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Chinese Science Bulletin 2003 Vol. 48 No. 21 2352ü2356

degradation has been established, that is, O2, NO3− , Mn4+,
Remobilization of trace metals Fe3+, SO 24 − and CO2[8], which also follows the classical
thermodynamics theory. But most studies are focused on
induced by microbiological marine sediments, but few on lacustrine sediments, and
the microbiological process and the mechanism of trace
activities near sediment-water metal cycling during early diagenesis are poorly docu-
ü
interface, Aha Lake, Guiyang mented[9 14].
The Aha Lake is a man-made reservoir with season-
1,2 1 1 ally oxygen-absent bottom water, located in the southwest
WANG Fushun , LIU Congqiang , LIANG Xiaobing
1,2 of Guiyang City. Since over 200 coal mines are scattered
& WEI Zhongqing
in the drainage area, plenty of acidic mining drainage
1. The State Key Laboratory of Environmental Geochemistry, Institute of
Geochemistry, Guiyang 550002, China; flows into the Aha Lake directly, causing excessive en-
2. The Graduate School of Chinese Academy of Sciences, Beijing richment of iron, manganese and sulfate in water and
100039, China sediments, while domestic sewages enter the lake from the
Correspondeuce should be addressed to Liu Congqiang (e-mail: wang- catchment area. The water column of this lake has not
fushun@ hotmail.com)
been obviously acidified for the lake is developed in the
Abstract The Aha Lake, as a seasonally oxygen-absent karst area, with pH equal to 7.28. The input of high-con-
man-made reservoir, has been polluted by acidic mining centration electronic acceptors in response to organic
drainage and domestic sewages for a long time, with iron, matter degradation under anoxic condition, substantially
manganese and sulfate excessively enriched in water and changed the water quality and the distribution mode of
sediment. By means of microbe counting, the analysis of trace metals in lake sediments, and organic matter degra-
trace metals in pore water and electronic acceptors for or- dation at the sediment-water interface is different from the
ganic matter decomposing, we have found that strong bio-
situation encountered in other freshwater lakes. Since the
geochemical remobilization of trace metals occurred near the
water-sediment interface. The microbial reduction of iron, strong acid-buffering potential of lakes in karst areas,
manganese and sulfate took place in different parts trace metals can easily be fixed in lake sediments if there
throughout the sediment core with the extend of iron reduc- is the sole acid mining drainage pollution, but if the or-
tion lower than that of sulfate reduction, which happened in ganic pollution is persistently introduced, the redox state
the surficial sediments and hampered the upward release of in lake sediments can be changed, and furthermore trace
some trace metals to some extent. Some trace metals in pore metals can be re-mobilized, causing serious “secondary
water, due to the “dual releasing” effects caused by the re- pollution”, which can threaten the safety of lake water,
duction of Fe3+ and Mn4+ at varying depth, show a tendency and become a “chemical bomb” buried at the bottom of
of being enriched excessively in the upper 10 cm of sediment.
the lake. In this study, the sample localities are near the
In this study, we discussed the microbiological mechanism of
trace metals enrichment in surficial sediments and the envi- dam of Aha Lake, for there has a composite feature of coal
ronmental condition, with an attempt to realize the unsteady mining drainage and domestic sewage pollution. This pa-
mobilization of trace metals and their potential harm to per deals with the relationship between the distribution of
overlying lake water in the Aha Lake, Guiyang. microbes responsible for iron and manganese reduction
Keywords: Aha Lake, trace metals, microbe, releasing effect. and the trace metals in pore water, and elucidates the
mechanism of trace metals enrichment in surficial pore
DOI: 10.1360/03wd0013
water.
Lake sediments, as the sink of various substances 1 Sampling and experimental
from a drainage area, especially from mining areas, (
) Sample collection. The Aha Lake, constructed
accommodate some harmful heavy metals. More and more in 1958 and put into operation in 1960, covers a lake area
attention has been paid to the “sink/source” transformation of 3.4 km2 and a catchment area of 190 km2, and has an
of trace metals due to various biogeochemical processes altitude of 1108 m, with the water residence time of 0.44 a.
near the sediment-water interface, for the sake of water The maximum water depth is 24 m, averaging 13.2 m. By
ü
resource management[1 4]. The distribution of different means of a portable non-disturbing sediment sampler[15],
geochemical phases of trace metals in lake sediments, has sediment cores were collected at the site of lake center
ü
been particularly emphasized in previous studies[5 7]. It near the dam of Aha Lake in May 2002. Bottom water was
has been realized that the continuous input of organic very clear, indicating a success in sampling. After siphoning
matter and the seasonal change of redox condition are the out bottom water, sediment was segmented in-situ at inter-
important factors affecting the geochemical cycling of vals of 1.0 cm. Pore water was collected by centrifugating
trace metals in lake sediments, and the preferential reduc- the sediment at 3500 r/min under low temperature (4).
tion sequence of primary oxidants due to organic matter (  ) Experimental. Pore water was divided into

2352 Chinese Science Bulletin Vol. 48 No. 21 November 2003

 REPORTS
three portions after 0.45 µm filtration: the first portion was reduction process is relatively complex, involving inor-
used to measure SO 24 − by liquid chromatography ganic and microbiological reduction. Furthermore, some
metal reducing bacteria, such as some of the DIRB, can
(HP1100); the second was used to measure dissolved Fe
reduce Mn as well, so dissolved Mn concentration profile
after being acidified with super pure HNO3 by atomic ab-
is usually taken to indicate Mn reducing process. Fig. 4
sorption spectrophotometry (ASS PE5100PC); the third
shows that Mn reduction is prior to sulfate and iron reduc-
was used to measure Mn, Co, Ni, Pb, Mo and Sc by
tion, but has a relatively wide reducing range down to
ICP-MS (Finnigan MAT-ELEMENT), with Rh as the in-
9-cm depth.
ternal standard, after being acidified with super pure
HNO3. Analytical error is lower than 5% for the above
elements.
Microbe counting: 1.0 g sediment was dissolved in
20 mL bacteria-free water, after dilution step by step, in-
cubating under strict anoxic condition, at 30. SRB (sul-
fate reduction bacteria) culture medium was prepared with
the following ingredients: lactic acid, 2.5 mL; yeast ex-
tract, 1.0 g; DL-Cysteine, 0.6 g; Na2SO4, 1.0 g; NH4Cl,
1.0 g; CaCl2, 0.1 g; K2HPO4, 0.5 g; (NH4)2SO4, 0.5 g; re-
sazurin (0.1%), 1.0 mL; agar, 15.0 g, and filtrated lake
water, 1000 mL. The pH value was adjusted to 7.0.
Dissimilatory Iron Reducing Bacteria (DIRB) culture
medium[16,17]: NaHCO3, 2.5 g; NH4Cl, 1.5 g; KH2PO4, 0.6 Fig. 1. Distribution of SRB near the sediment-water interface in the
g; KCl, 0.1 g; vitamin mixture 10.0 mL; trace element Aha Lake.
mixture 10.0 mL; sodium acetate, 1.5 g; amorphous
Fe(OH)3, 50.0 mmol/L; resazurin (0.1%), 1.0 mL; agar,
15.0 g, and filtrated lake water, 1000 mL. The pH was
adjusted to 7.0.
2 Discussion and results
(
) Microbiological activities and reduction to elec-
tronic acceptors. According to the results of counting for
DIRB and SRB in Aha Lake sediments, it was found that
DIRB and SRB have different preferential growth areas,
Fig. 2. Distribution of DIRB near the sediment-water interface in the
as shown in Figs. 1 and 2. The process of sulfate reduction, Aha Lake.
as is controlled by SRB distribution, has played an impor-
tant role in organic matter degradation in an anoxic envi-
ronment[1,18]. Fig. 1 shows that in this study, SRB have
maximum activities at 2 cm below the sediment-water
interface, with little activity below 6-cm depth. Sulfate
concentrations in pore water tend to decrease rapidly in
the top 5-cm sediment, strictly obeying the SRB distribu-
tion, which indicates that sulfate reduction occurs in the
surficial sediment, as shown in Fig. 3.
Just like sulfate reduction, iron reduction is also an
important factor leading to organic matter degradation in
ü
anoxic sediments as well[17,19 22]. But unlike SRB, DIRB
have the strongest activity at the 10-cm depth under the
water-sediment interface, with weak activity in surficial
sediments, which is in concordance with the iron concen-
tration profile in pore water (Fig. 4), that is, the stronger
the DIRB activity is, the higher the dissolved iron concen-
trations will be. The distribution profiles of DIRB and
SRB indicate that sulfate reduction is prior to iron reduc-
tion, which is different from the preferential reduction Fig. 3. Distribution of sulfate near the sediment-water interface in the
sequence in the marine anoxic environment[8]. Manganese Aha Lake.

Chinese Science Bulletin Vol. 48 No. 21 November 2003 2353

REPORTS
lake sediments and lake water still keeps neutral, owing to
the strong acid buffering potential of lake in karst areas,
and the neutralizing treatment of coal mining drainage
using lime in the recent decade. Along with increasing pH,
dissolved iron and manganese will become oxides or hy-
droxide, while trace metals are adsorbed or co-precipitated
synchronously.
In the Aha Lake, when the sediment-water interface
becomes anoxic, organic matter still continues to be min-
eralized by way of reducing other electronic acceptors,
such as Fe3+, Mn4+ and SO 24 − , depending on their concen-
trations in the environment. From the above data, it is
clear that manganese reduction restrained iron reduction in
the upper part of the sediment core. DIRB activities began
to increase in going downward, with decreasing Mn re-
ducing ability, leading to the release of adsorbed trace
metals on iron and manganese oxides or hydroxides, re-
Fig. 4. Distribution of Fe and Mn in pore water of sediment in the Aha
spectively[16,24], as shown in Figs. 2 and 4. Consequently,
Lake. the desorbed trace metals may show “dual concentration
peaks” at depth during the iron and manganese reducing
() Distribution of trace metals in pore water. In process. The upper peak may be caused by manganese
natural environments, microorganisms can utilize some reducing, while the lower one by iron reducing. The re-
trace elements as life-indispensable ingredients to take leased trace metals may diffuse toward overlying water
part in some physiological functions in organism, which column, along the concentration gradient.
require a little amount of such trace elements, and hence () Factors affecting the precipitation of trace met-
would exert a negligible influence on trace element mobi- als. During the process of iron and manganese reducing,
lization. But environmental media, in cases the materials dissolved Mn and Fe and released trace metals may dif-
contain trace metals, can be changed by physiological fuse upwards, but in some cases they may be restricted by
activities of microorganisms to some extent, exerting a the sulfate reducing process and dissolved oxygen content.
One particularity of the Aha Lake is that sulfate reduction
great influence on the mobilization of some trace metals.
happens in the surface layer of the sediment core, just
As shown in Fig. 5, Co, Ni, Sc, Ba, Mo and Pb in
overlapping the manganese reducing position, and higher
pore water tend to be enriched excessively in surficial than the iron reducing position. Part of the released Fe and
10-cm depth sediments, with respective concentration trace metals diffusing from lower pore water may react
peaks appearing at different positions. Co and Ni, with the with H2S, produced by sulfate reduction near the sedi-
same distribution characteristics, show “dual peaks” at ment-water interface, to form sulfide precipitants (FeS,
2-cm and 4-cm depths, respectively. Mo only has a single FeS2), on which some trace metals even can be ad-
concentration peak at 2-cm depth, while Sc has a peak at 3 sorbed[11]. Fe () diffusing into the overlying water col-
4-cm. A good correlation (r = 0.98) exists between Ba umn can be oxidized to Fe () rapidly, even in the low
and Mn. Dissolved Pb decreases rapidly from the sedi- oxygen condition, and then hydrolyzed to form hydroxyl
ment-water interface to 3-cm depth, and shows a concen- compounds, which can capture trace metals in water syn-
tration peak at 5-cm depth. As a whole, the trace metals chronously, and be re-precipitated on the water-sediment
listed above have the same feature, i.e. strong enrichment interface. In seasons with oxygen enrichment in lake water,
in surficial pore water, and at the same time, they also redox boundary can lie just below the SWI (sediment-
show different distribution characteristics controlled by water interface), thus forming an adsorption layer consist-
their unique geochemical properties. ing of iron and manganese oxides or hydroxides, which
baffles greatly the upward-diffusion of trace metals,
() The release of absorbed trace metals induced by
caused by reduction process in lower-level sediments.
microbiological iron and manganese reduction. In most
( ) Mechanism of trace metal mobilization and en-
natural surface water environments, the concentrations of richment in pore water of surface sediment. Iron and
trace metals are restricted mainly by adsorption or manganese oxides or hydroxides are widespread in the
co-precipitation processes[23]. Plenty of acidic mining hypergene environment, and show strong adsorption po-
drainage, containing Fe, Mn, SO 24 − and other trace met- tential of trace metals in water owing to their huge
als, from upstream, enters the Aha Lake, but the pH of specific surface area and surfacial chemical activity.

2354 Chinese Science Bulletin Vol. 48 No. 21 November 2003

 REPORTS

Fig. 5. The concentration profile of Co, Ni, Sc, Ba, Mo and Pb in pore water of the Aha Lake.
Organic matter degradation, which needs the participation sisting of iron and manganese oxide or hydroxide. The
of microbes at ambient temperature, is the most important long-term effect of seasonal oxygen-absent process in this
geochemical process, and it can provide driving force for lake is that most trace metals are enriched in surficial
early diagenesis[27]. In 1988, two dissimilatory iron reduc- sediment and its pore water, with the gradual decrease of
ing bacteria (Shewanella putrefaciens and Geobacter met- trace metals present in reducible phase of the lower-level
alloreducens) were successfully separated, and the impor- sediments, caused by strong cycling of iron and manga-
tance of iron and other electronic acceptors in the process nese. This is why DIRB activity is stronger in the lower
of microbiological anoxic respiration has been gradually sediment layers, but the released trace metals are ex-
realized[28]. tremely low in amount. On the contrary, most trace metals
Seasonal oxygen absence in lake water, persisting are released in surface layers with weak DIRB activity.
input of organic carbon, coupling with the excessive load- Previous studies, mainly on marine sediments, have also
ing of iron, manganese and sulfate, provide necessary revealed the enrichment of trace metals in surficial sedi-
conditions for trace metal-remobilization at the sediment- ments, and the significance of iron and manganese cy-
water interface. (1) In an anoxic season, with the propa- cling[3,25,26,29], but the extent of enrichment is not so typical
gating of anaerobic bacteria, dissimilatory reduction is as compared with that observed in our study. The change
enhanced, causing the activation and mobilization of some of trace metals concentrations in pore water depends on
trace metals. But as discussed above, sulfate reduction, homeostasis between releasing and precipitation processes.
which happened in surficial sediments, may restrict the As discussed above, iron, manganese and sulfate reduction
upward-diffusion of trace metals in pore water to some happen at different depths. Since iron and manganese ox-
extent, and iron and manganese cycling between water ides and hydroxides are good sorbents, their reduction will
and sediment can capture trace metals diffusing into the lead to the release of adsorbed trace metals, causing the
overlying water column and return to the sediment-water dual peaks of trace metals in pore water. Specifically, Co
interface. (2) In a season with oxygen enrichment in bot- and Ni have the same distribution curves, since both be-
tom water, both the growth of anaerobe and anoxic respi- long to the iron-family elements, with the similar atomic
ration in surficial sediments are restrained, and trace met- structure and geochemical behavior. The dual peaks of Co
als, released in response to reduction in the lower layer, and Ni, as discussed above, are caused by iron and man-
are retained in the surface adsorbing layer, mainly con- ganese reduction, respectively, while the upper peaks of

Chinese Science Bulletin Vol. 48 No. 21 November 2003 2355

REPORTS
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