Assessing the role of bacterial (dissimilatory) sulfate reduction in neutralising acid mine drainage

lakes: isotopic results from column experiments

Andrea Fauville1, Bernhard Mayer 2, Ren Frmmichen3, Kurt Friese3, Jan Veizer1, 4
1

Institut fr Geologie, Mineralogie und Geophysik, Ruhr-Universitt Bochum, D 44780 Bochum,

Germany
2
Department of Physics & Astronomy and Geology & Geophysics, University of Calgary, Calgary,
Alberta, Canada T2N 1N4
3
UFZ Sektion fr Gewsserforschung, D 39104 Magdeburg, Germany
4
Ottawa-Carleton Geoscience Center, University of Ottawa, Ottawa, Ontario, Canada K1N 6N5

Lusatia, a region in the eastern part of Germany, was an economically important lignite-mining district in
the former German Democratic Republic. After mining activities ceased in the majority of the pits, acid
mine drainage lakes developed in numerous strip mine dumps as a results of oxidation of pyrite, a process
which produces acidity according to equation 1.
2

4 FeS2 + 15O2 + 14 H 2O 4 Fe(OH )3 + 8SO4 + 16 H +

(1)

The generated acid solutions were flushed by surface water runoff or by the ascending groundwater into
the developing lakes. Todays challenge is to increase the pH values of the acid lakes to near neutral levels
in order to make them accessible for recreational activities in the near future.
The main objective of this study was to evaluate the current physico-chemical and biogeochemical
conditions of selected acid mining lakes in Lusatia. A second goal was to determine whether naturally
occurring biogeochemical processes such as bacterial (dissimilatory) sulfate reduction (BSR) can
potentially generate enough alkalinity to neutralise acid mine drainage lakes in the study area.
During BSR, sulfate is used by bacteria under anaerobic conditions as an electron acceptor for the
oxidation of organic carbon (eq. 2).

2CH 2 O + SO4

H 2 S + 2 HCO3

(2)

During this process, H2S is formed, which can precipitate after reaction with reduced iron as iron sulfide
minerals (iron monosulfides and/or pyrite) in the sediments according to equation 3.

2 Fe 2+ + 4 SO4

+ 4 H + + 7CH 2 O 2 FeS 2 + 7CO2 + 9 H 2 O

(3)

Since the generation of H2S by BSR and the subsequent fixation of reduced S in sedimentary sulfide
minerals (eq. 3) is a process which generates alkalinity (Cook et al. 1986, Schindler et al. 1986), intensive
BSR can potentially lead to an effective neutralisation of acid mine drainage lake water, if the reduced S is
permanently fixed in the sediments.

BSR in neutralising acid mine drainage lakes

BSR is a process which involves a kinetic isotope effect for both sulfur and oxygen isotopes. Since
32 16
S O42- is preferentially metabolised by bacteria, the residual dissolved sulfate becomes progressively
enriched in 34S and 18O, as sulfate concentrations decrease. Consequently, the isotopic composition of
dissolved sulfate can be an indicator for the occurrence of BSR in the studied system. The enrichment
factor =34S is about 2.5 to 4.5 times higher than 18O during BSR, as observed experimentally (Fritz et al.
1989, Pierre 1989). Note that the evolution of 18O values of dissolved sulfate also depends on 18O values
of the surrounding water (Mizutani & Rafter 1973). The observed sulfur isotope fractionation between
sulfate-S and H2S varies, dependent on environmental conditions, between -4 and 46 (Chambers &
Trudinger 1979). Therefore, sedimentary sulfides are generally depleted in 34S compared to the residual
dissolved inorganic sulfate.
The water column and the sediments of two different acid mine drainage lakes were investigated using
chemical and isotopic techniques. Sulfur isotope data were obtained for dissolved sulfate from the water
column. Furthermore, the 34S values of several sedimentary sulfur compounds, such as monosulfide and
pyrite minerals, elemental sulfur, organic sulfur, and inorganic sulfate, were determined.
The epilimnion of lake ML 0622/3 was acidic with pH values between 3 and 4 and showed 34SSulfatevalues around 20 (Fig. 1). In the anaerobic hypolimnion of the lake, pH values around 6 and 34SSulfatevalues up to 26 were determined.

10

20

30

3
4
5
6

( )

34SSulfate

Depth (m)

1
Depth (m)

Depth (m)

3
4
5
6

10

20

3
4
5

pH values

Oxygen content (mg/l)

Fig. 1: 34SSulfate-values (in rel. to CDT), pH values, and oxygen content (mg/l) within the water column
of ML 0622/3.
Chemical and isotopic analyses of sediments of ML 0622/3 revealed substantial quantities of monosulfide
minerals with 34S-values more than 40 lower than those of the lake water sulfate. This was interpreted
as evidence for bacterial (dissimilatory) reduction of dissolved sulfate in the anaerobic hypolimnion of
lake 0622/3 with the preferential conversion of 32Ssulfate by bacteria to sulfide minerals. BSR obviously
resulted in the effective neutralisation of acidity below the chemocline, where pH values above 6 were
established.
The second investigated lake ML 111 was characterised by pH values of 2.7 and 34SSulfate-values around
3 throughout the water column (Fig. 2). No monosulfide minerals were found in the surface sediments
and the 34S-values of pyrite were similar to those of sulfate in the lake water.

BSR in neutralising acid mine drainage lakes

10

20

30

3
4

3
4

34SSulfate()

Depth (m)

1
Depth (m)

Depth (m)

10

20

3
4
5
6

pH values

Oxygen content (mg/l)

Fig. 2: 34SSulfate-values ( rel. to CDT), pH values, and oxygen content (mg/l) within the water column of
ML 111.
The results from chemical and isotopic analyses of water and sediments from lake ML 111 indicated that
BSR was not a prevalent process, presumably because of a limited supply of degradable organic carbon to
the lake (Friese et a. 1998).
In order to evaluate, whether bacterial (dissimilatory) sulfate reduction could be stimulated by addition of
degradable forms of organic carbon to acid water and sediments from lake ML 111, laboratory
experiments were performed. Suitable organic carbon sources were determined by bottle experiments (2 l
lake water + 250 g sediment). Then, the ability of the most suitable organic carbon compounds to
stimulate BSR was tested in column experiments ( 88 l lake water + 15 kg sediment) over a period of one
year (Fig.3).

PVC- Cover

20C
88 l Lake Water ML 111

Sampling Port
10C

Straw
14.8 0.3 kg Sediment

Fig. 3: Experimental set-up of the column experiments.

Ten Duran glass columns with various experimental set-ups were installed as shown in Fig. 3. A
temperature-initiated stratification within the water column was adjusted. Two substances, ethanol and
carbonate slurry (a technical by-product resulting from sugar production) were tested as organic carbon
sources for stimulating BSR.

BSR in neutralising acid mine drainage lakes

By monitoring concentrations and isotopic compositions of dissolved sulfate and inorganic carbon in the
water column, and by determining concentrations and isotopic compositions of various reduced
sedimentary sulfur compounds, detailed information about the rates of BSR were obtained. The addition
of carbonate slurry and straw to the columns resulted in decreased sulfate concentrations and in a marked
increase in 34S values of dissolved sulfate indicating the occurrence of bacterial sulfate reduction. Large
quantities of the sulfur were precipitated as iron sulfide minerals within the sediments. pH-values in the
column water increased to 6.4 indicating that BSR generated enough alkalinity to effectively neutralise the
acid lake water within some columns.

Literature
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