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Modelling and simulation of heavy metals transport in water and sediments

Article  in  Environmental Engineering and Management Journal · March 2007

DOI: 10.30638/eemj.2007.021

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Environmental Engineering and Management Journal, March/April 2007, Vol. 6, No. 2, 153-161
http://omicron.ch.tuiasi.ro/EEMJ/

“Gh. Asachi” Technical University of Iasi, Romania

______________________________________________________________________________________________

MODELLING AND SIMULATION OF HEAVY METALS TRANSPORT

IN WATER AND SEDIMENTS

Simona Pintilie1, Loredana Brânză, Camelia Beţianu1, Lucian Vasile Pavel1,

Florina Ungureanu2, Maria Gavrilescu1∗

1
Technical University Iasi, Faculty of Chemical Engineering, Department of Environmental Engineering and Management, 71
Mangeron Blvd.700050 Iasi, Romania
2
Technical University Iasi, Faculty of Automatic Control and Computer Engineering, Department of Computer Engineering, 53
Mangeron Blvd.700050 Iasi, Romania

Abstract

Heavy metals can be transported by rivers which flow through areas with industrial pollution, both as metal in solution and metal
adsorbed to suspended solids. They can settle in lakes and accumulate in the sediment, exhibiting significant effects on wildlife
and humans if they enter into the food chain.
In this work, heavy metals transport and sedimentation is simulated based on an analytical model proposed in literature,
considering the material balance and complementary equations, under dynamic conditions. The model was validated previously,
while the simulation was performed at various inflow water flow rates and inflow metal concentrations.
The simulation can be used as a tool for fast evaluation of metal transport in water and sediments, because it requires a minimal
number of measurements.

Keywords: heavy metals, modelling, sediment, simulation, water column

1. Fate of heavy metals in aquatic environment
Transport of the metals may result in
increased contents of heavy metals in the ground
water or surface water, so that contamination of the
environment by heavy metals poses a serious
environmental and health risk (Gavrilescu, 2004;
Gavrilescu, 2006; He et al., 2004; Kelderman et al.,
2005; Prokop et al, 2003; Purves, 1985).
Human activity promotes the accumulation
of contaminated sediments in water courses. These
activities sometimes indirectly increase the amounts
of heavy metals released into the environment by
natural processes. Heavy metal inputs included those
from commercial fertilizers, liming materials and
agrochemicals, sewage sludges and other wastes used
as soil amendments, irrigation waters, and
atmospheric deposition (Prokop et al., 2003; Senesi et
al., 1999). The origins of sediment contamination can
be divided into point and nonpoint sources of
pollution. Point source pollution comes from a
specific, identifiable source such as a pipe. Nonpoint
source pollution can be traced to a specific area. Point
sources include municipal sewage treatment plants,
overflows from combined sanitary and storm sewers,
stormwater discharges from municipal and industrial
facilities, and waste discharges from industry. No
point sources include stormwater runoff from
hazardous and solid-waste sites, runoff from
croplands, livestock pens, mining and manufacturing
operations, and storage sites. Atmospheric deposition
is another source of nonpoint pollution.
Upon entry into surface waters, heavy metals
deposition occurs on the bottom of aquatic areas
(streams, sediments, lakes, estuaries). The
concentrations of various heavy metals (cadmium,
chromium, copper, iron, lead, manganese, nickel,
zinc) in water and bed sediments have been studied
and monitored over several years (Moss and
Constanza, 1998; Singh et al., 2005a, b; Snape et al.,
1995, van de Vrie E.M., 1987). Also, the relationships
between water flow, sediment distribution and metal
chemistry have been well studied for rivers and lakes
and karst systems (Avila-Perez et al., 1999; Vesper

∗
Author to whom all correspondence should be addressed: mgav@ch.tuiasi.ro
 Pintilie et al./Environmental Engineering and Management Journal 6 (2007), 2, 153-161
and White, 2004). The fate of heavy metal particles in
the environment is important because they tend to be
reactive, mobile, and highly toxic. Heavy metals are
contained in four reservoirs in an aquatic
environment, namely, the surface water, the pore
waters, the suspended sediment, and the bottom
sediment. During transport, sediment-bound metals
are removed from the water column and stored in
alluvial deposits for years before they are
reintroduced into the aquatic environment.
The behavior and fate of metals are
governed by a range of different physical and
chemical processes, which dictate their availability
and mobility in the soil or sediment system. In the
water phase, the chemical form of a metal determines
the biological availability and chemical reactivity
(sorption/ desorption, precipitation/ dissolution)
towards other components of the system. Also, the
mobility and bioavailability of metals bound to
sediments depend on multiple factors, with sediment
characteristics and the physical–chemical form of the
metal being the key factors (Prokop et al., 2003).
All heavy metals exist in surface waters in
colloidal, particulate, and dissolved phases, although
dissolved concentrations are generally low (Kennish,
1992). The colloidal and particulate metal may be
found in 1) hydroxides, oxides, silicates, or sulfides;
or 2) adsorbed by clay, silica, or organic matter. The
soluble forms are generally ions or unionized
organometallic chelates or complexes. The solubility
of trace metals in surface waters is predominately
controlled by the water pH, the type and
concentration of ligands on which the metal could
adsorb, and the oxidation state of the mineral
components and the redox environment of the system
(Connell et al., 1984).
Living organisms require trace amounts of
some heavy metals, including cobalt, copper, iron,
manganese, molybdenum, vanadium, strontium, and
zinc. Excessive levels of essential metals, however,
can be detrimental to the organism. Non-essential
heavy metals of particular concern to surface water
systems are cadmium, chromium, mercury, lead,
arsenic, and antimony (Kennish, 1992).
Heavy metals at or near the soil surface can
be transformed to overland flow in solution form by
the mixing of rainwater with soil solution, dissolution
of the heavy metal partly present in solid form,
desorption of an adsorbed or absorbed chemical from
the soil and residues in place, and desorption of the
chemical from eroded sediment.
The behavior of metals in natural waters
depends on substrate sediment composition,
suspended sediment composition, and water
chemistry. Sediments composed of fine sand and silt
will generally have higher levels of adsorbed metal
than quartz, feldspar, and detrital carbonate-rich
sediment. Metals also have a high affinity for humic
acids, organo-clays, and oxides coated with organic
matter (Connell et al., 1984).
In this paper, the simulation of heavy metals
transport in water column and sediments is carried out
154
for a lake with inflow and outflow water streams,
based on an analytical model developed in literature
by van den Vrie (1987) and discussed by Snape et al.
(1995). The model was built considering the material
balance of both dissolved and adsorbed to solid
particle forms of the heavy metal in the water column
and the top sediment layer, together with
complementary equations: rate of sedimentation of
suspended particles settling with a certain velocity,
diffusion between the top layer of sediment and the
water column. The simulation considers different
values for water inflow rates and various metal
concentrations. The results of simulation are
presented as dynamic profiles of heavy metal
concentration.
3. Modelling and simulation of heavy metal
behavior in waters and sediments
3.1. Background
Rivers passing through industrial and mining
areas transport metals, partly as metal in solution and
partly as metal adsorbed to suspended material. This
suspended material settles to the bottom of lakes and
estuaries and accumulates in the sediment. Aquatic
organisms may be adversely affected by heavy metals
in the environment. The toxicity is largely a function
of the water chemistry and sediment composition in
the surface water system.
Metals may enter the aquatic organisms via three
main pathways (Branza et al., 2005a, b; Connell et al.,
1984):
1. Free metal ions that are absorbed through
respiratory surface (e.g., gills) are readily
diffused into the blood stream.
2. Free metal ions that are adsorbed onto body
surfaces are passively diffused into the blood
stream.
3. Metals that are sorbed onto food and
particulates may be ingested, as well as free
ions ingested with water.
In order to be able to assess the water-quality
impacts of sediments on receiving water bodies,
predictions on variations of metal concentration and
contaminant movement are needed under specific
hydrodynamic conditions.
There are few published modeling studies on
sediment and metal transport in rivers that simulate
storm events and use comprehensive data sets for
model input and model calibration. The overall goal
is to obtain a tool for fast evaluation of metal
transport and accumulation in water and sediments
through simulation, which requires a minimal number
of measured physical and chemical parameters
(Gavrilescu et al., 2005; Snape et al., 2005).
This approach may be useful during storm
events or dredging activities. These heavy-metal
contaminants are often absorbed to clay particles in
fine, cohesive sediments where they tend to
accumulate without degradation. Heavy metals tend
to be associated with clay particles comprising
 Modelling and simulation of heavy metals transport

cohesive sediments because of the high specific CD2 = fD2 CT2 (4)
surface area and reactivity of these particles. Once
mobilized in the water column, the adsorbent CA1 = (1-fD1) CT1 (5)
contaminants are exposed to a different chemical
environmental and increased interaction times that CA2 = (1-fD2) CT2 (6)
may result in desorption and/or dissolution with an
accompanying change in water quality. The dissolved fraction, fD, is given by the
distribution coefficient, KD (Eqs. 7-9):
3.2. Model presentation
1
The model was elaborated based on the fD = (7)
1 + mK D
balance and complementary equations and can be
applied to analyze the accumulation of heavy metals
in lake waters and sediments, under dynamic 1
f D1 = (8)
conditions in connection with simulation tools. 1 + mK D1

3.2.1. System description 1

The system is based on the assumption and f D2 = (9)
1 + mK D 2
models of van de Vrie (1987), predicting the
concentration of zinc, cadmium and lead in the
sediment and water of a lake in the southwest of the where m is the total concentration of the suspended
Netherlands, validated and analyzed by Snape et al. particles.
(1995). The rate of sedimentation of suspended
particles settling with velocity vs is given by Eq (10).

Js = vs A CA = vs A (l – fD) CT (10)

The particles in the top layer of sediment

also settle until they reach a certain depth at which
they are no longer influenced by the water column.
Due to differences in the dissolved metal
concentration in the water column and in the top layer
of the sediment, a diffusion exchange between the
two compartments will occur, proportional to the
difference in concentration and the area of the
sediment-water interface. This exchange is defined by
the proportionality constant KL (Eq. 11).

Jd = KL A (CD1 – CD2) (11)

Fig. 1. Model regions for heavy metal transport in a lake
(Snape et al., 2005) Water flows into the water column at a
volumetric flow rate Q, with a total metal
3.2.2. Mathematical model concentration Cin. It is assumed that the water flows
The lake is divided into vertical elements, through the water column element at the same rate
each of them consisting of a column of water and the and at the same concentration as in the whole water
top layer of sediment. The results of the simulation column. Mass balances on the water column and top
can be extended to many elements. sediment layer are expressed by Eqs. 6, 7.
It is assumed that the metals are distributed
homogeneously in the water column as well as in the dCT1
V1 = Q(Cin − CT ) − J s1 − J D (6)
upper sediment layer. In both compartments, the dt
metals with concentration CT can exist in either a
dissolved form (with concentration CD) or adsorbed to dCT2
solid particles (with concentration CA), both in the V2 = J s1 + J D − J s 2 (7)
water column (index 1) or in the top layer of dt
sediment (index 2) (Eqs. 1-6).
where V1 and V2 are the volumes of the water column
CT = CD + CA (1) and top layer of sediment, respectively, and H1 and H2
are the corresponding heights.
CD = fD CT (2)
After substitutions and rearrangement, it will result
CD1 = fD1 CT1 (3) Eqs. 8, 9.

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 Pintilie et al./Environmental Engineering and Management Journal 6 (2007), 2, 153-161

flow rate (Table 2). The individual adsorption

dCT1
dt
(
= Q Cin − CT1 − ) vs
H1
(
(1 − f D )CT − K1 C D1 − C D2
H1
) (8)
characteristics of different metals were not taken into
consideration, but instead were treated as a group
with the average values of the distribution coefficient
dCT2
dt
=
v s1
H2
(1 − f D )CT
t 1
+
KL
H2
( ) vs
(
C D1 − C D2 − 2 1 − f D2 CT2
H2
) (9)
and diffusion exchange coefficient. Fig. 2 shows the
dynamic profiles of metal concentration at Q =
3.3. Simulation 1m3day-1, considering the lowest inflow metal
concentration, Cin = 0.001 g/m3.
3.3.1. Simulation conditions Metals accumulate continuously in the water
The mass balance for heavy metals in the column for 120 days, when a maximum of
lake is connected to equations that describe concentration CT1 = 6.10-4 g/m3 is reached. After that,
contaminant transport, intermedia exchange, phase the concentration remains almost constant, even when
distribution, in both water column and sediments. the influent water flow rate drops to 50% of its initial
In order to simulate the behavior of the value (Fig.2a, curve CT1). Also, the concentration of
system, the model is solved using the Matlab software the dissolved metals in the water column is almost a
and considering the initial conditions. Data from half of the overall concentration of heavy metals (Fig.
Table 1 are used to simulate the behavior of the 1a, curve CD1). Analyzing the dissolved and/or
contaminated lake water and sediments, analyzing the adsorbed heavy metal concentrations in the water
dynamic profiles of heavy metal concentrations at column and sediment (Fig.1b), it is obvious that they
different values of influent flow rate Q and the inflow accumulate in 120 days, after which they slowly
heavy metal concentration. diminish or remain constant. In the water column (1)
the dissolved heavy metal concentration is less than
Table 1. Initial conditions for mathematical model solving the adsorbed metal concentration on solids dispersed
in liquid phase (Fig. 1b, curves D1, A1). Therefore,
Characteristic Value metals are more likely to be adsorbed on solid
Height of water column, H1 (m) 10 surfaces, than to be dissolved in water. In the
Depth of top sediment layer, H2 (m) 0.39 sediment layer, the concentration of dissolved metals
Volume of water column, V1 (m3) 100 is almost the same as that of adsorbed metals (curves
Volume of sediment layer, V2 (m3) 3.9 A2 and D2) and tends to a constant value of 3.5 10-4
Distribution coefficient of metal in 114 g/m3.
water, KD1 (g-1) If the influent water has a higher
Distribution coefficient of metal in 18.8 concentration of heavy metals (Cin =0.01 g/m3), then
sediment, KD2 (g-1) metals will accumulate continuously in the lake,
Diffusion exchange coefficient, KL (m 1
beyond 7x10-3 g/m3 even if inflow water flow rate
day-1)
diminishes after 120 days at 50% of the initial value
Sedimentation velocity in water, vs1 (m 0.1
day-1) (Fig. 2c). This is a different behavior when compared
Settling velocity, vs2 (m day-1) 0.01 to a value of Cin = 0.001 g/m3 (Fig. 2a).
Particle concentration, m (g m-3) 0.01 The dissolved and adsorbed concentrations
of the metals in the water column and the sediment
Also, values of the parameters that were layer will increase continuously for as long as 150
modified during simulation - influent water flow rate, days with a significant slope (Fig. 2d). Afterwards,
Q, and inflow metal concentration - are presented in the concentration of the dissolved metals in the water
Table 2. The simulation was performed for a duration column remains almost constant (D1~ 0.5x10-3 g/m3),
of 250 days. while the other concentration increases, so that metals
accumulate (curves A1, A2, D2 – Fig. 2d), over 3.5x10-
3
Table 2. Values of model variables Q and Cin g/m3.
A similar behavior can be observed if the
Variable Values inflow metal concentration becomes Cin = 0.1 g/m3
Influent water flow rate, Q 1 (Figs. 2, e, f). The maximum value of the heavy metal
(m3 day-1) 10 concentration in the water column tends to 0.07 g/m3,
100 (Fig. 2e, curve CT1) while the dissolved metal
Inflow metal concentration, 0.001 concentration is around 0.03 g/m3, after 250 days,
Cin (g m-3) 0.01 with a slight tendency to increase (Fig. 1e, curve
0.1 CD1).
The highest concentration of metals can be
3.3.2. Influence of inflow concentration of pollutants found in the adsorbed form and in sediment (Fig. 2f,
on dynamic behavior of metals in water column and curves A1, A2, D2), reaching 0.035 g/m3 after 250
sediments days, while the concentration of metal dissolved in
The simulation of metal accumulation in water remains at 0.005 g/m3 (Fig. 2f, curve D1).
water column and sediments was first performed with
different inflow metal concentrations ranging from
0.001 to 0.1 g/m3 at a certain value of influent water

156
 Modelling and simulation of heavy metals transport

3.3.3. Influence of influent water flow rate on
dynamic behavior of metals in water column and
sediment
An increase of the influent water flow rate to
Q = 10 m3/day will change the behavior of the
system, when the three levels of inflow heavy metal
concentrations are considered. For an inflow metal
concentration Cin = 0.001 g/m3, the time necessary to
reach a total maximum metal concentration will only
be 30% from the maximum found at Q = 1 m3/day
(Fig. 3a). Therefore, the hydrodynamic aspects play
an important role in metal transport in the water
column. After this duration (between 30-40 days),
any decrease in inflow rate will result in constant CT1
and CD1 values.

a) b)

c) d)

e) f)

Fig. 2. The dynamic profiles of heavy metal concentrations in sediments and water column for an influent water flow rate,
Q=1 m3 day-1

A similar situation can be observed for the column (D1 and A1) and sediment layer (A2, D2),
dissolved and adsorbed metal concentrations in water respectively (Fig. 3b).

157
 Pintilie et al./Environmental Engineering and Management Journal 6 (2007), 2, 153-161

As in the previous simulation (Q = 1 most significant part of the metals. It is important to

m3/day), the sediment and solid particles retain the note that the steady state appears after 40 days.

a) b)

c) d)

e) f)

Fig. 3. The dynamic profiles of heavy metal concentrations in sediments and water column
for an influent water flow rate, Q=10 m3 day-1

For a higher value of metal concentration, x10-3 g/m3 and CD1 = 4.5x10-3 g/m3, which are greater
Cin = 0.01 g/m3, the system behaves as previously, than those for Cin = 10-3 g/m3 (Fig. 3c). The same
excepting for the steady – state values of CT1 ≈ 9.5 profile of the concentrations of metals was found for

158
 Modelling and simulation of heavy metals transport

adsorbed metal concentrations, in sediment and
dispersed solid particles, A2, D2, D1 (Fig. 3d). If the
metal inflow concentration becomes higher, Cin = 10-1
g/m3, the maximum value of adsorbed and dissolved
metal concentration increases, compared to that
observed for Cin = 10-2 g/m3 (Figs. 3e, f). The increase
of water inflow rate at Q = 100 m3/day (for example,
during rainfall) leads to steady – state almost
instantaneously, with the maximum values of
concentration depending on the inflow concentration
values (Fig. 4, a-f).

b)
a)

d)
c)

e) f)

Fig.4. The dynamic profiles of heavy metal concentrations in sediments and water column
for an influent water flow rate, Q=100 m3 day-1

159
 Pintilie et al./Environmental Engineering and Management Journal 6 (2007), 2, 153-161
4. Conclusions
The simulation of the heavy metals transport in
water column and sediments was carried out for a
lake with inflow and outflow water streams. The lake
was considered as consisting of a number of vertical
elements that comprise water columns and top layer
sediments, where the metal is distributed
homogeneously. The simulation was performed for
only one such element, for the metal existing in either
a dissolved form or as adsorbed to solid particles.
Nomenclature
A Area of water-sediment interface in each element
C Concentration of metal
fD Fraction of metal that is dissolved
H1 Height of water column
H2 Depth of top sediment layer
J Fluxes of metals
KD Distribution coefficient
KL Diffusion exchange coefficient
m Concentration of suspended particles
Q Volumetric flow rate of water into water column
T Time
V1 Volume of water column
V2 Volume of top sediment layer
vs Sedimentation velocity
Subscripts
1 Water column
2 Top sediment layer
A Adsorbed
D Dissolved
s Settling
T Total
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