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Journal of Geochemical Exploration 73 (2001) 75±86

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Redox and pH conditions in the water column and in the sediments
of an acidic mining lake
T.M. Bachmann a,1, K. Friese b,2, D.W. Zachmann a,*
b

a
Institute for Geosciences, Technical University of Braunschweig, Pockelsstr. 4, D-38106 Braunschweig, Germany
Department for Inland Water Research, UFZ-Centre for Environmental Research Leipzig-Halle Ltd., Brueckstr. 3a,
D-39114 Magdeburg, Germany

Received 7 December 1999; accepted 13 December 2000

Abstract
Physico-chemical parameters of the acidic mining lake (ML) 111 in the Lusatian region (Germany) were determined in April
and August 1997 using a multiparameter probe for the water column and punch-in pH and Eh electrodes for the sediment,
respectively. Samples of the sediment pro®le were taken by a gravity corer. Besides determination of the physico-chemical
parameters, grain size and water contents were determined after sediment slicing.
Differences in the redox state of the water body, deduced from oxygen saturation between April and August, could not be
inferred. However, a shift in pH to lower values was apparent. Data support the conclusion that the enhanced oxygen content
was consumed for oxidation of ferrous iron to ferric iron (oxides/hydroxides) coupled with the release of protons.
In the sediment, different buffer systems of iron compounds could be detected within separate zones with values below and
above pH 3. At higher pH values, the redox conditions are controlled and stabilized by the presence of Fe-oxide-hydroxides and
possibly Fe-sulfates. q 2001 Elsevier Science B.V. All rights reserved.
Keywords: acid mining lake Ð acid mine drainage; lakes; redox potential Ð Eh; pH; grain size fractions Ð grain size; lake sediments; lake
strati®cation Ð strati®cation; lakes; iron oxides±hydroxides Ð iron oxides; iron hydroxides

1. Introduction
Acid sulfate-bearing waters are produced by the
aerobic leaching of sul®de-bearing materials. In the
case of the open pit lakes in the Lusatian region
* Corresponding author. Tel.: 149-531-391-7250; fax: 149-531391-8130.
E-mail address: d.zachmann@tu-bs.de (D.W. Zachmann).
1
Present address: Institute of Energy Economics and the Rational
Use of Energy, University Stuttgart, Heûbruehlstr. 49a, D-70565
Stuttgart, Germany.
2
Present address: UFOP-Universidade Federal de Ouro Preto,
DEGEO-Departamento de Geologia, Campus Universitario,
Morro do Cruzeiro s/n, CEP 35.400-000 Ouro Preto, MG, Brazil.

(eastern Germany, Fig. 1), these waters developed
due to the lowering of the ground water table and
following oxidation of pyrite and marcasite, during
open-cast lignite mining. These minerals are ubiquitous accessories of lignite horizons and associated
sediments. Acidi®cation is currently considered to
be the most severe environmental problem affecting
the water quality of mining lakes in Lusatia (Schultze
and Geller, 1996; Friese et al., 1998a). Different
research projects in Germany deal with the chemical
and ecological state of mining lakes. Their goal is to
serve as a basis for the development of restoration and
remediation techniques.
Due to the origin of acidi®cation, the lake waters

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T.M. Bachmann et al. / Journal of Geochemical Exploration 73 (2001) 75±86

Fig. 1. Location of study site ML-111 (modi®ed after BuÈttner et al., 1998).

and sediments are also enriched in Fe. The speciation
and solution of Fe is controlled by the dimictic character of the lakes, with overturns in spring and fall
(Herzsprung et al. 1998). During seasonal overturns,
the waters are oxygenated and cycles of Fe and Mn
solution/precipitation are expected. The behavior of
several elements (e.g. heavy metals) in lakes is essentially ruled by the Fe and Mn cycles as well as the
growth of algae and the decay of its organic matter
(Salomons and FoÈrstner, 1984; Sigg et al., 1987, 1996;
Balistrieri et al., 1992; Hamilton-Taylor and Davison,
1995; Bloesch, 1996; Weyhenmeyer et al., 1997; Xue
et al., 1997). In general, the organic matter is said to
be more important with respect to heavy metal sorption in water bodies than Fe and Mn compounds
Table 1
Physical, chemical (mean values) and morphometric characteristics
of ML-111 (taken from Friese et al., 1998b)
Surface area (10 4 m 2)
Volume (10 6 m 3)
Maximum depth (m)
Mean depth (m)
pH (median)
Sulfate (mg/l)
Iron (mg/l)

10.7
0.5
10.2
4.6
2.6
1310
156

(Tessier, 1992; Bendell Young and Harvey, 1992;
Davison, 1993; Xue et al., 1995). However, in the
investigated mining lake, the extreme acidic environmental conditions, together with the photoreduction
of ferric to ferrous iron and the subsequent oxidation
of organic carbon, lead to a sustained abiotic elimination of carbon compounds (Herzsprung et al., 1998).
The latter, therefore, are unlikely to be an important
scavenger phase in such acid mining lakes and the Fe
precipitation as hydroxide is probably the prevailing
mechanism, which controls the sorption processes.
The aim of this paper is to give an example of the
variation and dependencies of the pH and redox
conditions in the water body and sedimentation of
acid sulfate mining lakes and to relate redox conditions to mineral phases present in the system.

2. Materials and methods
2.1. Study site
The mining lake 111 (ML-111) is located in the
Lusatian mining district in Brandenburg (eastern
Germany; Fig. 1). Table 1 presents some of the

T.M. Bachmann et al. / Journal of Geochemical Exploration 73 (2001) 75±86

77

Fig. 2. Site map of ML-111 (modi®ed after BuÈttner et al., 1998).

essential physical, chemical and morphometric data
for the lake. ML-111 is a closed lake with no open
in¯ow or out¯ow. It consists of three basins separated
by narrow and shallow interconnecting zones (Fig. 2).
Normally, a thermal strati®cation develops in summer
leading to oxygen consumption in the hypolimnion. In
the middle basin of ML-111, there is a monimolimnion at about .5.5 m depth that was observed for the
®rst time in 1995 (Herzsprung et al., 1998).
In April and August 1997, sediment cores with 10
subsamples were taken from a location of about 7 m
water depth in the middle basin (mictic and strati®ed

situation, respectively). This depth corresponds to the
prevailing depth of ML-111 (BuÈttner et al., 1998; Fig.
2). Using a Differential Global Positioning System,
the sediment cores could be taken at nearly the same
position at both sampling times (Fig. 2).
2.2. Sampling
The data of measurements of physico-chemical
parameters in the water body are given in Table 1.
The parameters were measured by a temperature and
pressure compensated multiparameter probe, just

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T.M. Bachmann et al. / Journal of Geochemical Exploration 73 (2001) 75±86

2.3. Pore water contents and grain size fractions

Fig. 3. Division of the sediment cores and analyses performed (scaling 1 cm intervals, gray samples were taken for analysis, white
samples were discarded).

before sediment sampling (Idronaut Ocean Seven 316,
Brugherio Italy; accuracy of measurement: pH:
^0.05, T: ^0.058C, Eh: ^25 mV, electrical conductivity: ^10 mS/cm (in situ; 1% after temperature
correction according to Schimmele and Herzsprung
(2000)), O2: ^2%). The probe was calibrated immediately before the measurements, e.g. pH and Eh by
certi®ed commercial solutions (Orion, Mettler), O2
against air. Detailed sampling protocols were
recorded immediately.
Using a modi®ed Kajak gravity corer, undisturbed
cores were collected in polycarbonate tubes. The top
20 cm of sediment were recovered. Sediment was
extruded and sectioned in vertical intervals of
1 cm. Since the pore volume and thus the in¯uence
of the water body decrease with depth, the sampling
density was adjusted (c.f. Fig. 3). Therefore, between
5 and 10 cm, every second sample was discarded.
From the remainder only the depths at 15 and
20 cm were taken. Each sample was split into two
subsamples. One subsample was transferred into
sterile, preweighed polyethylene centrifuge tubes
with screwcaps (Sarstedt), the other into precleaned
polypropylene screw cap vials (Nalgene). On the
latter subsamples, pH and Eh were determined in
the ®eld, immediately after sampling. Measurements
were performed with punch-in pH and Eh electrodes
(Rifex). All samples were ¯ushed with argon and
stored in a cool temperature (,48C) until further
processed in the laboratory.

The pore water contents were determined in a twostep procedure. After centrifuging at 3800 rpm (gmax.
ca. 3000) for 20 min and decanting the supernatant
¯uid, the samples were oven dried at 608C. Having
reached a constant weight, the subsamples were
analyzed for the distribution of grain size. A
combined sieving (.63 mm) and ¯otation procedure
(,63 mm) was used. In order to avoid a grain size bias
by aggregates, the samples underwent an ultrasonic
treatment (Bandelin Sonopuls HD 200; 200 W,
20 kHz, amplitude 130 mm, 6 mm Ti-disc; 30 s at
40% of maximum power) in a solution of NH4OH
as a dispersing agent (0.01%; MuÈller, 1964; Moore
and Reynolds, 1989). The percentage of the sand
fraction was determined by wet sieving at 63 mm in
stainless steel sieves. The ®nes were rinsed into Atterberg cylinders to a height of 26 cm above the outlet.
After 19 h of settling time, the suspension above the
outlet containing most of the clay-fraction was transferred to preweighed centrifuge tubes and centrifuged
(10 min at 3800 rpm). The pellet was oven dried in the
centrifuge tubes at 608C. The decanted supernatant
¯uid still contained the micro®nes of the total clay
fraction. The ¯uid was acidi®ed by the addition of
HCl (pH ca. 1) in order to ¯occulate the micro®nes,
which were then centrifuged and oven dried as above.
The remaining suspension below the outlet of the
Atterberg cylinder contains the silt as well as another
part of the clay fraction. Therefore, the whole procedure for clay separation was repeated with the remaining suspension in the Atterberg cylinders. Finally, the
silt fraction was retrieved by transferring the suspension containing silt, below the cylinder's outlet to
centrifuge tubes. After centrifugation, the silt material
was dried at 608C until constant in weight.
2.4. Mineralogy, chemical composition
The mineral composition of the samples was
examined by XRD using a Philips PW 1370 equipped
with Cu-Ka radiation …l ˆ 0:5418 nm† and C-monochromator. The diffractograms were taken from raw
sediment materials as well as from materials treated
by washing with distilled water. The diffractograms
were recorded from 3±658(2u ) with a sample rotation
of 18(2u )/min. The chemical composition of the

T.M. Bachmann et al. / Journal of Geochemical Exploration 73 (2001) 75±86

79

Fig. 4. pH and Eh depth pro®les (note: the scale change at 0 cm, the sediment water interface (´´´)).

samples was examined by ICP-OES (equipment:
Fisons Maxim and ARL 3520) after digestion in a
HF±HNO3 ±HClO4-solution. The methods are veri®ed by analyzing internationally certi®ed reference
materials (SARM 1-6; Abbey, 1983).

3. Results and discussion
3.1. Water column
The pH and the redox potential in the water body
are given in Fig. 4 (upper part). Obviously, the redox
and pH values differ between the samples taken in
April and August. The temperature distribution of

the water column is given in Fig. 5(a). The August
distribution of these variables displays the strati®cation of the water body very well with an epilimnion
between 27 and 24.5 m, a following transition zone
down to about 1 m and a monimolimnion that can be
observed more clearly at deeper locations of the lake.
Fig. 5(b) shows the electrical conductivity of the
water pro®les. The values match the very high
amounts of dissolved ions generally found in the
water bodies of acid mining lakes. Schimmele and
Herzsprung (2000) found that the strati®cation of
the lake goes along with higher amounts of dissolved
ions. The higher electrical conductivity in the epilimnion (Fig. 5(a) and (b)) can be explained by near
surface in¯ow of high concentrated seepage waters,

Fig. 5. (a) Temperature and O2 saturation and (b) electrical conductivity pro®les in the water body.

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T.M. Bachmann et al. / Journal of Geochemical Exploration 73 (2001) 75±86

Table 2
pH-values at 4.5 and 1 m above the sediment±water-interface in a
time series from August 1995 to August 1997 (data for 1995 and
1996 taken from Becker, 1997)
Year

Month

Depth 4.5 m

Depth 1 m

1995
1996

August
May
August
April
May
June
July
August

2.4
2.6
2.7
2.7
2.65
2.6
2.6
2.3

2.4
2.6
2.7
2.7
2.7
2.65
2.65
2.4

1997

which drain the tips around the lake. This seepage
water contains the dissolution products of the pyrite
oxidation process, mainly sulfate, calcium, ferrous
iron and protons. Due to the thermal strati®cation in
summer, these ions would then be enriched in the
epilimnion of the lake leading to the observed higher
electric conductivity.
According to the August data, the division of the
water column into three zones as indicated by the
temperature distribution is followed by the redox
values. The uppermost zone matches the epilimnion
(see Fig. 4 and Fig. 5(a) for temperature) with redox
values corresponding fairly well to the ones from
April. Similar values at both sampling campaigns
(April and August 1997) could also be observed in
the monimolimnion at depths below 1 m. However,
the zone between the epilimnion and monimolimnion
(4.5±1 m), shows an increase in the redox potential
from April to August. An increased ¯uorescence of
chlorophyll-a was observed at this depth in summer,
which might be an explanation for the increased
values of the redox potential at this depth (Packroff
et al., 2000). The main pattern of the oxygen saturation and the redox values is generally similar.
However, the redox increase in the transition zone is
not consistent with the oxygen saturation. Besides a
slight indication of a positive correlation in the lowermost part of the transition zone, the oxygen saturation
decreases with increasing redox values. In addition,
the whole water pro®le of pH measurements in August
is shifted to lower values as compared to the ones in
April. The pro®le patterns and values of the other
months in 1997 resemble very much with the ones
of the April data (cf. Table 2). It is therefore

concluded that the higher oxygen content was subsequently consumed due to the oxidation of ferrous iron
to ferric iron oxides/hydroxides with subsequent
precipitation. According to the equation
‰Fe31 Š 1 3H2 O ˆ Fe…OH†3 1 3‰H1 Š;
the intensi®ed production of ferric iron ®ts the higher
acidity of the lake waters in August (Fig. 4). The
generation of ferrous iron in the water column could
be the result of photoreduction processes near the
water surface as described in Herzsprung et al.
(1998) and by the in¯ow of enriched ferrous iron
with seepage waters from the surrounding tips.
3.2. Sediment composition
A physical description of the sediment samples can
be found in Table 3. The mean iron concentration of
the uppermost sediments is 18:1 ^ 8:3 wt% (n ˆ 65;
without extreme values). The maximum concentrations reach values of about 33 wt%. In the upper
sediments, the Fe-concentrations are controlled by
grain size with higher values in the fractions of silt
and ®ne sand. Most of these sediments consist of
X-ray amorphous materials, and in some cases, only
with minor indications of goethite and ferrihydrite.
From these ®ndings, it follows that the uppermost
sediments have been formed as precipitates of amorphous Fe-oxide±hydroxides, which aggregated to the
size of silt and ®ne sand in the course of early diagenetical processes.
The Fe concentrations generally decrease with
depth and admixtures of clay minerals, especially
kaolinite, feldspars (Na, K) and quartz, occur. The
occurrence of pyrite could not be observed. Below
15±20 cm, the sediments nearly consist of monomineralic quartz sand. It is considered as the primary
sediment, which formed the base of the open pit mine.
When the Fe-rich sediments were not washed free
of sulfate bearing pore waters, prior to X-ray examination, peaks of Fe-sulfates could be found as
artefacts (jarosite, karphosiderite, possibly also
schwertmannite). This was also observed by GoÈttlicher and Pohlmann (2000).
3.3. Grain size and water contents
In the investigated sediment cores, all parameters

Table 3
: Description of the sediment samples from ML-111 (1997)
Depth (cm)

April core
Physical appearance

August core
Sand (wt%)

Clay (wt%)

Physical appearance
Mostly darkish brown, beigebrown and patchy
Mainly light brown with ochre or
brown patches, ¯aked
Ochre to brownish beige, darkish
brown patch
Ochre to yellow with darkish
brown pathches, in parts with
black particles
Beige to brown, mostly with
dark patches, little ochre; black
particles
Mostly darkish brown, beige and
brown schlieren, partly black
particles, more creamy
Mostly brown, darkish brown
patches with ochre schlieren,
black particles
Mostly brown, rusty brown with
brown schlieren, black particles,
creamy
Brown, partly black particles
Mostly brown, beige and darkish
brown parts
Brown to greyish brown, creamy
Brown

0±1

Ochre, brown, olive; ¯aked

4

81

15

1±2

1

92

7

1

90

9

17

69

14

4±5

Ochre to greyish brown and
darkish brown
Greyish brown, brown with
ochre parts
Greyish brown, brown with
ochre and light beige to white
parts; black grains
Various colours

9

68

23

5±6

±

6±7

Mainly brown with black
patches, dark brown

4

75

21

7±8

±

8±9

Mainly brown, light beige to
orange; ®ne size granulous
±

4

76

20

±

±

3
7

77
62

20
31

36

40

25

2±3
3±4

9±10
10±11
15±16
20±21

Brownish green to light ochre
Brownish green to light ochre,
lower parts darkish grey;
creamy consistency
Olive and light grey; sand with
ochre slurry

±

Greyish brown to brown, partly
ochre to orange; coal chunks, a
bit sandy

Sand (wt%)

Silt (wt%)

Clay (wt%)

5

77

18

2

76

22

2

84

14

3

75

22

4

68

28

4

67

29

3

68

29

5
9

65
65

30
26

35

45

20

T.M. Bachmann et al. / Journal of Geochemical Exploration 73 (2001) 75±86

Silt (wt%)

81

82

T.M. Bachmann et al. / Journal of Geochemical Exploration 73 (2001) 75±86

Fig. 6. Composition of the sediment samples collected in (a) April and (b) August (note: the water contents refer to the original wet samples, the
grain size fractions to dried samples).

(Eh, pH, T, O2), except for the sand and clay contents,
show signi®cant increase or decrease with depth
(Spearman correlation 3, 5% level; Figs. 4 and 6).
The water contents decrease from more than 90 to
40 ^ 3 wt% of total weight (including pore water;
Fig. 6). Silt is the prevailing grain size fraction
(. ^ 40 dry wt.%) in the upper sediment sections.
It signi®cantly correlates with the water contents in
both cores, whereas the sand as well as the clay
contents does not. Both, water and silt contents
show a highly signi®cant, negative correlation with
depth, which indicates that compaction is responsible
for the water contents to decrease. Due to the very
high Fe concentrations in the silt fraction, the decrease
in the silt proportion is coupled with the decrease of
Fe concentrations with depth.
3.4. pH and redox potential
Due to the very high water contents (.90%) in the
uppermost sediment sections, the transition from free
water to sediment takes place gradually. Therefore,
the transition from the water body into the sediment
of pH and redox also occurs gradually (Fig. 4).
The pH within both sediment cores increased from
values of about 2.7 at the sediment water interface to
values of 5.5 in April or even 3.6 in August (Fig. 4).
This increase in pH, i.e. the progressive neutralization with depth is consistent with data from sediments
of other mining lakes (e.g. Peine und Peiffer, 1998;
Blodau et al. 1998, 2000). The neutralization is
3
According to the Kolmogorov±Smirnov test one cannot assume
a normal distribution for all of the parameters.

explained by the reduction of Fe 31 and SO422 by
microorganisms and the formation of iron sul®des.
In the investigated sediments (ML-111), sul®de
mineralizations could not be detected by X-ray
diffraction methods. However, the long lasting anoxic
conditions in the hypolimnion of ML-111 supported
enhanced microbial reduction processes in the
sediment resulting in higher pH values in April.
Therefore, the signi®cant difference in the pH pro®les
between the investigated sediment cores is believed to
be caused by the extremely long lasting ice cover in
the winter 1996/97 which lead to a permanent thermal
strati®cation and hypolimnetic anoxia in ML-111
until spring 1997 (Herzsprung et al., 1998). In contrast
to the divergent pH values, there was no obvious
change in the redox conditions between the spring
and summer core (Fig. 4). Both Eh pro®les show similar shapes. The overall Eh values decrease from the Eh
of the free water with 650 mV at the sediment water
interface to 360 and 260 mV at the core bottom, in
August and April, respectively. Here, the recurring Eh
increase in the depth between 5 and 7 cm is not
considered signi®cant because of the accuracy of the
punch-in electrodes (^20 mV). Both Eh and pH
pro®les of April and August 1997 con®rm an increase
in iron reduction processes with depth as described by
Friese et al. (1998b) for the deepest site of this lake.
Due to the redox controlled solution processes, the Eh
values signi®cantly correlate positively with the Fe
concentrations in the sediment (April: 10.98; August:
10.90).
The ®ndings of highly oxidizing Eh values at low
pH are consistent with the physico-chemical characteristics of mine lakes described by Baas Becking et

T.M. Bachmann et al. / Journal of Geochemical Exploration 73 (2001) 75±86

83

Fig. 7. Eh±pH-values of sediment cores of ML-111 (according to Friese et al., 1998b Fe 21 concentrations of about 5 £ 1023 mol=l in the pore
waters of the sediments have been assumed).

al. (1960). In Fig. 7, the pH and Eh results of ML-111
are compared with the predominant lines of
amorphous Fe(II) and Fe(III) hydroxides as well
as for Schwertmannite and Jarosite (Bigham et al.,
1996) in a pH±Eh-diagram. The occurrence of
poorly crystalline Fe hydroxides is indicated by
the comparison of X-ray diffraction examinations
with chemical analyses (X-ray amorphous in spite
of Fe amounts .25 wt%). According to Bigham et
al. (1996), goethite is ultimately the most stable
mineral phase associated with acid sulfate waters.
Note that the points in Fig. 7 are plotted in sequence
from the top of the core on the left to the bottom on
the right. The graphs for April and August show
similar patterns with a change of slope at about a
pH 3. At this pH, the gradual decrease of Eh with
depth became inconsistent at both times of observation.
Above pH 3, the Eh±pH-values measured in the
sediment cores follow a line with a slope parallel to
the slope of the transition of Fe-hydroxides species
(Fig. 7) whereas, the transition lines for Schwertmannite and Jarosite show a steeper slope. According to

Davis et al. (1988), the formation of Fe-hydroxides
becomes predominant at pH . 3: This ®nding
suggests a control of the Eh±pH-conditions in the
sediment by the presence of redox coupled mineral
associations. The transition of e.g. amorphous
Fe(OH)2 to Fe(OH)3 can be described by
Fe…OH†2am 1 H2 O ˆ Fe…OH†3am 1 ‰H1 Š 1 e2

…1†

Using the thermodynamic values …DG8r † given in
Wagman et al. (1982), a transition line of predominance at
Eh …V† ˆ 0:28 2 0:06pH

…2†

can be derived for the amorphous Fe hydroxides
redox couple. A similar calculation could be
performed using (crystalline) goethite instead of
Fe(OH)3 with a shift of the transition line to lower
values. Due to missing reliable thermodynamic data
for amorphous Fe precipitates, it is not possible to
de®ne the transition lines for the present sediments.
However, it will be situated at higher values as calculated by Eq. (1).
The steeper slope of the transition line below pH 3

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T.M. Bachmann et al. / Journal of Geochemical Exploration 73 (2001) 75±86

in Fig. 7 suggests a transition between Fe 31-precipitates
and soluted Fe 21, as described by
Fe…OH†3am 1 3‰H1 Š 1 e2 ˆ ‰Fe21 Š 1 3H2 O

…3†

Using the thermodynamic values by Wagman et al.
(1982), Eq. (3) yields
Eh …V† ˆ 1:11 2 0:18pH 2 0:06 log‰Fe21 Š

…4†

In the literature, E 0-values for the same redox
couple have been reported leading to transition lines
of the same slope although with a lower offset (e.g.
E0 ˆ 1:065 V by Kamei and Ohmoto, 2000, 0.97 V
by Krauskopf and Bird, 1995 (state of crystallinity not
de®ned)).
However, the measurements as displayed in Fig.
7 show a slope which is at least twice steeper.
This ®nding would indicate a redox process,
which not only affects the Fe components of the
sediment. Considering the low pH values which
are triggered by high sulfate concentrations, the
redox processes may include sulfur species. As
the low pH values occur in the uppermost sediments with high Eh values (Fig. 4), a redox
couple sulfate±sul®de is very unlikely. In addition, the data for the transition of schwertmannite
and jarosite given by Bigham et al. (1996) do not
®t the slope of the measured Eh±pH-values (c.f.
Fig. 7). Therefore, at a pH , 3; the slope of the
Eh±pH-values of the core sediments is considered
to be due to the occurrence of a redox buffer
similar to the coupling of Fe 21/Fe 31-hydroxides,
possibly including some Fe-sulfate species and/or
organic species, which have not yet been identi®ed.
4. Conclusions
The seasonal controlled lake strati®cation goes
along with redox changes of the free water whereas
a change in Eh in the lake sediments could not be
observed. At the same time, a seasonal change in
pH occurs in the free water as well as in the sediment.
Higher Eh values occur in the free water in the
transition zone between the epilimnion and the
hypolimnion during the strati®cation stage

(August). This phenomenon is coupled to an
increased ¯uorescence activity of chlorophyll-a.
However, an increase in oxygen saturation was
generally not observed. The increase in Eh values
goes along with an increase in acidity. The lower
pH values indicate the consumption of phytogenic
oxygen by the oxidation of ferrous iron, which
results in the precipitation of (amorphous) ferric
iron hydroxides.
The increase in pH of the sediment with depth
is especially high during the mictic stage (April).
A long lasting (about 4 months) closed ice cover
caused more anoxic conditions in the hypolimnion
of ML-111, which supported enhanced microbial
reduction processes in the sediment. The reduction
of sulfate and Fe 31 in sediments causing an
increase of pH is well known from the literature
(e.g. Peine und Peiffer, 1998; Blodau et al. 1998;
2000).
In the pH range of 5.5 to 3 the Eh±pH data follow
the predominance lines of amorphous Fe(II) and
Fe(III) hydroxides. This indicates a sediment
sequence which is buffered by the transition Fe(II)±
Fe(III) hydroxides. In the pH range ,3 (top sediments), the Eh±pH values approximately follow the
transition of Fe 21 to Fe(III) hydroxide. However,
systematic deviations from calculated Eh±pH values
indicate additional redox components. Due to the
more oxic conditions in the uppermost sediment
layers, a sulfate±sul®de redox couple is unlikely and
the buffer system at this pH range possibly includes
some (amorphous) Fe-sulfate species, which have not
yet been identi®ed.
Acknowledgements
The authors gratefully acknowledge the support
of the staff members at UFZ-Department for Inland
Water Research Magdeburg and Institute for Geosciences at the Technical University of Braunschweig. We are thankful for the critical reading of
Rene FroÈmmichen and the comments given by R.
Swennen, A. Harasuchi, H. Poellmann and two
anonymous reviewers. This study was supported
partly by the Bundesministerium fuÈr Bildung,
Wissenschaft, Forschung und Technologie (BMBF,
Fkz. 0339684).

T.M. Bachmann et al. / Journal of Geochemical Exploration 73 (2001) 75±86

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