Proceedings of the XVI ECSMGE

Geotechnical Engineering for Infrastructure and Development

ISBN 978-0-7277-6067-8

© The authors and ICE Publishing: All rights reserved, 2015

doi:10.1680/ecsmge.60678

Use of derived terms for sulfur-species in geological

materials
L'utilisation de termes dérivés de soufre-espèces dans des matériaux
géologiques
T.W. St John*1
1
Department of Earth Sciences, University of Bristol, Bristol, UK
*
Corresponding Author

ABSTRACT An assessment of the sulfur/sulfide content of ground materials for civil engineering purposes is essential in order to under-
stand the potential for sulfate development. In the absence of detailed petrographic/mineralogical data, terms such as "total potential sul-
fate", "oxidisable sulfides" and "equivalent pyrite" are often derived from sample test results for total sulfur, water-soluble sulfate and acid-
soluble sulfate. Their most common application is in the routine classification of aggressive ground. Despite the widespread use of these
terms in highways and earthworks specifications, there is little discussion in the literature concerning the limitations and suitability of their
application. This paper reviews the common derived sulfur-species terms and discusses the factors that should be considered when inter-
preting chemical data. A simple graphical approach for interpreting the sulfur-speciation of geological materials is presented and practical
applications are discussed.

RÉSUMÉ Une évaluation de la teneur en soufre / sulfure de matériaux du sol à des fins d'ingénierie civile est indispensable pour com-
prendre le potentiel de développement du sulfate. En l'absence de données pétrographiques / minéralogique détaillée, des termes tels que
"total potential sulfate", "oxidisable sulfides" et "equivalent pyrite" sont souvent tirées des résultats de test de l'échantillon pour soufre total,
sulfate soluble dans l'eau et le sulfate soluble dans l'acide. Leur application la plus courante est la classification systématique des sols agres-
sifs. Malgré l'utilisation répandue de ces termes dans les routes et les travaux de terrassement cahier des charges, il est peu question dans la
littérature concernant les limites et les qualités de leur application. Ce document passe en revue les dérivés soufrés termes communs à l'es-
pèce et examine les facteurs qui devraient être considérés lors de l'interprétation des données chimiques. Une approche graphique simple
pour l'interprétation de la spéciation en soufre des matériaux géologiques est présenté et les applications pratiques sont discutées.

1 INTRODUCTION ture and guidance documentation, with some repre-

The presence of sulfur-species in geological materi-
als can lead to a range of engineering problems, in-
cluding acid-corrosion and/or sulfate attack on buried
structures as well as sulfate-induced expansion of ag-
gregates. An assessment of sulfur-species is therefore
essential for classifying materials. Within a typical
geological material, the speciation of sulfur can vary
considerably (Figure 1).
Over the past two decades, the use of derived
chemical terms for assessing sulfur-species in geo-
logical materials has gained popularity, particularly
for earthworks and highways schemes. At least 20
terms have been described in the engineering litera-
senting the same derivation with different nomencla-
ture. Of these 20, eight are regularly used and are de-
termined as mathematical calculations (Table 1).
In the UK, the tests from which the terms are de-
rived are known as water-soluble sulfate (WS), acid-
soluble sulfate (AS) and total sulfur (TS). Tradition-
ally, the results have been provided in units of
mgSO4/l, % SO4 and % S for WS, AS and TS respec-
tively. As recommended by Reid et al. (2005), these
results are easiest to compare when provided consist-
ently in units of percent sulfur (% S). The acronyms
WSS, ASS and TS are used in this paper to represent
water-soluble sulfur, acid-soluble sulfur and total sul-
fur respectively.

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tion. This paper discusses existing and proposed de-

rived terms and examines the factors that should be
considered if the terms are to be suitably applied.

2 ASSESSMENT OF DERIVED TERMS

Derived chemical terms can be used in combination

with mineralogical/petrographic information (such as
X-ray diffraction (XRD) or Scanning Electron Mi-
croscopy (SEM) data) to provide a detailed investiga-
tion of sulfur-species in geological materials. If the
terms are to be applied meaningfully, an understand-
ing of their definition, derivation and limitations is
important. Knowledge of the geochemistry of the as-
sociated test methods is also useful for interpretation
of the results.

2.1 Sulfate terms

Figure 1. Typical sulfur-species in geological materials. Common
minerals also shown. Rare and gaseous sulfur-species excluded. In order to assess the worst-case ground aggressivity
conditions with respect to sulfate production, the “to-
tal potential sulfate” (TPS, units % SO4) is often used
Table 1. Derived terms. Pyr: pyrite, gyp: gypsum, TS: total sulfur,
ASS: acid-soluble sulfur, AS: acid-soluble sulfate, WSS: water-
(Reid et al. 2005, BRE 2005). The TPS is derived by
soluble sulfur, WS: water-soluble sulfate. 1Reid et al. (2005), converting the TS test result to sulfate; making the
2
Hawkins and Pinches (1997), 3CTQ (2001), 4NSAI (2013), 5BRE assumption that all sulfur in a sample could ultimate-
(2008). ly oxidise to produce sulfate. Alone, the TPS gives
Term Equation Units no indication as to what proportion of sulfate is cur-
Total potent. SO4 (TPS)1 TPS = 3 x TS % SO4 rently in a sample, or what proportion could develop.
Sulfide content (SC)2 SC = TS-ASS %S In practice, this conservative estimation is unlikely
Oxidisable sulfides (OS)1 OS = TPS-AS % SO4 to develop in most ground-engineering environments
Equiv. pyrite (EP)3 EP = 1.87 x (TS-WSS) % pyr within the design life of a structure. However, certain
Estimated pyrite (EsP)4 EsP = 0.623 x OS % pyr conditions such as material exposure and/or heating
Pyrite content (PC)1 PC = 1.87 x TS % pyr may cause oxidation. The rapid high-temperature
Actual pyrite (APC)5 APC = 0.623 x OS % pyr combustion (HTC) process for TS extracts all sulfur
Equiv. gypsum (EG)3 EG1 = 1.79 x WS % gyp (BRE 2011) and consequently, the presence of low-
solubility sulfates (such as barite, BaSO4 or celestite,
SrSO4) can render the TPS unrepresentative in terms
Two major groups of derived terms can be distin-
of the sulfate that might be leached from the material.
guished; those that estimate sulfate contents and
A more realistic approach to estimating sulfate
those that estimate sulfide contents. Estimations may
development is the determination of total reduced
be in the form of strict chemical derivations (with
sulfur (TRS) (Reid et al. 2005) followed by conver-
units of % SO4 or % S) or may represent equivalenc-
sion to sulfate (TRSS) (1). This approach assumes
es of mineral phases (such as pyrite or gypsum). Due
oxidation of reduced sulfur-species (such as pyrite)
to the historic nature of many of the terms, there is
only and circumvents the problems introduced by the
often inconsistency in the units used.
presence of insoluble sulfates. Unfortunately the use
The terms are found in most major UK and Irish
of this test in industry is rare.
engineering codes/guidance for assessing sulfur-
species, but little information exists as to the limita- TRSS (% SO4) = 3 x TRS (1)
tions that require consideration during their applica-

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2.1.1 Equivalences of sulfate minerals
Sulfate mineral equivalences involve a conversion
from the WS, AS or TS value based on the ideal pro-
portions of sulfate or sulfur in the composition of the
mineral. For equivalences of gypsum (CaSO4.2H2O),
examples include those of Razouki et al. (2011)
(based on AS) and Beech et al. (2003) (using TS).
Calculation of gypsum equivalents using the TS or
AS content assumes that all sulfur or sulfate (respec-
tively) in a sample is derived from gypsum. Whilst
gypsum is globally the most common sulfate, this as-
sumption may be invalid for certain materials, espe-
cially evaporite sequences and low pH soils. Use of
the WS content may underestimate the gypsum con-
tent, particularly if WS values indicate gypsum satu-
ration in the soil extract. Gypsum over-saturation (>
c. 1.5 gSO4/l) indicates the presence of sulfates
sourced from minerals other than gypsum.
“Equivalent gypsum” (EG) was formalised in
Canada (CTQ 2001) and converts the WS to gypsum.
However, the CTQ extract uses boiling water and a
12:1 (water:soil) dilution ratio, inconsistent with
UK/EN methods. Consequently, consideration should
be given to test methods before derivations are made.
2.2 Sulfur/sulfide terms
In the simplest case the non-sulfate sulfur (TS minus
ASS) can be assumed to represent sulfide-sulfur.
This may be described with various terms including
“insoluble sulfur” “sulfide-sulfur” and commonly,
the “sulfide content” (SC). Alternatively, the non-
sulfate sulfur can be calculated in units of % SO4
(TPS-AS) to derive the “oxidisable sulfides” (OS)
content. The OS has been applied to the classification
of aggressive ground for a range of purposes, includ-
ing as an indicator of the presence of pyrite if the
value exceeds 0.3 % SO4 (BRE 2005). The units used
for this term are misleading and do not necessarily
represent the speciation of sulfur in the sample.
The major limitation in approximating non-sulfate
sulfur in this manner is the assumption that the TS
accounts for all sulfur and that the ASS accounts for
all sulfate-sulfur, in the sample. The former is rea-
sonable in most cases whilst the latter may be invali-
dated in the presence of low-solubility sulfates.
The assigning of non-sulfate sulfur to the sulfate
phase (the OS) relies on the assumption that the for-
St John
mer can be oxidised to SO4. Complete oxidation is
unlikely in the presence of low-reactivity sulfur-
species and where coatings of oxidation products
form on sulfides allowing them to remain largely in-
tact. A more accurate estimate of the oxidisable sul-
fur-species is given by the TRS.
2.2.1 Equivalences of sulfide minerals
Non-sulfate sulfur can be used to estimate the abun-
dance of sulfide minerals such as pyrite (Reid et al.
2005). In a simple case, the TS can be assumed to be
sourced entirely from pyrite (“pyrite content”, PC).
This is reasonable in unweathered pyritic deposits,
devoid of primary sulfates or other sulfur sources.
This method can be used to estimate the original py-
rite content of a material (Maher et al. 2011).
Milner (1962) proposed that pyrite could be esti-
mated by converting non-sulfate sulfur (% S) to py-
rite, reducing the influence of sulfate phases. The OS
(% SO4) can also be converted to pyrite to derive the
“actual pyrite content” (APC) and the “estimated py-
rite” (EsP) (BRE 2008, NSAI 2013). “Equivalent py-
rite” (EP) may be estimated using the difference be-
tween the TS and the WSS (CTQ 2001). Since the
CTQ aqueous extract may not leach all sulfate from a
sample, pyrite can be overestimated.
Pyrite estimations ignore the potential for other
sulfides to account for sulfur. Whilst less abundant,
pyrrhotite and other metal-sulfides may be present in
some lithologies. Pyrrhotite equivalences could be
determined, however the composition (Fe1-xS, 0 ≤ x ≤
0.125) is such that the conversion factor from OS
would range from around 0.84 to 0.92. A simple
chemical test for the determination of monosulfides
such as pyrrhotite is outlined in Reid et al. (2005).
2.3 Limitations of derived terms
In addition to the term-specific limitations, the fol-
lowing are common to all terms and may require
consideration depending on the materials end-use.
a) No indication of sample’s sulfur distribution.
b) No indication of mineral form or reactivity.
c) Static indications at time of testing only.
d) Errors inherited from sampling and testing.
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Geotechnical Engineering for Infrastructure and Development

2.3.1 Example sulfur-speciation problems cisely or visually estimated. Sulfur-sulfate plots can
be used to assess the weathering of materials, com-
A sulfur-speciation analysis determined for lignite-
pare datasets, identify implausible results and classify
bearing clay (with 27 % Corganic) demonstrates the ef-
geological materials using consistent units.
fect of organic sulfur (Table 2). In this example, the
TRS and ASS summate to 5 % S less than the TS, in-
dicating that the remaining sulfur is neither in the
form of sulfate or sulfide (reduced) and may be par-
tially organic bound. Without knowledge of the TRS,
equivalences based on TS and AS could be in error.

Table 2. Sulfur-species data for UK lignite-clay and barite-rich

mineralised sandstone, after Reid et al. (2005).
Lignite Mineralised
Sulfur species (% S)
clay sandstone
Water-soluble sulfur, WSS 0.15 0.001
Acid-soluble sulfur, ASS 0.69 0.3
Total sulfur, TS 16.06 7.75
Total reduced sulfur, TRS 10.28 -

Practically insoluble sulfate minerals such as bar-

ite do not leach significant concentrations of SO4 dur-
ing water or acid (dilute HCl) extraction. However,
the HTC TS test can extract sulfur from these phases.
As a result, the TPS value can overestimate the max-
imum concentration of sulfate that may develop over
time. The non-sulfate sulfur, any derived terms and
potential material classifications may also be in error.
An example for a barite-rich sandstone has a high
TS content of 7.75 % S and corresponding TPS value
of around 23 % SO4 (Table 2). As a result of the
presence of barite, the ASS and WSS values are low
and the apparent non-sulfate sulfur content (7.45 %
S) may lead to overestimates of sulfide equivalences.
In general, pure sandstones have low primary sulfide
contents, however post-depositional sulfide minerali-
sation may have occurred. In such cases petrographic
examination is essential for clarification and precise
assessment.
3 GRAPHICAL APPROACH
A factor of three (2.996) separates % S and % SO4
for sulfur-species data, such that a straight-line rela-
tionship exists when the two are plotted against one
another (Figure 2). Using a simple spreadsheet with
plotting capabilities, the OS and non-sulfate sulfur
can be displayed and assessed; either calculated pre-
Figure 2. Sulfur-sulfate plot for TS = 0.9 % S, AS = 0.8 % SO4
and WS (2:1) = 1500 mgSO4/l, with appropriate conversions.
3.1 Weathering assessment
Sulfur-sulfate plots can be used to interpret the
weathering of sulfide-bearing geological materials.
For a dataset of stockpiled Carboniferous (Cracking-
ton Formation) mudrock (near Barnstaple, Devon,
UK), sulfur-sulfate plots can be used to understand
unusual sulfur-speciation developed over 10 or more
years (Hyder 2012). On average, samples recovered
from the stockpile surface (Figure 3) have much low-
er sulfate contents than samples towards the base, at
1.5-2 m depth (Figure 4). This is likely a result of ox-
idation of sulfur (sulfides) at the surface following by
downward leaching of sulfates (particularly the wa-
ter-soluble sulfates).
The weathering history of the material prior to
placement is not known however if it is assumed that
the material was relatively homogeneous, (e.g. the
spoil was derived from a particular horizon) then it
would be anticipated that the initial TS would be
generally consistent throughout the stockpile depth.
Lower TS in the surface material suggests that it
has oxidised and leached out and/or downward. WS
values approaching gypsum saturation suggest that
this mineral may be present in the deeper samples.

3380

The stockpile observations show that total sulfur may
not be static in placed materials, such that the TPS
can only provide an indication at the time of testing.
Figure 3. Average (N=3) sulfur-sulfate plot for surface samples of
stockpiled Carboniferous mudrock, after Hyder (2012).
Figure 4. Average (N=4) sulfur-sulfate plot for 1.5-2.0 m deep
samples of stockpiled Carboniferous mudrock, after Hyder (2012).
Also highlighted by the use of sulfur-sulfate plots
is the high proportion of non-sulfate sulfur (% S) in
the two material types. The surface and deeper sam-
ples have high non-sulfate sulfur at 63 and 76 % of
the total sulfur, respectively. Based on a theoretical
estimate considering linear oxidation, static TS and a
10-year stockpiling duration, it may take at least a
further 20 years for the non-sulfate sulfur in the up-
per material to completely oxidise to sulfate. In prac-
tice complete oxidation is unlikely.
St John
3.2 Materials classification
Sulfur-sulfate plots can be used to consider groups of
similar samples. The use of bars representing the
range from the minimum to maximum value delimits
the typical sulfur-speciation for samples from the
same source, whilst also displaying averages. Toler-
ance criteria may also be added to aid assessments of
material suitability with respect to specifications.
In Ireland, the NSAI (2013) outlined pass and
failure criteria for sulfur-species in sub-floor hard-
core material following extensive damages to struc-
tures as a result of sulfate-induced heave (Table 3).
Table 3. Pass and failure criteria for sub-floor hardcore, tested in
accordance with IS 398-1 (NSAI 2013). Values converted to % S.
Sulfur species (% S) Pass Fail
Total sulfur, TS ≤ 0.3 > 1.0
Acid-soluble sulfur, ASS ≤ 0.067 > 0.067
Water-soluble sulfur, WSS ≤ 0.033 > 0.1
An averaged (N=5) dataset of pyritic mudrock
used as sub-floor aggregate in Dublin, Ireland, shows
the range of sulfur-species values and the exceedance
of all relevant NSAI (2013) chemical criteria (Fig-
ures 5 and 6). The high non-sulfate sulfur indicates
the potential for continued oxidation and expansion.
Figure 5. Average (N=5) sulfur-sulfate plot for calc. mudrock
used as sub-floor hardcore. Data from Hawkins & Stevens (2013).
Bars represent the range of values. NSAI (2013) criteria shown.
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Geotechnical Engineering for Infrastructure and Development
Figure 6. Enlargement of low sulfate region of Figure 5.
3.3 Limitations of sulfur-sulfate plots
Whilst the graphical approach is simple and quick to
produce with a pre-established spreadsheet, sulfur-
sulfate plots are limited by assumptions outlined for
derived chemical terms, impracticalities of plotting
single (non-averaged) results for large datasets and
difficulties in accurately representing the low sulfur
content of most WS values and tolerances.
4 CONCLUSIONS
This paper reviews the applications and limitations of
derived terms for the assessment of sulfur-species.
a) Derived terms can be used to estimate abun-
dances and mineralogy of typical sulfur-species
in the absence of detailed petrography, provided
assumptions are valid.
b) Assumptions are inherent in all derived terms.
Whilst reasonable in homogeneous materials,
these may be invalidated if other sulfur sources
are present, particularly insoluble sulfates.
c) Derived chemical terms only attribute the abun-
dance of sulfur-species at the time of testing.
d) Derived terms should be used as indicators of
sulfur-species and should not replace the use of
advanced techniques such as XRD and SEM to
substantiate mineral phases present.
A simple graphical approach for displaying and
interpreting chemical data is presented. Such plots
3382
present TS, TPS, AS, ASS, WS, WSS, OS and non-
sulfate sulfur in one graph, allowing comparison be-
tween samples and averaged datasets.
a) Sulfur-sulfate plots provide a simple means for
displaying data in consistent units. Modifica-
tions (including ranges and tolerances) can be
added for detailed interpretation.
b) Plots can be used for a range of applications, in-
cluding interpretation of weathering, classifica-
tion/comparison of materials and identification
of implausible data.
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