken that such
a device is capable of withstanding the pressure of the sample,
and that no local or national safety regulations prohibit such an
arrangement. An alternative approach, which can be used in
conjunction with the other pressure-regulation devices, or by
itself (if the sample is at a low pressure), is to use a back-pressure
regulator downstream of the analyzer. As the device is located after
the analyzer, it does not need to be passivated. However, when using
a back-pressure regulator, it must be noted that it is possible
for a pressure gradient to form across the length of the transfer line,
which must be avoided for an analyzer that cannot internally control
pressure.

4.3. Transfer lines

The selection of a transfer line of appropriate material is essential in order to achieve accurate, repeatable analysis results. The use
of a material that is unsuitable may cause articially low results to
be reported due to adsorption of the sulfur-containing compounds onto the internal surfaces of the transfer lines, and a large
number of repeat measurements are likely to be required before a
stable reading is obtained.
When analyzing sulfur-containing compounds, the best practice is to use a narrow-bore (such as 1/16-inch external diameter)
stainless-steel transfer line passivated with a treatment (e.g., Sulnert
or Silcosteel). The ISO standard for handling calibration gases, ISO
16664 [48], also suggests that transfer lines of the following materials are suitable for use with hydrogen sulde at amount fractions
less than 10 mol mol1: nickel, PEEK, silica-lined PEEK, glass quartz
and uorinated ethene-propene.
The effects of using different tubing materials on gas standards
of sulfur-containing compounds have been investigated in a number
of literature studies (see Table 2). Kim et al. [36] investigated biases
in the measurement of 10 nL L1, 50 nL L1 and 2 L L1 hydrogen
sulde, methanethiol, dimethyl sulde, carbon disulde and dimethyl disulde in nitrogen using a GC with PTFE and stainlesssteel transfer lines and a range of different gas-ow rates. The losses
from PTFE were almost insignicant, whereas those from stainlesssteel transfer lines were shown to be up to 45%, with the losses being
greatest when low ow rates were used.

A.S. Brown et al./Trends in Analytical Chemistry 64 (2015) 4252

In a different study, Kim et al. [37] compared the performance

of Silcosteel-treated stainless-steel tubing against ve other materials (i.e., stainless steel, silicone, PTFE, Tygon and copper) using
10 nL L1 hydrogen sulde, methanethiol, and dimethyl sulde and
dimethyl disulde in nitrogen. Silcosteel-treated stainless-steel tubing
was generally found to result in lower levels of losses of the sulfurcontaining compounds compared to any other material, although,
for dimethyl sulde, the performance of all materials (except copper)
was found to be similar, and, for dimethyl sulde, little difference
was observed between Silcosteel-treated stainless steel and untreated stainless steel. In general, use of copper tubing resulted in
greatest losses of the lighter compounds (hydrogen sulde and
methanethiol), whereas losses of dimethyl sulde and dimethyl
disulde were greatest with silicone tubing.
Rosenberg et al. [38] tested the performance of tubing made from
three materials (i.e., silicon, PTFE and PVC) when used to ll Tedlar
bags with a gas mixture of hydrogen sulde (3.7 L L1) and six other
sulfur-containing compounds (all at 2.32.5 L L1). The results
showed that, of the three materials tested, PTFE resulted in the least
losses. The use of silicon tubing resulted in the greatest losses of
sulfur-containing compounds with, as expected, losses increasing
with the length of tubing used.
5. Conclusions
This article reviewed the current state of the art for the sampling of standard gas mixtures containing low-concentration sulfurcontaining compounds. Because synthetic gas standards have known
compositions and their stability can be determined from a priori
knowledge of identical mixtures, they are ideally placed to test the
storage and transfer losses of sulfur-containing compounds, thereby
elucidating the performance of the sampling media under ideal
conditions.
When sampling sulfur-containing compounds, the selection of
a cylinder with suitable passivation is shown to be crucial to the
stability of the compounds. Results presented here for the rst time
show that hydrogen sulde at low mol mol1 amount fractions can
be stable in suitably passivated cylinders for at least three years in
a matrix of methane, and for at least two years in a matrix of synthetic biogas (including oxygen). By comparison, the stability of sulfurcontaining compounds in commercially available sample cylinders
is highly variable, and is deleteriously affected by the presence of
water, which is expected to be present in most samples of real biogas.
The data from tests on sample bags showed that signicant losses
of sulfur-containing compounds occur as soon as the gas is sampled
into the bags. The rate of decay of the compounds after these initial
losses is dependent on the bag material and the compound (hydrogen sulde is particularly unstable), but, in general, these
compounds are much less stable in sample bags than in cylinders.
The studies in the literature on sorbent materials show that Tenax
TA appears to be a suitable choice of sorbent for all but the lowestmolecular-weight sulfur-containing compounds. Studies using
Carboxen-PDMS SPME and glass sampling bulbs to sample sulfurcontaining compounds have also been presented although the
available data are limited, we can conclude that the use of passivated cylinders or Tenax TA sorbent tubes is likely to lead to lower
losses of these compounds when sampling. However SPME may be
a suitable candidate for sampling heavier-molecular-weight sulfurcontaining compounds.
We also discussed best practice for transferring gas from sample
vessels to analyzers, with recommendations made on issues such as
the selection of regulators (or other pressure-reducing devices) and
transfer lines. A review of the available literature for transferring gas
standards of sulfur-containing compounds into analytical instrumentation showed that the use of Silcosteel-treated stainless steel or PTFE
tubing generally results in the lowest losses of these compounds.

51

Overall, the work shows that losses of sulfur-containing compounds are likely to occur when taking and storing samples, and
when transferring the gas sample into an analyzer. The key issue
preventing accurate measurement of these compounds is that there
is unlikely to be a piori knowledge of their concentration so that
corrections for these losses cannot be applied based on the data in
the studies reviewed in this article.
One possible approach to correct for these losses would be to
treat the calibration-gas mixture in exactly the same manner as the
standards (i.e., storing the calibration gas in the same medium as
the sample for the same period for time before injecting into the
analyzer). The drawback with this approach is that losses to adsorption of the internal walls of cylinder and sample bags are not
proportional to the concentration of the analyte, so some prior
knowledge of the concentration of the analyte in the sample would
still be needed.
A second possible approach would be to use a tracer compound to model the losses. If a known amount of the tracer (ideally
a compound with physico-chemical characteristics similar to the
analyte that is not expected to be present in the sample) is added
to the sample immediately after it is taken, measurement of the concentration of this compound can elucidate information about the
losses of the analyte, thus allowing a correction factor to be applied.
A third possibility is to use a standard-addition approach [49],
in which analysis of the sample is performed after incremental additions of known amounts of the analyte, and the concentration of
the analyte is determined by extrapolating the response function
generated.
However, in order to ensure that accurate measurement of biogas
can be performed routinely and at low cost by testing laboratories,
further development of novel passivation chemistries is likely to be required in order to tackle the problem at source by reducing the losses
experienced in cylinders and sample bags, and on sorbent tubes.
Acknowledgements
This article was written under the European Metrology Research Programme (project ENG01: Characterisation of Energy
Gases), and the authors would like to acknowledge the funding of
this Programme by EURAMET (The European Association of National Metrology Institutes) and the European Commission.
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