Acid Sulfate Soils: Formation

Martin C. Rabenhorst
Delvin S. Fanning
Steven N. Burch
University of Maryland, College Park, Maryland, U.S.A.

INTRODUCTION
Soils containing sulde minerals that have not yet been
oxidized through acid sulfate weathering are referred
to as potential acid sulfate soils (potential acid SS).
The processes involved in the formation and accumulation of sulde minerals in soils leading to the formation
of potential acid SS will be discussed rst. Subsequently, processes related to the oxidation of suldes
in the formation of active acid SS will be examined.
The extent of acid SS worldwide has been estimated
to be approximately 1215 MHa.[1]

POTENTIAL ACID SULFATE SOILS AND SULFIDE

MINERAL FORMATIONSULFIDIZATION
Biogeochemistry of Sulde Mineral Formation
Several factors are required for sulfate reduction.
These include a source of sulfate, a source of oxidizable
carbon, reducing conditions and the presence of sulfate
reducing bacteria.[2] Any of these components could
theoretically limit sulfate reduction. In saturated soil
or sedimentary environments where the required factors are present, heterotrophic microbes utilize sulfate
as an electron acceptor that becomes reduced to sulde
according to Eq. (1).
SO4

2

10H 8e

! H2 S 4H2 O

Sulfate
Provided that the other required factors are met, the
quantity of sulfate may limit the rate of sulfate reduction. Goldhaber and Kaplan[3] reported sulfate reduction to be independent of concentration when sulfate
levels are above 10 mM (320 mg=l). Work by Haering,[4]
in Chesapeake Bay, indicated that sulfate levels may
begin to limit sulfur accumulation in marsh soils when
levels drop below 1 mM (32 mg=l). Some degree of
sulfate reduction will continue as long as sulfate is
present at minimal levels (>520 mM, 0.160.6 mg=l).[5]
Because sulfate-reducing bacteria are better able to
20
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complete for electron-donating substrates than are

methane-generating bacteria, methanogenesis is of
minimal signicance so long as sulfate levels are above
0.030.4 mM.[6] Therefore, sulfate reduction dominates
in brackish systems. In freshwater, sulfate reduction
may become overshadowed by methanogenesis as
sulfate is depleted.
Oxidizable organic carbon
The oxidation of organic matter provides the energy
microorganisms need to facilitate sulfate reduction.
Plant materials rich in labile components are more
easily decomposed than humied soil organic matter
or peat. In sediments low in organic matter, sulfate
reduction may be limited by the paucity of oxidizable
carbon. This can be demonstrated in thin sections from
mineral horizons in tidal marsh soils where iron sulde
minerals have accumulated in pores occupied by
decaying plant roots (Fig. 1). The intimate association
of pyrite with the decomposing organic minerals, and
its near absence from the surrounding soil matrix suggests that organic matter is limiting the formation of
sulde.[7]
Reducing=saturated conditions
Because diffusion of gases through saturated soils and
sediments is very slow, oxygen becomes depleted under
saturated conditions and microbes which utilize other
electron acceptors become active. Nitrate, Mn(IV) and
Fe(III) are so utilized as the environment becomes progressively reduced (Fig. 2). If the conditions permit the
entry of oxygen, then redox potentials may never become
sufciently low to foster sulfate reduction. More typically, diffusion of oxygen into a saturated soil or sediment is sufciently slow, and if other necessary factors
are present, sulfate reduction will occur. Fig. 2 illustrates
that pH, as well as Eh, must be specied in assessing sulfur phase equilibria. For example, as the pH increases
from 5 to 7, the minimum Eh at which sulfate reduction
is expected decreases from approximately 50 to 200
(based on a SO42 concentration of 10 mM and a pH2S
of 0.0001 atm).
Encyclopedia of Soil Science DOI: 10.1081/E-ESS-120001777
Copyright # 2006 by Taylor & Francis. All rights reserved.

Acid Sulfate Soils: Formation

21

rate of sulfate reduction generally increase with temperature across this range. Some groups of sulfate reducers
are thermophyllic and can function at temperature up
to 85 C. Thus, in tropical coastal wetlands, sulfate reduction occurs all year round. In higher latitudes, where soil
and sediment temperatures may approach biological
zero, rates may become very slow during winter.
Reactive iron

Fig. 1 Micrograph of a thin section from the mineral (Cg)

horizon of a tidal marsh soil illustrating accumulation of
pyrite framboids in the channel occupied by decaying plant
roots. Plane polarized light; frame length 1.2 mm.

Sulfate-reducing bacteria
Some 15 genera of bacteria have been recognized as
sulfate reducers including Desulfovibrio, Desulfotomaculum, and Desulfobacter.[8,9] These organisms thrive
under strongly reducing conditions, but many are able
to persist in aerobic conditions for signicant periods
of time. Thus, if the other factors necessary for sulfate
reduction are present, sulfate reducing bacteria will
also become active.
As with most heterotrophic bacteria, rates of sulfate
reduction are temperature dependent. Optimum temperature for most sulfate reducers is 3040 C,[8] and the

Once formed, sulde is available to form a variety of

minerals provided there is adequate reactive iron
present. Most of the iron enters coastal environments
as iron oxides sorbed to the surface of clay and silt
particles. When iron oxides in the sediments and marsh
soils become reduced to Fe(II), they can form iron
sulde minerals. While monosulde species may form
rst [Eq. (2)], and minerals such as greigite (Fe3S4)
may persist in recent sediments, disulde forms such
as pyrite are energetically more stable and will form
at the expense of the monosuldes.
Fe2 S2 ! FeS

FeS and SX Y  ; loss of e ; or H2 S

! FeS2 various

Mechanisms for pyrite formation may follow several

possible pathways including 1) reaction of monosulde
with polysulde; 2) partial oxidation of monosulde;
and 3) reaction of monosuldes with H2S[10] [Eq. (3)].
Sulde itself has the ability to reduce Fe(III) to Fe(II)
on the surface of iron oxides.[11] Pyrite can occur either
as small (<2 mm) individual crystals or as spherical
clusters of crystals called framboids. In low organic
mineral sediments, reactive iron is usually present in
excess, resulting in a low degree of pyritization.[12]
However, in organic-rich soils iron may limit the
accumulation of sulde minerals, and the degree of
pyritization is generally high. This has been demonstrated experimentally in salt marsh Histosols.[13]
Environments of Sulde Formation
and Accumulation

Fig. 2 pe-pH diagram illustrating location of stability elds for

redox sensitive components. The sulfate-sulde lines (Green) is
based on a (SO)42 concentration of 10 mM and a pH2S of
0.001 atm. (Blue line separates the pyrolucite-Mn2 stability
elds; red line separates the goethite-Fe2 stability elds.)

Copyright 2006 by Taylor & Francis

It is clear that in environments which provide a source

of oxidizable carbon and sulfate and which are sufciently saturated to enhance reducing conditions, sulfate reducing bacteria will generate sulde. If reactive
iron is present, then solid phase ferrous minerals will
accumulate. This process of suldization[14] is shown
schematically in Fig. 3. The obvious settings for these
processes are coastal marine and brackish environments, where sulfate is abundant. Under permanently
submersed conditions, detrital carbon is added by ora

22

Acid Sulfate Soils: Formation

Fig. 3 Schematic diagram illustrating the generalized process

of suldization which leads to
the formation of iron sulde
minerals and potential acid SS.
(From Ref.[26].)

and fauna to the sediment. In shallow water settings

(<3 m) where various pedogenic processes are at work,
these accumulated sediments have been recognized as
subaqueous soils[15] and are classied to reect the
sulde components.
The soils of coastal marshes (in temperate environments) and mangroves (in tropical settings) also are
ideal for sulde formation and accumulation. The high
primary productivity of these ecosystems (up to
3 kg m2 yr1 in marshes and up to 5 kg m2 yr1 in
mangroves)[16] makes these an exceptionally good
environment for sulfate reduction. Such soils may
contain up to 2030 g=kg of pyrite sulfur, and estimates of pyrite S accumulation rates in estuarine
marshes are as high as 7 g m2 yr1.[17]
Sulfate reduction can occur in other settings, so long
as a source of sulfate is available. While generally
small, atmospheric deposition of sulfate may be
enough to induce sulfate reduction in the sediments
of some interior freshwater lakes. Sulfate reduction
has also been documented in prairie potholes where
sulfate has apparently been contributed by the weathering of sulfur-bearing shales.[18]

FORMATION OF ACTIVE ACID SULFATE

SOILSSULFURICIZATION

sulde bearing coal, but may also occur due to tectonic

uplift or oceanic regression. Under humid or moist
aerobic conditions, sedimentary sulde minerals can
oxidize chemically[19] but this is a slow process, probably due to particular rate-limiting reactions. Various
microorganisms are adapted to oxidize suldes either
directly through sulfur transformations or by facilitating (catalyzing) such rate-limiting reactions as the
oxidation of Fe(II) to Fe(III).[20] While there are many
possible intermediate reactions in the oxidation of
pyrite, the overall reaction is summarized in Eq. (4).
One mole of pyrite eventually yields two moles of
sulfuric acid and a mole of iron hydroxide.
FeS2 3 34 O2 3 12 H2 O ! 2H2 SO4 FeOH3

The oxidation of pyrite proceeds along two fronts

(Fig. 4). First the S is oxidized (through intermediates)
to sulfate yielding sulfuric acid and the remaining
Fe(II). The generated Fe(II) sulfate salts are very soluble and potentially mobile. Secondly Fe(II) is oxidized
to Fe(III), which when hydrolyzed produces additional
acid. At high pH, the oxidation of sulde is accomplished with oxygen, but under low pH conditions
sulde is oxidized by Fe(III). Microorganisms such as
Thiobacillus ferrooxidans facilitate this reaction by
oxidizing Fe(II) to Fe(III). For more details refer to
Gagliano and Bigham.[21]

Chemistry of Sulde Oxidation

Suldes begin to oxidize once they are exposed to more
oxidizing conditions. This occurs most often as a result
of such human activities as drainage or dredging of
sulde-bearing soils or sediments, or the mining of

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Other Aspects of Sulfuricization and Properties

of Acid Sulfate Soils
Sulfuricization is the overall process by which suldebearing minerals are oxidized, minerals are weathered

Acid Sulfate Soils: Formation

23

schwestmannite and goethite. If the soil pH falls below

four while maintaining an oxidizing environment
(Eh > 400 mV) then the mineral jarosite (KFe3
(SO4)2(OH)6) can form.[23] Because jarosite forms
under conditions of high Eh and very low pH, which
can only develop from the generation of sulfuric acid,
it is considered a diagnostic mineral for acid SS.[24]
Jarosite has been reported in soils, which are not
extremely acid and which may even contain carbonates.[22] These are interpreted to be postactive acid
SS, meaning that earlier in their pedogenic history, they
had undergone acid sulfate weathering. Subsequently,
the soil pH has risen due to weathering of silicate minerals or addition of eolian carbonates. Because the redox
potential has remained strongly oxidized, the jarosite
has persisted as a metastable species. A recent review
of acid sulfate soils including a discussion of the modeling of associated processes was recently completed.[25]

REFERENCES

Fig. 4 Schematic diagram illustrating the generalized process of sulfuricization which involves the oxidation of iron
sulde minerals and the production of acidity and the formation of new sulfate and other minerals. (From Ref.[26].)

by the sulfuric acid produced and new mineral phases

are formed from the dissolution products.[14,21] When
CaCO3 minerals are present, the sulfuric acid reacts
with them to form the mineral gypsum, according
to Eq. (5).
CaCO3 H2 SO4 H2 O
! CaSO4  2H2 O CO2

As long as sufcient CaCO3 is present, the pH is

prevented from becoming very low and the soil does
not become acid. When insufcient acid neutralizing
minerals are present, the oxidation of pyrite in soils
will lower the pH. The pH of active SS commonly
drops to below four and in extreme can go below
two. As iron is oxidized and hydrolyzed, various iron
minerals form in the soil including ferrihydrite,

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