Lakes & Reservoirs: Research and Management 2000 5: 11–21

Role of bottom sediments in the secondary pollution of

aquatic environments by heavy-metal compounds
Peter M. Linnik* and Irina B. Zubenko
Department of Ecotoxicology and Hydrochemistry, Institute of Hydrobiology, National Academy of Sciences,
Geroev Stalingrada Avenue 12, Kiev 254210, Ukraine

Abstract
The results of long-term investigations into the concentrations of some heavy metals (Fe, Mn, Cu, Zn, Pb, Cr, and Cd) in the
bottom sediments of the Dnieper reservoirs and the Dnieper–Bug estuary are considered. Maximum quantities of the metals
studied are characteristic of southern water bodies located within industrial zones (the Zaporozh’e and Kakhovka reservoirs
as well as the Dnieper–Bug estuary). The highest concentrations of the metals studied occurred in the clay silts (Fe,
11 600–32 400; Mn, 1504–3450; Cu, 38.9–85.5; Zn, 89.8–186.5; Cr, 48.6–193.0; and Cd, 1.9–4.4 mg kg-1 dry weight). Accumulation
of heavy metals in the bottom sediments is an important factor in the self-purification of aquatic environments. However, this
process is reversible and therefore provides a constant threat of secondary water pollution. Secondary water pollution is
observed in summer and autumn when water consumption increases. The concentrations of heavy metals increase by a factor
of 1.5–3 after the drawdown of the water level. The main reason for the rise in the concentrations of metals is exchange between
the bottom sediments and the water column. The rate of heavy metal migration is connected with the forms of occurrence
in solid substrates and pore solutions in the bottom sediments, as well as with physico-chemical conditions arising at the
sediment/water boundary. Therefore, our investigations concentrated on the study of the fractional distribution of heavy metals
among solid substrates and their forms of occurrence in interstitial solutions. This distribution depends, most of all, on the
chemical properties of metals as well as the chemical and mineralogical composition of the sediments and the chemical
properties of pore solutions. Most of the supply of Mn, Zn, Fe, and Cd is associated with oxides and hydroxides of iron and
manganese (Mn, 74–93%; Zn, 43–70%; Fe, 27–59%; and Cd, 28–41%). Most copper and chromium is bound to organic matter
and to scarcely soluble minerals. In the interstitial solutions studied, metals (except manganese) are found mainly as complex
compounds with dissolved organic matter of a different molecular weight. Nevertheless, the fraction of complexes with a
relatively low molecular weight (500–5000 Da) prevailed (40–70%). Dissolved manganese in the pore solutions consists chiefly
of free (hydrated) ions Mn21 (80–95%). The results obtained were used for a comparative evaluation of heavy metal mobility
and the exchange ability of their associated compounds in the bottom sediment–water system.

Key words
bottom sediments, diffusion, heavy metals, migration mobility, pore solutions, reser voirs.

INTRODUCTION than in elevated concentrations in water. The ecological

The accumulation of pollutants in the bottom sediments of
water bodies and the remobilization of these substances from
the latter are two of the most important mechanisms in the
regulation of pollutant concentrations in an aquatic environ-
ment. Heavy metals (HM) are an important group of chem-
ical pollutants in natural waters. The HM pollution of
aquatic ecosystems is often most obviously reflected in high
metal levels in sediments, macrophytes and benthic animals,
*Corresponding author.
Accepted for publication 8 September 1999.
effects of HM in aquatic ecosystems and their bioavailability
and toxicity are closely related to species distributions in the
solid and liquid phases of water bodies. Unlike organic con-
taminants, which can be degraded to various degrees, HM
do not undergo such transformations. They are always pres-
ent in aquatic ecosystems and redistribute only among differ-
ent components. Water bodies with slow water-exchange
rates (e.g. lakes and reservoirs) accumulate HM in their
bottom sediments in considerable quantities. This phenom-
enon has both positive and negative features. On one hand,
the bottom sediments promote self-purification in the aquatic
12 P. M. Linnik and I. B. Zubenko

environment because of HM accumulation. On the other
hand, HM accumulation in the bottom sediments can be
reversed. Under certain conditions, bottom sediments can
be a strong source of secondary water pollution (Denisova
et al. 1989; Linnik et al. 1993). The release of HM from
bottom sediments is promoted, for example, by a deficit in
dissolved oxygen, a decrease in pH and redox-potential (Eh),
an increase in mineralization and in dissolved organic
matter (DOM) concentration.
The mobility of HM depends on their forms of occurrence
in the solid substrates and pore solutions of the bottom sedi-
ments, as well as on the physico-chemical conditions that
arise on the boundary of solid and liquid phases, as noted
previously. HM flow from pore solutions is one of the most
important ways of exchange between bottom sediments
and water.
One aim of this paper is to present data concerning
both HM distribution among different fractions of bottom
sediments, and the coexisting forms of HM in interstitial
solutions in some Dnieper water bodies. Another aim is to
assess the migration mobility of HM in the bottom
sediment/water zone. Such information will increase
understanding of the reasons for the secondary pollution of
aquatic environments by HM compounds from bottom
sediments.
with direct aspiration of the extract into an acetylene–air
flame, was used for analysis.
The interstitial solutions were separated from freshly
collected samples by centrifugation for 30–40 min at 5000
revolutions per minute. HM analysis of interstitial solutions
involved chemiluminescence methods (Fe, Mn, Cu, Cr) and
an anodic stripping voltammetry method (Zn, Pb, Cd)
(Nabivanets et al. 1981; Linnik & Nabivanets 1988; Linnik
& Iskra 1994). The concentration of so-called free (hydrated)
metal ions was determined in situ immediately. For deter-
mination of the concentration of the dissolved metals after
photochemical destruction of DOM, and to determine
molecular weight distribution of metal complexes, the pore
solution samples (25–50 mL) were stored frozen in poly-
ethylene bottles. Ultraviolet-irradiation of the pore solution
samples (pH ~ 1) was carried out in quartz glasses by using
a DRT-1000 mercury lamp (Electromedical apparatus plant,
Ekaterinburg, Russia) for 4–5 h. The molecular weight dis-
tributions of metal complexes were investigated after their
separation on a column with neutral sephadex G-75
(Pharmacia, Uppsala, Sweden).
RESULTS AND DISCUSSION
The investigation was carried out on the Dnieper River,
which is 2201 km long (981 km is within the Ukraine) and

METHODS
Bottom sediment samples were collected by an Ekman
bottom grab (SBS-100; St Petersburg, Russia) during scien-
tific expeditions in 1990–1994. To investigate the fractional
distribution of heavy metals in the bottom sediments of
Dnieper water bodies, a five-step sequential extraction pro-
cedure was applied (Tessier et al. 1979). A series of chemical
reagents, which extract metals from different geochemical
fractions in a specific sequence, was used. This approach
simulated the natural conditions under which the metals may
become mobile and available. It is impossible to reproduce
natural conditions and processes exactly, and therefore the
results do not fully reproduce the true distribution found in
nature (Rendell et al. 1980; Hart 1982). When using this
method, allowance must be made for the possibility of sec-
ondary adsorption, and for other sources of error. Even so,
the procedure is widely used by both soil scientists and
hydrochemists.
To compare our results with data on specimens from other
sources, the < 63 mm particle-size fraction was obtained after
passing the sediments through a capron screen. The concen-
trations of HM in the separated fractions were determined
(with three replications) after their dissolution in a mixture
of concentrated acids (HF, HCl, HNO3). A Carl Zeiss Jena
(Jena, Germany) atomic absorption spectrophotometer, Fig. 1. Map of Dnieper water bodies.
Bottom sediments and secondary water pollution 13

drains an area of 504 000 km2. The Dnieper has six reservoirs
and drains into the Dnieper–Bug estuary (Fig. 1). The main
morphometric characteristics of the water bodies investi-
gated are shown in Table 1. The annual mean discharge of
the Dnieper River is approximately 48 km3.
The construction of a reservoir cascade on the largest
river in the Ukraine has turned the Dnieper into a multi-
purpose water basin of great importance to the Ukrainian
national economy. The Dnieper provides the main source of
drinking water for up to 75% of the population of the Ukraine
and irrigates more than 1.8 3 106 ha of agricultural land. It
is also a source of cheap hydroelectric energy and a major
transportation artery. However, the creation of a cascade of
reservoirs has had both positive and negative effects.
Undoubtedly, it led to an amelioration of the water deficit
problem in the Ukraine because of a more rational use of
water resources and a redistribution of the water among
poorly irrigated regions. At the same time, the slower water
flow of the river and the decrease in the extent of water
exchange, as well as changes in the circulation of substances
in reservoirs compared to the river, caused changes in the
hydrological regime of the Dnieper river and in the hydro-
chemical regime in the reser voirs. Such undesirable
phenomena as the significant formation of bottom silt,
eutrophication, and reservoir pollution have resulted from
the suspension of sediments and the accumulation of nutri-
ents, organic substances, HM and radionuclides. Our earlier
results indicated that HM accumulated in greater amounts
in the sediments of Dnieper water bodies (Table 2).
Investigations of migration and accumulation of HM in reser-
voirs have further shown that the metals are often associ-
ated with fine suspended particles of mineral and organic
matter (Tsvetkova & Novikov 1995). Assessment of the total
level of contamination by HM in bottom sediments requires
the selection of comparative criteria. The established limits
for the concentration of chemical substances in soil
(Goncharuk & Sidorenko 1986) appear reasonable in this
context, if bottom sediments are to be dredged and used as
a natural fertilizer. The concentrations of HM in the sedi-
ments of freshwater reservoirs not affected by human
activity were used as standard background concentrations
(Förstner 1977; Salomons & Förstner 1984). However, this

Table 1. Main morphometric characteristics of the Dnieper reservoirs and the Dnieper–Bug estuary

Reservoirs
Characteristics Kiev Kanev Kremenchug Dnepro-dzerzhynsk Zaporozh’e Kakhovka Dnieper–Bug estuary

Surface area (km2) 922 675 2250 567 410 2150 1006
3
Volume (km ) 3.73 2.62 13.5 2.45 3.30 18.20 4.24
Length (km) 110 123 149 114 129 230 63
Width (km)
Maximum 12.0 8.0 28.0 8.0 7.0 25.0 15.0
Mean 8.4 5.5 15.1 5.1 3.2 9.3 6.7
Depth (m)
Maximum 14.5 21.0 20.0 16.0 53.0 24.0 12.0
Mean 4.0 3.9 6.0 4.3 8.0 8.5 4.4

From Denisova et al. (1989).

Table 2. Concentration of HM in the surface layer (0–5 cm) of the bottom sediments of the Dnieper water bodies

Reservoirs
Metals Kiev Kremenchug Zaporozh’e Kakhovka Dnieper–Bug estuary

Fe 1.1–32.4 1.6–14.2 – 1.1–17.3 0.9–11.6

Mn 380–3450 245–2575 410–2920 183–1905 318–1504
Cu 19.0–38.9 20.7–56.8 27.0–85.5 25.5–76.4 15.5–69.4
Zn 38.6–105.8 35.2–89.8 50.6–186.5 41.5–142.0 34.5–155.0
Pb 19.8–56.5 17.2–48.9 23.2–61.5 21.8–63.3 18.5–153.0
Cr 24.5–48.6 22.8–58.0 91.6–147.5 15.6–84.5 64.5–193.0
Cd 0.7–2.2 0.5–1.9 1.2–3.8 0.8–3.9 0.9–4.4

Data are expressed as mg kg–1 dry weight, except for the concentration of iron in the bottom sediments, which is expressed in g kg–1 dry
weight. –, not investigated. Data on the heavy metal content in different types of sediments (from sand to clay silt) are presented.
14
criterion must be used with caution, as aquatic pollution has
become a global problem. We used clay silts from the main
part of the Dnieper reservoirs to assess the contamination
levels of HM in the water bodies studied. Values for sedi-
mentary rock served as assessment criteria: Fe, 33300; Mn,
670; Zn, 90; Cr, 100; Pb, 39; Cu, 34; and Cd, 0.3 mg kg–1 dry
weight (Vinogradov 1957). At present, the concentrations of
manganese, zinc, lead, copper, and chromium in the clay silts
of the reservoirs substantially exceed (by 1.5–5-fold) those
found in sedimentary rocks. In a sense, the bottom sedi-
ments are indicators of the extent of reservoir pollution by
HM compounds (Nakhshyna & Belokon’ 1990; Korableva
1993; Tsvetkova & Novikov 1995). In the bottom sediments
of the Dnieper reservoirs, the total HM concentration tends
to increase down the cascade. Zaporozh’e and Kakhovka
reservoirs, as well as the Dnieper–Bug estuar y, are the most
polluted. The high HM concentrations in the sediments of
the southern water bodies were associated with high HM
concentrations in water in both reser voirs and the
Dnieper–Bug estuary (Fig. 2). The main source of HM,
especially in the most polluted southern reservoirs, is
insufficiently treated wastes from mining and metallurgical
and chemical factories.
The undesirable functional features of the reservoir
cascade are: first, that they act as sinks for pollutants; low
flow rates allow the formation of a lentic regime (with active
blooming of blue-green algae) which degrades water quality.
Second, toxic components accumulate in bottom sediments,
creating a threat of secondary aquatic pollution, especially
at times of excessive reservoir drawdown (Linnik et al.
1993). Finally, the likelihood of secondary pollution by HM
compounds becomes more probable. Secondary aquatic
pollution by HM is observed not only in winter, but also in
summer, when water consumption for industrial and agri-
cultural needs is increased. In summer, metal concentrations
increase several-fold after drawdown (Fig. 3). This is
common in Kremenchug reservoir and somewhat less so
in Kakhovka reservoir. The extent of the increase largely
depends on hydrological conditions; in years with
P. M. Linnik and I. B. Zubenko
Fig. 2. Average concentrations
of heavy metals in the water
of the Dnieper reservoirs and
the Dnieper–Bug estuary. (h),
Kiev reservoir; (j), Kremenchug
reservoir; ( ), Kakhova reservoir;
( ), Dnieper–Bug estuary.
Fig. 3. Concentrations of heavy metals in the Kremenchug reser-
voir (1) before and (2) after drawdown. (h), Cu; ( ), Zn; (j), Cr;
( ), Pb.
pronounced spring high-water periods (for example 1988),
the summer rise in the concentration of HM does not exceed
50–100%. This is probably because of increased water
exchange and decreased stagnation in the reservoirs
following spring flushing. In low-water years, or when there
is an insufficient spring high-water period, the concen-
trations of HM increase by a factor of 2–3 after drawdown.
This occurred in 1989 and 1990 (see Fig. 3).
The main reason for the rise in the concentrations of HM
after drawdown is the increased rate of exchange between
bottom sediments and the water column, which is promoted
by an accelerated oxygenation of both water and sediments,
but which ultimately results in a depletion of dissolved oxy-
gen. The development of reducing conditions in the surface
layer of the bottom sediments promotes the reduction of iron
and manganese hydroxides, so that they enter into solution.
Because these hydroxides absorb large amounts of HM
(30–95% in the Dnieper reservoirs), HM will enter the water
column following desorption. In summer, the dissolved
metals, except manganese, consist mostly of complexes with
DOM (75–90%). They pass from the bottom sediments to the
water together with the organic substances. Among these
organic complexes, complex compounds of low molecular
weight (500–5000 Da) are predominant (40–70%).
Bottom sediments and secondary water pollution 15

A decline in the amount of fresh water released from
Kakhovka reser voir to the lower Dnieper River has
increased the concentrations of HM in the estuary
(Zhuravleva & Linnik 1989). Long-term investigations reveal
that in summer and autumn, HM concentrations were gen-
erally two- to five-fold higher than those in spring (Fig. 4).
There was an especially large rise in the concentration of
manganese, which has a mobility that depends on the pH
and redox potential in the bottom sediment–water system
(Table 3). Under anaerobic conditions, manganese rapidly
builds up in the water as a result of exchange with the inter-
stitial solution in the bottom sediments. Its concentration in
bottom waters sometimes reaches several mg L–1. The main
reason for the rise in the concentrations of other HM in the
water is the reduction of iron and manganese hydroxides,
which actively absorb Zn, Pb and Cd, as noted above for
reservoirs after drawdown. It is also possible that HM pass
from bottom sediments to water as a result of exchange reac-
tions involving the principal ions of seawater (Na1 and
Mg21), as a decline in the volume of river runoff increases
the effect of the Black Sea on the estuary.
The Dnieper cascade has been completed, and its reser-
voirs have well-established ecosystems. However, the
approach to investigation of heavy metals in the waters, and
especially in water bodies with regulated discharge, has
changed. Investigators now stress the need for more pro-
found studies of bottom sediments as the most important
factor governing the behaviour of metals in water bodies.
The earlier approach (determination of total concentration)
only indicated the supply of a given metal, but revealed virtu-
ally nothing about its circulation or its involvement in sec-
ondary pollution, for example. A five-stage successive
extraction method allows the separation of metal compounds
in the exchangeable and carbonate fractions, in the iron and
manganese oxide fraction, in organic matter, and in the resid-
ual fraction (in the crystal lattices of primary and secondary
minerals). The results of such investigations are important
in assessing the migration mobility of HM in the bottom
sediment/water zone.
The distribution of those metals investigated in different
fractions of Dnieper reservoir sediments is shown in Fig. 5.
The total cadmium concentration in silts of Dnieper water
bodies comprises 1.9–4.4 mg kg–1 dry weight (see Table 2)
and is considerably higher (by 6–15-fold) than in sediment-
ary rocks (Vinogradov 1957). Most of this metal is found
in three fractions: exchangeable fraction (22–32%), the iron
and manganese oxide fraction (28–41%), and organic mat-
ter fraction (20–34%).
The total concentration of copper in the surface layer of
the same silts is 38.9–85.5 mg kg–1 dry weight. These values
Fig. 4. Concentration of heavy metals in the water of the
Dnieper–Bug estuary and the annual distribution of water flow (Q)
in the lower Dnieper from 1985–1989. (h), Cu; ( ), Zn; (j), Cr;
( ), Pb; (j), Q.

Table 3. Concentration of dissolved manganese in water of the Dnieper–Bug estuary, July 1988

Surface layer Bottom layer

Mn O2 Salinity Mn O2 Salinity
Place of water sample (mg L–1) (mg L–1) pH (g L–1) (mL–1) (mg L–1) pH (g L–1)

Dnieper estuary
Eastern part
Station 3 35.6 8.3 8.2 0.2 920.0 0.2 7.2 19.9
Central part
Station 8 53.4 11.0 8.9 – 116.8 7.5 8.3 –
Western part
Station 15 92.3 10.4 8.5 1.8 160.0 3.8 8.2 16.6
Station 17 – 14.0 9.1 2.5 1750.0 0.0 7.0 12.6
Station 20 36.0 11.4 9.1 2.1 265.0 1.5 7.7 15.7
Bug estuary
Station 11 28.0 12.0 9.1 1.6 128.0 2.7 8.1 15.9
Station 13 140.0 7.9 8.6 3.3 286.0 4.1 8.0 7.4
16
are higher than in sedimentary rocks by almost 1.5–2.5-fold.
Most copper is bound to organic matter (67–77%). With
regard to this connection, it should be noted also that there
is a high concentration of organic matter in silt sediments
(approximately 6.5–12%; Denisova et al. 1989). Considerable
binding of copper by organic matter also occurs in the bot-
tom sediments of Canadian rivers (Tessier et al. 1979). Thus,
copper can be mobilized only by the breakdown of organic
matter. However, in the river sediments of Central Europe,
nearly 80% of Cutot is bound to the oxides and hydroxides of
P. M. Linnik and I. B. Zubenko
iron and manganese (Calmano & Förstner 1984). In the
residual fraction of the sediments investigated, copper was
up to 8–31% of Cutot. The concentration of the most mobile
exchangeable form of copper is 8% or less of Cutot in all
reservoirs.
Maximum quantities of manganese are typical for silts of
the Kiev reservoir. Long-term investigations of HM in the
bottom sediments have revealed tendencies for some
decrease in manganese concentrations down the cascade.
This is also the case for iron. Probably, most of the
Fig. 5. Forms of occurrence of heavy
metals in the silt sediments of the
Dnieper reservoirs. 1, Kiev; 2, Kanev;
3, Kremenchug; 4, Zaporozh’e; 5,
Kakhovka. (a) Cd; (b) Cu; (c) Mn; (d)
Fe; (e) Zn; (f) Cr. (j), Exchangeable;
(h), carbonate; ( ), oxides; ( ),
organic; ( ), lithic.
Bottom sediments and secondary water pollution 17

manganese (74–93% of the total content) is found in the iron
and manganese oxides fraction. Hydrated manganese oxides
(MnO2 . xH2O) are a component of one of the main geo-
chemical phases, and they play an important role in the
removal of other metals from the aquatic environment by
self-purification (Sager 1992). At the same time, the dis-
tribution of iron among different fractions of the sediments
is characterized by its domination in both the iron and
manganese oxide fraction and the organic matter fraction
(27–59 and 33–63%, respectively).
The concentration of zinc in the silts of the Dnieper water
bodies varied from 89.8 to 186.5 mg kg–1 dry weight. The zinc
concentration in the silts of the Zaporozh’e and Kakhovka
reservoirs, as well as the Dnieper–Bug estuary, is almost two
times higher than its concentration in sedimentary rocks.
Although zinc concentrations in the sediments of the
Dnieper reservoirs are well correlated with organic matter
concentrations (Denisova et al. 1987), most of the supply of
zinc is associated with the oxides and hydroxides of metals
(43–70%). Large amounts of zinc in iron and manganese
hydroxides have also been found in the Yamaska and St
Francois rivers in Quebec (nearly 40%) and some small rivers
in northern France (up to 72%; Sager 1992). Zinc in the
organic matter fraction is less significant and comprises
24–40%. In its exchangeable form, the concentration is lower
(2.3–5.1%).
Maximum values of chromium are found in the silts of
the southern reservoirs and the Dnieper–Bug estuary.
Concentrations are higher by 1.5–2-fold than levels in sedi-
mentary rock (Vinogradov 1957). Its distribution among
different solid fractions differs from that of other metals. In
the bottom sediments of the reser voirs investigated,
chromium is associated with sediment organic matter
(37–45%) and also occurs in scarcely soluble form (residual
fraction, 31–53%). It is probably present in chromites and
heavy minerals (Sager 1992). Thus, chromium in the
residual fraction is buried in the bottom sediments as
insoluble compounds and cannot re-enter circulation.
Overall, data on the fractional distribution of some HM
among solid sediment substrates in the Dnieper reservoirs
indicate that cadmium has the highest migration mobility.
It is characteristically enriched in the more mobile cation
exchange and moderately reducible fractions. At the same
time, the migration mobility of cadmium in the bottom
sediment/water zone is insignificant so long as most of it is
bound in the residual fraction of the sediments. As shown
earlier, the ease with which metal leach from sediments
decreases in the order: Cd > Pb > Zn > Cu > Mn > Ni > Cr > Co
(Lund 1990). For the Dnieper reservoirs, in accord with
migration mobility, the metals investigated can be placed
in the sequence: Cd > Mn > Zn > Fe > Cu > Cr (Zubenko &
Linnik 1997).
As noted, the flow of HM from interstitial solutions is one
of the most important methods of exchange between bottom
sediments and water. Changes in the concentration equilib-
rium and the formation of differential HM concentrations at
the boundary of the solid and liquid phases are the neces-
sary preconditions for diffusion flow to begin. However, the
rate of molecular diffusion depends not only on the concen-
tration gradient but also on the coefficient of molecular (ion)
diffusion, that is,
dm dc
5–D S
dt dx
where m is the quantity of diffused matter, D is the diffusion
coefficient depending on the properties of diffused particles
and the medium, dc/dx is the gradient of concentration, S
is the square which the diffusion flow crosses and t is the
diffusion duration. The diffusion coefficient is related to the
molecular weight of diffusible particles. When the molecular
weight of these is high, the value of the diffusion coefficient
is low. The diffusion coefficient of most free metal ions is

Table 4. Concentration of heavy metals in the pore solutions of (1) the silt sediments and (2) the aquatic environment of the Dnieper water
bodies

Kiev reservoir Kremenchug reservoir Kakhovka reservoir Dnieper–Bug estuary

Metals 1 2 1 2 1 2 1 2

Fe 3.69 0.28 2.20 0.14 1.68 0.12 2.85 0.13

Mn 4.65 0.08 2.85 0.08 1.96 0.07 2.76 0.07
Cu 0.24 0.02 0.16 0.03 0.18 0.04 0.21 0.06
Zn 0.36 0.04 0.42 0.05 0.59 0.06 0.60 0.07
Pb 0.13 0.02 0.12 0.03 0.24 0.03 0.15 0.03
Cr 0.16 0.02 0.14 0.03 0.22 0.05 0.18 0.06

Data are averages and expressed as mg L–1.

18
approximately n.10–5 cm2 sec–1. For some carbohydrate mol-
ecules, for example arabinose (molecular weight, 160 Da)
and raffinose (molecular weight, 504 Da), it is 6.25 3 10–6 and
3.65 3 10–6 cm2 sec–1, respectively (Voyutsky 1976). Thus, the
diffusion rate of free metal ions and their low molecular
weight complexes are higher than those of metal complex
compounds of high molecular weight, for example humic
and fulvic acids, protein-like compounds and polypeptides.
The molecular diffusion rate of free manganese, copper and
zinc ions is 0.1–1.5 3 10–2 mg cm–2 sec–1. The same parameter
for their complexes with humic acids (~5000 Da) and fulvic
acids (~2200 Da) is 0.2–3.5 3 10–4 mg cm–2 sec–1, that is,
almost 100-fold lower (Romanova 1987).
Data on HM concentrations in water and interstitial sol-
utions in the bottom sediments of Dnieper water bodies are
shown in Table 4. There are important differences in their
concentrations, especially for manganese and iron. The con-
centrations of these metals in the interstitial solutions are
from 30 to 50 times higher than in the bottom water layer.
There are not such differences in the concentrations of other
metals. For this reason, attention has been focused on the
migration mobility of manganese and iron. Because of the
high gradient of their concentrations, increased rates of flow
from the interstitial solutions into the bottom layer water can
be expected. This is typical for manganese, which passes
quickly (2–3 days), and in greater quantities than iron into
the overlying water (Fig. 6). The principal factors that inten-
sify this process are the dissolved oxygen deficit and a pH
decrease at the boundary of the liquid and solid phases. Note
that a pH decrease is an especially important factor. At the
same time, the exchange intensity of iron depends on the
P. M. Linnik and I. B. Zubenko
lowering of the oxygen concentration and pH to a lesser
degree than does that of manganese (see Fig. 6). The cause
of the different behaviour of manganese and iron is their
state in the interstitial solutions (Fig. 7). Here, almost all
manganese (80–95%) is found as free ions. This form of HM
is known to be the most mobile. Compared with manganese,
iron is a more typical representative of HM, which bind
mostly with DOM of different molecular weights. In particu-
lar, the share of the organic complexes for those metals
investigated with relatively low molecular weight (500–
5000 Da) reaches to 40–70%. Least mobile high molecular
weight HM compounds (> 30 000–50 000 and > 60 000–
70 000 Da) make up 30–48% of the total concentration of
organic complexes in interstitial solutions. The rate of flow
of such compounds from interstitial solutions into the
aquatic environment will be minimal. The results of our
experimental investigations agree well with the field data on
manganese migration mobility in the bottom sediment/water
zone (Fig. 8). Thus, in Kiev reservoir water, the concen-
tration of manganese can increase to 0.5–0.8 mg L–1 in the
winter when the concentration of dissolved oxygen and pH
decrease to 0.8–1.2 mg L–1 and 7.0–7.2, respectively. Most
manganese then is not bound in complexes with DOM. It is
evident that manganese passes from bottom sediments in
the form of Mn21 ions. At the same time, the high concen-
trations of manganese create problems for supplies of
drinking water for Kiev. An analogous increase of manganese
concentration was often obser ved in summer in the
Dnieper–Bug estuary following the development of anaer-
obic conditions in bottom-layer waters (see Table 3).
The vertical extent of manganese diffusion flow (and
Fig. 6. Change in concentration of
(a;1,2) dissolved oxygen, (a;3,4) pH,
(b) chemical oxygen demand, (c) man-
ganese and (d) iron in the aquatic
environment in accord with the con-
tact time of the water and bottom
sediments (Kanev reservoir, upper
part, June 1996; ratio of silt to water
1 : 11). (r), 1; (j), 2; (d), 3; (
*), 4.
Initial data: CMn 5 24.5 mg L–1; CFe 5
0.56 mg L–1; O2 5 10.5 mg L–1; pH 5
8.3; COD 5 53.3 mg O L–1. 1,3,
Without addition of Na2SO3 saturated
solution and CH3COOH; 2,4, after
addition of Na2SO3 saturated solution
and CH3COOH for the sharp decrease
of dissolved oxygen and pH (third
day).
Bottom sediments and secondary water pollution
perhaps that of other metals) depends on the position of the
redox boundary. If the bottom-layer water has high Eh
indices when there is a low degree of oxygen absorption by
Fig. 7. Ratio of different forms of HM in pore solutions of the bot-
tom sediments in (a) the Kiev reservoir and (b) the Dnieper–Bug
estuary. Data are the percentage of Medissolved. (j), Free metal ions;
( ), 500–5000 Da; ( ), 5000–15 000 Da; ( ), 30 000–50 000 Da;
( ) > 60 000–70 000 Da.
Fig. 8. Changes in (a) dissolved oxygen concentration and pH and
(b) dissolved manganese concentrations in Kiev reservoir water in
1997. (m), dissolved oxygen concentration; (r), pH.
19
bottom sediments, the redox boundary is deep in the bottom
sediments. In this case, the manganese diffusion flow has
no time to pass through the sediments to their surface
because manganese oxidation and precipitation begin more
quickly. If the redox boundary exists near the boundary of
the bottom sediment/water zone, then diffusible man-
ganese will be oxidized and precipitate into the bottom layer
water. Finally, if the redox boundary is higher than the sur-
face of the bottom sediments, then mobile manganese dis-
solves and diffuses into the layer of bottom water. When
there is an oxygen deficit, this diffusion spreads for a con-
siderable depth and manganese exists as Mn21 ions for a
long time in the water mass. The latter case is more typical
in winter when the Dnieper reservoirs are covered by ice
for extended periods of time. The second case occurs in sum-
mer in the Dnieper–Bug estuary when there is a decrease
in the volume of fresh water flowing from the Kakhovka
reservoir. Iron is less mobile, as it binds with DOM of dif-
ferent molecular weights (see Fig. 7). Because of this, the
behaviour of iron is less dependent on oxygen concentration
and pH changes than is manganese. Iron probably migrates
from bottom sediments as organic complexes. The migra-
tion rate of these complexes will be different since their
molecular weight varies. Naturally, this rate is lower than the
migration rate of manganese, as shown by our experimen-
tal results (see Fig. 6). Nevertheless, the migration rate of
iron from bottom sediments increases in conditions of low
values of dissolved oxygen concentrations and pH. In such
circumstances, the intensity of flow for both organic matter
and iron increases because this metal is in the form of
organic complex compounds (see Fig. 6b,d). Similar mech-
anisms of migration are characteristic for other metals inves-
tigated. However, their mobility can be slightly different from
that of iron, depending on the proportion of free metal ions
and their organic complexes.
The concentration of manganese in water above the sedi-
ments (in anaerobic conditions) is nearly 100-fold that of its
concentration in the natural water, which was used for the
experimental investigation (see Fig. 6c). However, iron con-
centration in the aquatic phase after contact with silt (in
anaerobic conditions) increases only 3–3.5-fold (see Fig. 6d).
As observed, most HM pass from interstitial solutions into
water above the sediments in organic complexes of relatively
low molecular weight (≤ 5000 Da). Their share in the total
balance of complex compounds reaches 60–65% (Fig. 9). The
migration flow of complexes of higher molecular weight is
less intensive, and so the rise in the concentration of such
complex compounds in water above sediments is less.
The results of long-term investigations enable the deter-
mination of metal mobility in the bottom sediment/water
zone when the concentration of free ions and low molecular
20
Fig. 9. Distribution of heavy metals among organic complexes of
different molecular weight in (h) the initial water and (j) the aquatic
environment after contact with silt in anaerobic conditions. (a) Fe;
(b) Cu; (c) Zn.
P. M. Linnik and I. B. Zubenko
weight organic complexes (500–5000 Da) in the interstitial
solutions are taken into account. The relative mobilities are:
Mn >> Zn > Cu ≥ Cr > Fe ≥ Pb. Rates of flow for HM diffusion
can increase according to the character and intensity of inter-
nal aquatic processes, as considered earlier.
CONCLUSIONS
The bottom sediments of Dnieper reservoirs and the
Dnieper–Bug estuary are active HM accumulators. Because
of this, the quality of the aquatic environment is improved
and the process may be considered as a positive factor for
the functioning of Dnieper aquatic ecosystems. At the same
time, the bottom sediments pose a threat of secondary water
pollution by HM. Data on existing forms of HM in the solid
phase and in interstitial solutions of bottom sediments are
useful in evaluating HM mobility and the ability of HM to
move between bottom sediments and overlying water. The
greatest threat is posed by cadmium, which mostly occurs
as an highly mobile element in bottom sediments of the
Dnieper reservoirs, so long as most of it exists in the ion-
exchange fraction (from 22 to 32%). Manganese and zinc
show a preference for the oxide fraction, whereas other
metals investigated (copper, iron, and chromium) mostly
occur in organic and residual fractions. The lowest mobility
is typical for copper and chromium because most of these
metals are concentrated in the organic and residual fractions.
The results of our investigations of coexisting forms of HM
in the interstitial solutions confirm this. However, our
results have shown that manganese mobility and the ability
of manganese to exchange is the highest of the metals
studied because most manganese is found as free Mn21 ions.
Other metals investigated (including cadmium) are mainly
bound to DOM of different molecular weights. The inten-
sity of the exchange of such metals between the bottom sedi-
ments and the overlying water depends on the migration flow
of organic substances. If the molecular weight of organic
complex compounds increases, the mobility of metals and
their ability to pass into the water column decrease. Field
data and laboratory experiments indicate that complexes of
HM with relatively low molecular weight play the principal
role in secondary water pollution. However, decreases in
dissolved oxygen concentrations and pH values in the
sediment/water zone promote metal compound flow from
the bottom sediments into overlying waters.
REFERENCES
Calmano W. & Förstner U. (1984) Chemical extraction of
heavy metals in polluted river sediments in Central
Europe. Sci. Total Environ. 28, 77–90.
Denisova A. I., Nakhshyna Ye. P., Novikov B. I. & Ryabov 21
A. K. (1987) Bottom Sediments of Reservoirs and Their
Bottom sediments and secondary water pollution
Influence on the Water Quality. Naukova Dumka Press,
Kiev (in Russian).
Denisova A. I., Timchenko V. M., Nakhshyna Ye. P. et al.
(1989) Hydrology and Hydrochemistry of the Dnieper and
its Reservoirs. Naukova Dumka Press, Kiev (in Russian).
Förstner U. (1977) Metal concentration in recent lacustrine
sediments. Arch. Hydrobiol. 80, 172–91.
Goncharuk E. I. & Sidorenko G. I. (1986) Concentration
Standards for Chemical Substances in Soils. Meditsina
Press, Moscow (in Russian).
Hart B. T. (1982) Uptake of trace metals by sediments and
suspended particles: A review. Hydrobiologia 91/92,
299–313.
Korableva A. I. (1993) Possibility of evaluation of the eco-
logical capacity of the Zaporozh’e reservoir (using heavy
metals). Gidrobiologicheskiy Zhurnal 29(2), 85–90 (in
Russian).
Linnik P. N. & Iskra I. V. (1994) Application of anodic strip-
ping voltammetry to the investigation of the physico-
chemical state of cadmium in surface water in the
Ukraine. Microchem. J. 50, 184–90.
Linnik P. N. & Nabivanets Yu. B. (1988) Application of
anodic stripping voltammetry to the determination of free
and bound complexes of zinc and lead ions in natural
waters. Gidrobiologicheskiy Zhurnal 24(1), 68–71 (in
Russian).
Linnik P. N., Zhuravleva L. A., Samoilenko V. N. &
Nabivanets Yu. B. (1993) Influence of exploitation regime
on quality of water in the Dnieper reservoirs and mouth
zone of the Dnieper river. Gidrobiologicheskiy Zhurnal
29(1), 86–99 (in Russian).
Lund W. (1990) Speciation analysis: Why and how? Fresenius
J. Anal. Chem. 337, 557–64.
Nabivanets B. I., Linnik P. N. & Kalabina L. V. (1981)
Catalytic Methods of Natural Water Analysis. Naukova
Dumka Press, Kiev (in Russian).
Nakhshyna Ye. P. & Belokon’ V. N. (1990) Forms of occur-
21
rence of heavy metals in bottom sediments of the
Dnieper reservoirs. I. Manganese. Gidrobiologicheskiy
Zhurnal 26(1), 76–81 (in Russian).
Rendell P. S., Batley G. E. & Cameron A. J. (1980) Adsorption
as a control of metal concentration in sediment extracts.
Environ. Sci. Technol. 14, 314–8.
Romanova G. I. (1987) Migration and accumulation of iron,
manganese, copper and zinc in the bottom sediments of the
Ivan’kov reservoir. Abstract of PhD Thesis. Moscow
State University, Rostov-on-Don (in Russian).
Sager M. (1992) Chemical speciation and environmental
mobility of heavy metals in sediments and soils. In:
M. Stoeppler (ed.). Hazardous Metals in the Environment.
Elsevier Science Publishers, Amsterdam, pp. 133–75.
Salomons W. & Förstner U. (1984) Metals in the Hydrocycle.
Springer-Verlag, Berlin.
Tessier A., Campbell P. G. C. & Bisson M. (1979) Sequential
extraction procedure for the speciation of particulate
trace metals. Anal. Chem. 51, 844–51.
Tsvetkova A. M. & Novikov B. I. (1995) Anthropogenic pol-
lution of sediments in the Kakhovka reservoir by heavy
metals. Gidrobiologicheskiy Zhurnal 31(6), 79–85 (in
Russian).
Vinogradov A. P. (1957) Geochemistry of Rare and Dispersed
Elements in Soils. AN SSSR (Publishing House of the
Academy of Sciences of the Former Union of Soviet
Socialist Republics) Press, Moscow (in Russian).
Voyutsky S. S. (1976) Course in Colloid Chemistry. Khimia
Press, Moscow (in Russian).
Zhuravleva L. A. & Linnik P. N. (1989) Factors of formation
of extreme situations in the hydrochemical regime of the
Dnieper-Bug estuary. Gidrobiologicheskiy Zhurnal 25(3),
69–73 (in Russian).
Zubenko I. B. & Linnik P. N. (1997) Fractional distribution
of heavy metals in bottom sediments of the Dnieper
reservoirs. Gidrobiologicheskiy Zhurnal 33(3), 101–12 (in
Russian).