Journal of Environmental Science and Health Part A, 41:825847, 2006

C Taylor & Francis Group, LLC

Copyright

ISSN: 1093-4529 (Print); 1532-4117 (Online)
DOI: 10.1080/10934520600614454

Modelling the Fate

and Transport of Nickel
in the Mersey Estuary
Michael Hartnett,1 Binliang Lin,2 Peter D. Jones,3 and
Alan Berry4
1
MarCon Computations International Ltd. and Department of Civil Engineering,
National University of Ireland, Galway, Ireland
2
School of Engineering, Cardiff University, Cardiff, Ireland
3
U.K. Environment Agency, Warrington, England
4
MarCon Computations International Ltd., Galway, Ireland

Modelling heavy metals in estuarine environments is extremely complex for various

reasons; one of the primary complicating factors is that metals exist in two phases,
dissolved and particulate bound. Dynamic changes in water chemistry, and in particular salinity, affect the partitioning of metals between the two phases and hence
make it difficult to determine the relative fractions of each phase. A relatively simple
approach was developed to relate variations in partition coefficient for Ni to salinity
fluctuations in the Mersey Estuary. The functional relationship developed between
partition coefficient and salinity departs from the traditional exponential type curve,
providing a more realistic relationship.
A numerical model was then developed for predicting the transport and distribution of Ni about the Mersey Estuary. The model couples transport of metals
throughout the water along with incorporating the chemical processes controlling
how nickel is fractioned between dissolved and particulate phases through the newly
developed partition coefficient relationship. Model predictions of dissolved Ni along the
longitudinal axis of the estuary were compared with measurements of Ni for two events;
very good correlation was obtained between the model results and the data.
Key Words: Partition coefficient; Heavy metal modeling; Nickel modeling; Sediment
modeling; Mersey Estuary.

INTRODUCTION
Heavy metals such as Pb, Zn, Cd, Cu and Ni are toxic to many fish species
when present in water in quite low concentrations and are also very dangerous

Address correspondence to Michael Hartnett, Department of Civil Engineering, National University of Ireland, Galway, Ireland; E-mail: Michael.Hartnett@nuigalway.ie

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Hartnett et al.

in drinking water sources. The EC Dangerous Substances Directive[1] is

implemented to control the release of dangerous substances into water. In
this directive Ni has been assigned an environmental quality standard (EQS)
of 30 g/L for coastal and estuarine waters. In implementing EU Directives
such as the Dangerous Substances Directive,[1] the Shellfish Directive[2] and
the Habitats Directive[3] numerical models are used to make predictions of
various water quality parameters, including heavy metals. The development of
a numerical model to accurately predict the transport of heavy metals in water
is a complex task including dynamically coupling between hydrodynamics,
sediments and the metals. The task becomes more complex when modelling
the distribution of heavy metals in large estuaries due to salinity fluctuations.
One of the legacies bequeathed by the Industrial Revolution to the Mersey
Estuary is a that a large buildup of industrial discharges has left considerable
deposits of heavy metals bound to the fine sediments of the estuary. As a
result of the neglect of waste management, the estuary earned itself the
ignominious title of the most polluted estuary in Europe. During the period
18501950 increased industrial output resulted in many industries requiring
large volumes of water for cooling and processes such as bleaching, tanning and
metalworking. It is likely that during the 1960s the water quality status of the
Mersey Estuary was at its lowest being severely contaminated by toxic organic
and inorganic compounds from the local industries. At the beginning of the
1970s pollution effects from heavy metals caused serious concerns. Then, UK
Government laboratories reported that fish caught in Liverpool Bay contained
elevated levels of many heavy metals. These raised levels were attributed to
the contaminated waters of the Mersey Estuary due to the wanton discharging
of industrial wastes.[4]
Because of the serious nature of metal contamination of the Mersey
Estuary, many other studies have been undertaken to define and better
understand the nature of the problem and, in particular, nickel reactivity in
the Mersey Estuary. Campbell et al.[5] present and discuss the distribution
and behaviour of both dissolved and particulate bound nickel in the Mersey
Estuary. One of the main conclusions from their work is that the distribution
of nickel throughout the Mersey Estuary is complex and clearly deviates from
simple end-member mixing behaviour.
Turner et al.[6] undertook a detailed study of seven trace metals distributed throughout the Mersey Estuary including nickel. In their paper they
describe the estuary as a highly contaminated, organic-rich estuary and they
observed an increase in the sediment-water distribution coefficient, KD , with
increasing salinity for all metals considered except Cd. These observations
were inconsistent with inorganic speciation calculations and empirical modelling studies in other estuaries, predicting an inverse relationship between
KD and salinity. The primary focus of their paper was to investigate the
factors controlling the salinity distributions of metal data based on defining the

Modelling the Fate and Transport of Nickel

chemical processes that control the KD salinity relationship. They developed

an empirical model based on salting out of neutral organic chemicals that
reflected the salinity distribution of the data.
This is a different approach to the one adopted in this paper; however,
the model developed by Turner et al. has promise for incorporation into
numerical model simulations also. Ng et al.[7] carried out a detailed contaminant modelling study of the Humber estuary. They outline the difficulties
of making accurate predictions of heavy metals in the Humber due to many
controlling variables including: salinity, pH and availability of complexing
species. Within the model, the partition coefficient was allowed vary as a
function of salinity in either of two ways: using a relationship developed by
Millward and Turner[8] or using explicit tabulations of measured values of KD
as a function of salinity. Millward and Turners relationship is discussed in
more detail in a later section of this paper. The paper by Ng et al. illustrates
how a geochemical module based on empirically derived partition coefficients,
coupled to a two-dimensional hydrodynamic model, was developed to form the
basis of a geochemical contaminant transport model. This basic approach of Ng
et al. is the one followed in the research undertaken by the author; however,
the authors have extended this approach with regards to the formulation of
the partition coefficient for nickel.
Martino et al.[9] reported upon high resolution, seasonal distributions of six
dissolved trace metals in the Mersey Estuary. The purpose of this study was
to obtain a more detailed comprehension of the mechanisms controlling metal
reactivity in the estuary. An empirical sorption was used and reproduced, with
reasonable success, axial distributions of the metals that exhibited the largest
peaks, namely Co and Pb. One of the drawbacks of this research is that the
partition coefficients used were single-valued, unrelated to salinity. Further,
the approach adopted in the paper of Martino et al. does not base predictions
of metals on the physics of the dynamical interactions between hydrodynamics
and the mechanics of sediment transport.
Comber et al.[10] undertook research into the partitioning of trace metals
between the dissolved phase and suspended solids on both the Humber
Estuary and the Mersey Estuary. One of the aims of this research was to
develop partition coefficients for a number of metals. A single-valued partition
coefficient for nickel in the Mersey was estimated at ca. 1 104 and the
corresponding value in the Humber was ca. 5 103 . The reason for the higher
value of KD in the Mersey was attributed to higher loadings of sewage into the
Mersey along with differences in suspended particulate composition.
In this paper the authors describe a model that was developed to predict
distributions of Ni throughout the Mersey Estuary. An extensive water quality
monitoring programme was developed for the Mersey Estuary from the mid
1970s. Water samples are collected from up to 23 mid-stream locations and
analysed for various constituents including sanitary parameters and trace

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Hartnett et al.

contaminants. This programme has continued to date providing the UK

Environment Agency with an extensive data set for use in many aspects of
water quality management and planning of the Mersey Estuary. It is noted
that this monitoring programme is relatively expensive, in particular the
determinations of trace metals requires more sophisticated instrumentation
and skilled personnel than is required for the determination of sanitary
parameters. Because of the high costs of trace contaminant analyses the
development of accurate numerical models to aid in the development of
monitoring programmes and in predicting distributions of trace metals is
desirable.
The development of the Mersey Estuary transport model for Ni is detailed
below; particular emphasis is placed on how the model computes the partition
coefficient for the metal. Advantage is taken of the extensive database developed by the Environment Agency in model development and model calibration
and validation.

METHODOLOGY AND RESULTS

Overview of Approach Adopted
When metals are introduced into water containing suspended particulate
matter (SPM), a portion of the metal is dissolved in the water and the
remainder is absorbed onto surface of the SPM. The distribution of the metal
fractions between these two phases can be described by a partition coefficient,
KD , defined as:
KD =

P
C

(1)

where P is the concentration of heavy metal absorbed on suspended sediments

(g/L) and C is the concentration of heavy metal dissolved in the water column
(g/L). The coefficient KD is function of spatially varied water chemistry and
is notoriously difficult to quantify in marine waters. It is well documented
and generally accepted that there is a strong functional relationship between
KD and salinity. In many studies only the influence of salinity are considered
and other direct water chemistry effects are ignored; this approach is adopted
in this research also. Thus in order to model, hindcast and predict heavy
metals, with a reasonable degree of accuracy, the following staged approach
was adopted.
A hydrodynamic model of the Mersey Estuary was developed, calibrated
and validated. This model allowed current speeds and directions be predicted; these parameters were necessary for subsequent modelling of various
transport processes. A solute transport model was developed, calibrated and
validated and used to predict salinity distributions throughout the estuary

Modelling the Fate and Transport of Nickel

at various stages of the tide using the results from the hydrodynamic model.
From field data an expression was developed relating the partition coefficient
to salinity, this is a novel component of this research. From the model
salinity predictions and the KD versus salinity relationship, the model has
the capability of computing spatially varied and temporally varied partition
coefficients as the model calculations progress forward in time. A sediment
transport model of the Mersey Estuary was then developed, calibrated and
validated and used to predict estimates of cohesive sediments. Finally, having
predicted cohesive sediment concentrations and values of KD at each grid point
of the model for each computational timestep, the model computes the fraction
of the heavy metal which is dissolved and that fraction which is absorbed onto
the cohesive sediments.

Hydrodynamic Model of Mersey Estuary

The Mersey Estuary is one of the largest estuaries in the UK, having a
catchment of some 5,000 km2 that includes the major cities of Liverpool and
Manchester. The estuary is a macro-tidal estuary with tidal ranges recorded at
Gladstone Dock of between 10.5 m on extreme spring tide to 3.5 m on extreme
neap tides. Freshwater inputs from the River Mersey vary between approximately 10 m3 /s and 500 m3 /s at the extremes; typical flows are in the range
2060 m3 /s. A numerical model was developed of the estuary extending from
New Brighton at the seaward end to the tidal limit at Howley Weir, Figure 1
shows the extent of the model domain. The two-dimensional model DIVAST
was used during this research. The estuary was represented in the model by
a regular grid defined on two mutually orthogonal axes on a horizontal plane.
The grid spacing was set at 100 m resulting in a model size of 215 308
grid squares, or 66,220 computational grid points. At each model grid point
the bathymetry of the estuary was defined from a bathymetric survey of the
estuary carried out for the Environment Agency in 2002. Figure 2 shows a plot
of the Mersey Estuary bathymetry; this figure shows the complex geometry
and bathymetry of the study area. The Upper Estuary is a meandering channel
of approximately 15 km in length; below Runcorn the estuary opens into a wide
shallow basin to form the Inner Estuary with extensive mudflats and a large
salt marsh on the southern bank. Downstream further the estuary converges
to form the Narrows, a straight narrow channel of up to 30 m deep.
The hydrodynamic model is based on the following depth integrated
formulation of the Navier Stokes equations, for details of the derivation, see
Falconer.[11] The continuity equation and x, y momentum equations can be
respectively written as:
Q y
Q x
+
+
=0
t
x
y

(2)

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Hartnett et al.

Figure 1: Mersey Estuary Study Domain.



2
UQ x
VQ x
U 2 U
Q x
xw xb
(3)
+
+
= f Q y gH +

+ H
+
t
x
y
x

x2
y2


2
Q y
UQ y
VQ y
V 2 V
yw yb
(4)
+
+
= f Q x gH +

+ H
+
t
x
y
y

x2
y2
where = water elevation above (or below) datum; U, V = depth averaged
velocity components in x, y directions; Qx = UH, Qy + VH = unit width
discharge components in x, y directions; H = + h = total water depth,

Modelling the Fate and Transport of Nickel

Figure 2: Mersey Estuary Bathymetry 2002.

h = water depth below datum; = momentum correction factor; f = Coriolis

parameter; xw , yw = surface wind shear stress components in x, y directions;
xb , yb = bed shear stress components in x, y directions; and = depth average
eddy viscosity.
Falconer[5] also details how Equations 24 are numerically discretised
and incorporated into the DIVAST computer code. DIVAST is used to find a
numerical solution to Equations 24, resulting in the predictions of current
speeds and directions and water surface elevations at each computational
grid point for prescribed boundary conditions. In this research the boundary
conditions specified are the tidal dynamics at the seaward boundary and the
Mersey River discharges at Howley Weir. The model underwent extensive
calibration and validation to provide confidence in the model results. Model
predictions were compared against field measurements of currents and water
elevations at a number of different locations throughout the estuary. Figure 3
presents a comparison between model results and field data for current speeds.
The correlation between model predictions and data is considered to be good
and is typical of the correlation achieved during the calibration/validation
aspect of the research. The hydrodynamics model is now considered to be
acceptable for use in predicting the transport of nickel about the Mersey
Estuary.

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Hartnett et al.

Figure 3: Comparisons between model predictions and measured current velocities at (a)
Pluckingham and (b) Eastham.

Solute Transport Model of Mersey Estuary

Salinity is transported into the Mersey Estuary from the Irish Sea during
flood tides; the near constant concentration of salinity in flood waters is
35 psu. The Mersey River and the 13 other tributaries to the estuary, along
with diffuse runoff from the catchment bordering the estuary, discharge
considerable amounts of freshwater water into the estuary. Thus significant

Modelling the Fate and Transport of Nickel

gradients of salinity prevail from Howley Weir to the seaward end of the
estuary; these gradients vary with time due to tidal dynamics and the volumes
of freshwaters entering the estuary. The salinity from the seawater mixes
with the freshwater water to produce complex salinity patterns throughout
the estuary. The depth-averaged, two-dimensional advective-diffusion equation for the salt transport processes can be obtained by integrating threedimensional advective-diffusion equation over the water depth, Falconer[11] ;
the depth-averaged governing equation for the salt transport can be
written as:







H UH VH
+
+

HDx

HDy
=0
(5)
t
x
y
x
x
y
y
where = depth-averaged salinity; Dx , Dy = depth-averaged diffusion
coefficients in x, y directions, respectively, which can be calculated as
Preston[12] :
Dx =

(klU 2 + ktV 2 )H g
+ DW ,

U 2 + V 2C

Dy =

(klV 2 + ktU 2 )H g
+ DW

U 2 + V 2C

in which kl = longitudinal dispersion constant; kt = lateral diffusion constant;

DW = wind induced dispersion coefficient; C = Chezy bed roughness coefficient;
and g = gravitational acceleration. The values of constant kl and kt are 5.93
and 0.15, respectively in the literature.[13,14] However, in practical studies
these values tend to be rather low,[15] with measured value for kl and kt ranging
from 8.6 to 7500 and 0.42 to 1.61, respectively.
Equation 5 describes how a constituent, q, is transported about a water
body based on currents and turbulent diffusion. The UK EA have a considerable data base of measured values of salinity throughout the Mersey Estuary
for various environmental conditions. In developing the solute transport model
a total of 44 freshwater discharges were specified from rivers and other
point sources. The model was initiated by firstly specifying an initial zero
salinity concentration at all points throughout the estuary. The model was
then executed to simulate how salinity would be transported into the model
domain and mix with the freshwater. The model was run for 20 tidal cycles
until steady state conditions were attained.
Model salinity predictions were compared against measured data at many
locations along the axis of the estuary. Figure 4 shows the comparison of
salinity predictions against measured salinity at two points along the estuary
during model calibration; the points referred to in Figure 4 are located at
Princes Pier and Runcorn. Also, Figure 5 shows the comparison of salinity
predictions against measured salinity at two points along the estuary during
model validation. From Figure 4 it is seen that there is quite good agreement
between the predicted and measured salinity values. The correlation shown

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Hartnett et al.

Figure 4: Comparisons between model predictions and measured salinities at (a) Princes
Pier and (b) Runcorn.

is typical of the correlation achieved for many comparisons between predicted

and measured salinity values.
The accurate prediction of salinity was very important during the development of the Mersey Estuary model. First, by being able to accurately predict
salinity provided the confidence that the model would be able to accurately
predict the transport and dispersion throughout the estuary of material

Modelling the Fate and Transport of Nickel

Figure 5: Comparisons between model predictions and measured salinities at (a) Eastham
and (b) Fiddlers Ferry.

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Hartnett et al.

discharged into the estuary through rivers, outfalls and diffuse discharges.
Secondly, and equally important during this research, accurate salinity values
were required to compute the partitioning coefficient in Equation 1. As can be
seen from Figures 4 and 5, salinity varies significantly both temporally and
spatially with consequential changes in the partitioning coefficient, emphasizing the importance of accurate salinity predictions.

Development of Partitioning Coefficient-Salinity Relationship

The UK EA routinely collect water samples along the axes of the Mersey
Estuary at 23 locations; these samples are usually collected on a monthly
basis. The water samples are subsequently analysed for many water quality
parameters, including salinity, sediments, dissolved heavy metals and particulate bound heavy metals. A suite of heavy metals are analysed for, including
Ni. From this data a relatively simple approach was adopted to evaluate the
partitioning coefficient.
From the database of survey results for heavy metals the values for
dissolved and particulate-bound Ni were extracted, along with the associated
salinity values for each sample. Using the dissolved and particulate concentrations of Ni, a value for the partitioning coefficient was computed for each
sample. These partitioning coefficients were then plotted against the salinity
value associated with each sample; Figure 6 presents the plot of KD versus
salinity. A functional relationship was developed between KD and salinity from
the data presented in Figure 6. A general relationship was postulated of the
form:
KD (s) = A + B.S + C.S2 + D.S3 + E.S4 + F.S5

(6)

where S is salinity.
A regression analysis was carried out to find the coefficients of Equation
6 that would provide the best fit with data. From this analysis, the following
coefficients were derived relating partitioning coefficient to salinity for Ni:
A = 7310
B = 3003
C = 457
D = 23.4
E = 0.4
F=0
The curve in Figure 6 shows the graphical representation of Equation 6
when the preceding coefficient values are used. The following points are

Modelling the Fate and Transport of Nickel

Figure 6: Plot of partition coefficient for Ni versus salinity.

worth observing from the approach adopted and the relationship that has
been developed. First, there is a considerable spread between the data and
Equation 6. The data shows quite a degree of variation and by inspection we
can see that, due to the complex chemical relationships governing partitioning
coefficients, a simple relationship based purely on salinity will never be able
to fully capture the fluctuations in the partitioning coefficients. Second, it is
very interesting to notice that there is not a unique relationship between
partitioning coefficient and salinity; for example, low salinity values and
salinities in the range of 1525 psu give approximately the same value
of KD .
From Figure 6 it is clear that the values of KD are higher for low and
high salinity values than for intermediate values; Equation 6 reflects this
characteristic of the KD versus salinity relationship. Most other approaches
to computing KD are indeed based on unique relationships between KD
and salinity, obviously neglecting the important property illustrated above.
Further work undertaken by the authors show that other heavy metals in
both the Mersey Estuary and the Ribble Estuary exhibit salinity relationships
similar to that shown in Figure 6.

Sediment Transport Model of Mersey Estuary

The manner in which heavy metals are distributed and transported
about an estuary is significantly influenced by bed sediments and suspended

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Hartnett et al.

particulate matter; this is certainly the case in the Mersey Estuary. Bed
sediments throughout the Mersey Estuary have been heavily contaminated
with heavy metals, mineral oils and other toxic contaminants resulting from
industrial and municipal discharges and accidental spills. Due to spring tidal
ranges of in excess of 10 m, tidal dynamics throughout the estuary are often
quite strong resulting in the resuspension of bed sediments during periods of
strong tidal induced bed shear stresses. During periods of low hydrodynamic
activity, typically around times of low and high water, suspended particulate
matter is allowed settled to the bed again. Thus concentrations of SPM vary
quite considerably throughout the tidal cycle with relatively large amounts of
sediments being shunted up and down the estuary by tidal action.
The dynamics of the SPM in the Mersey Estuary is important for two
main reasons. Firstly, during certain periods of the tidal cycle the bed becomes
a source of heavy metals into the water column and at other times the bed
becomes a sink for heavy metals from the water column. Obviously, when
sediments are being resuspended we must know the mass of the heavy metal
that is bound to these sediments to quantify the source terms. Hence in order
to accurately model heavy metals it is necessary to know the distribution of
sediments throughout an estuary and also the mass of particulate bound heavy
metals. Second, as the amount of SPM changes in the water column more or
less metal is exchanged from the dissolved stage to the particulate bound stage.
Thus the accurate prediction of heavy metals relies on the accurate predictions
of sediments in the water column.
The two-dimensional equation governing the transport and dispersion of
cohesive sediments throughout the estuary is given as:







S
S
SH SUH SVH
+
+

HDx

HDy
= qero + qdep
(7)
t
x
y
x
x
y
y
where S = depth-averaged cohesive sediment concentration; qdep , qero = the
deposition and erosion rates, respectively.
For the non-cohesive sediment transport we have the following twodimensional depth-averaged equation for the non-cohesive sediment transport:







S
S
SH SUH SVH
+
+

HDx

HDy
= Eae + wsS
t
x
y
x
x
y
y

(8)

where Eae = erosion constant (kg m2 s1 ) and ws = settling velocity. Further

details of the derivation of Equations 7 and 8 can be found in Wu and
Falconer.[9]
The sediment model is an integral part of the DIVAST numerical water quality model. The sediment transport model uses the same computational/bathymetric grid as the hydrodynamic model and sediment concentrations are computed at the same computational timestep. In Equations 7 and

Modelling the Fate and Transport of Nickel

Table 1: Non-cohesive sediments grading.
Grain size finer than (%)

Effective grain size (m)

D16
D50
D84
D90

10
50
175
205

8 the U and V components of velocity at each mode grid point and each
computational timestep are obtained from the hydrodynamic model.
The bed of the Mersey Estuary contains both cohesive and non-cohesive
sediments. By and large, the non-cohesive sediments lie on the estuary bed
between Howley Weir and Runcorn as shown in Figure 1, from Runcorn
seawards the bed sediments are predominantly cohesive. These observations
are made from assessment of bed sediment data collected by the UK EA along
the axis of the estuary. The non-cohesive sediments grading distribution is
given in Table 1. The grading shown in Table 1 is based on an averaging of 15
sediment samples taken along the axis of the bed. Cohesive sediments are of
more importance in this research as heavy metals become adsorbed onto the
surfaces of these sediments; the cohesive floc size of the cohesive sediments,
C50, is 64 m.
Apart from the resuspension of bed sediments the other significant sediment load was from the River Mersey. The UK EA has extensive measurements
of flow rates and associated sediment loads discharging from the Mersey River
into the estuary. From these data it was decided to calibrate and validate
the model using a 10-day average river flow from the Mersey River with its
associated sediment load.
The suspended sediment transport model was calibrated by comparing
sediment concentrations model predictions against field measurements. Comparisons were made against data collected on 18th September 1989 at six
locations along the estuary. During the field survey a spring tide of 9.36 m
was recorded at Gladstone Docks and the 10-day average Mersey River flow
was estimated to be 1,050 103 m3 /day.
The model was calibrated so that model predictions were as accurate as
possible. The model empirical coefficients were tuned to improved accuracy,
the best fit between predictions and data were obtained when the coefficients
had the following values:
Empirical erosion constant 0.00004 kg/N/s
Critical shear stress for erosion 1.5 N/m2
Critical shear stress for deposition 0.25 N/m2

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Hartnett et al.

Figure 7: Comparisons between model predictions and measured concentrations of SPM at

(a) Princes Pier and (b) Fiddlers Ferry.

Figure 7 shows comparisons between model predictions and data at two

locations, Princess Pier and Fiddlers Ferry; similar correlations were achieved
at other locations along the estuary. From Figure 7 it is seen that the model can
reasonably accurately predict SPM and the model reflects the peaks in SPM at
various stages in the tide when bed shear stress are high. Figure 7 is typical
of SPM model calibration in general.

Modelling the Fate and Transport of Nickel

Heavy Metal Model of Mersey Estuary

As can be seen, modelling heavy metals in an estuary is dependent on
accurately modelling hydrodynamics, salinity and SPM as well developing a
good understanding of the relationship between KD and salinity. This section
of the paper details the numerical predictions of dissolved Ni throughout the
Mersey Estuary. Details of the formulation of the heavy metal differential
equations and the numerical model can be found in Wu and Falconer.[16]
The main sources of heavy metals in the Mersey Estuary are from: bed
sediments; river discharges; domestic discharges; and seawater.
Table 2 presents the average flow rates and concentrations of Ni in the
flows from the river (total Ni) and domestic/industrial (dissolved Ni) wastewater discharges. The Ni load derived from flooding seawater was prescribed by
specifying a concentration of 1.0 g/L of dissolved Ni in the concentration of
the seawater. Within the bed sediments the Ni concentration, mass of Ni per
unit mass of sediment, was specified at 60 g/g of cohesive sediment. At each
computational timestep the model tracks the mass of cohesive sediment being
deposited and resuspended and then computes the mass of Ni from this source.
When Ni enters from the water column above sources, the model computes
the salinity at each location, it then computes partitioning coefficients and
fractions the Ni between dissolved and sediment bound based on the available
cohesive sediments at each model grid point. All the sources of Ni defined in
the model were derived from field data collected by the UK EA.
Model calibration was necessary to ensure high correlation between model
predictions and actual concentrations of dissolved Ni in the estuary. In particular, calibration was necessary to evaluate the empirically derived KD -salinity
formulation presented in Equation 6 above. Model calibration was carried out
by comparing model predictions of dissolved Ni against measurements of Ni
taken by the UK EA on 9th February 2001. Figure 8 shows the correlation
Table 2: Sources of Ni discharging into Mersey Estuary.
Source
Wastewater Treatment
Plants
Sandon
Warrington
Croda Colloids
River Discharges
Weaver
Mersey
Sankey
Ditton
MSC@Easham
Dissolved

Flow rates (m3 /s)

Ni concentration (g/l)

3.385
0.941
0.045

25
6
6

5
30100
2.62
1
7

and particulate Niotherwise values relate to dissolved Ni.

7
7
7
7
8

841

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Hartnett et al.

Figure 8: Metal Calibrationcomparison between model predictions and measured

dissolved Ni concentrations along axis of Mersey Estuary on 9th September 2001.

between the model predictions and measured data for Ni along the axis of the
estuary downstream from Howley Weir.
Further, model validation was subsequently carried out against data
collected on 28th March 2002. During validation the model parameters remain
unchanged, the environmental conditions prevailing on the survey dates are
specified to the model and the model is executed. Figure 9 presents comparison
between model predictions and measured values of dissolved concentrations of
Ni.

DISCUSSION
The measured dissolved Ni data taken on both the calibration and validation
dates show different conditions prevailing with respect to dissolved Ni concentrations in the water column; the model results reflect these variations and
exhibit a high degree of correlation with the measured data. Data shows Ni
concentrations varying in both time and spatially due to varying flow rates and
tidal dynamics. Although the estuary bed has been modeled as having a sharp

Modelling the Fate and Transport of Nickel

Figure 9: Metal Validationcomparison between model predictions and measured

dissolved Ni concentrations along axis of Mersey Estuary on 28th March 2002.

divide between the locations of cohesive and non-cohesive sediments, model

predictions are still quite good considering how complex it is to understand
and then model heavy metals. The general equation of the form shown in
Equation 5 relating partitioning coefficient to salinity has departed from
previous approaches and has given a greater degree of flexibility in defining the
form of the KD -salinity relationship. Conventionally the chemical behaviour of
heavy metals in brackish waters have been based on exponential KD -salinity
relationships, such as the following relationship developed by Turner and
Millward:[8]
ln KD = b[ln(S + 1)] + ln K0D

(9)

where b is the slope of ln(KD ) versus ln(S + 1) and K0D is the partitioning in
freshwater.
Turner and Millward[12] provide values of b and K0D for three heavy metals,
Cd, Cs and Zn; these values are presented in Table 3. Figure 10 graphical
illustrates KD for Zn using Equation 9 and the values from Table 3. From

843

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Hartnett et al.
Table 3: Partitioning coefficient parameters for various metalsSource Turner and
Millward.[8]
Metal
Cd
Cs
Zn

K0D

1.36
0.688
0.374

199
3.5
32.9

Figure 10 the exponential shape of KD is obvious, showing that KD has a unique

relationship with salinity and is shown to decrease with increasing salinity.
Importantly, by inspection of Figure 6 we see that the exponential decrease
of KD with salinity, that is often adopted by modellers, does not happen for the
case of Ni in the Mersey Estuary. The data shows relatively high values for
KD at low salinities, a drop in KD values at intermediate salinities and a rise
again in KD values for high salinities. There is an obvious trend to this data
and so the model must take this into account. Equation 6 as plotted in Figure
6 also exhibits this trend and hence is considered to define a more realistic
relationship between KD and salinity than an exponentially decreasing function. Equation 6 importantly allows the non-unique relationship between KD
and salinity be expressed mathematically, so that for two different salinities
the relationship may compute the same KD value.

Figure 10: KD -salinity plot for Zn-based on Turner and Millward.[12]

Modelling the Fate and Transport of Nickel

The development of Equation 6 is conceptually very simple, it is based on

sampling estuarine water and analysing the sample for dissolved and particulate metals and salinity. The methodology inherently includes variations in
the salinity of the actual estuarine waters that provides an indicator for variations in water chemistry. Based on this approach, once the numerical model
accurately predicts the spatial and temporal salinity variations partitioning
coefficients can be simply calculated.
Figure 6 shows that there is a considerable spread in the KD values
computed from data for a given salinity for Ni, however, this spread is
relatively small when we consider other metal constituents of the Mersey
Estuary such as lead. Figure 11 shows a KD -salinity plot for Hg based on measured data of dissolved and particulate Hg and on measurements of salinity.
Equation 6 represents an average relationship for KD -salinity; however, from
the model results this relationship appears to work quite well in predictions
the transport and dispersion of Ni throughout the Mersey Estuary. Thus by
developing KD -salinity relationships from field measurements the extent of
fluctuations in water chemistry becomes apparent and can be incorporated into
the relationship in an averaged manner.
The authors are aware of the work done by Turner and Millward[8]
in considering conceptual aspects of KD -salinity relationships to develop
improved predictive bio-geochemical models. Their work was based on a
series of laboratory experiments. Issues addressed by Turner and Millward
included the dependency of solid-solution partitioning on particle size and
isotope speciation in solution, and the relative contribution and implications of
flocculant products to absorbed contaminant concentrations. However, in order

Figure 11: Plot of KD -salinity for Hg in the Mersey Estuary.

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Hartnett et al.

to use the approaches outlined by Turner and Millward it is necessary to have

considerable more information on estuarine processes such as floc formulation.
Even if these processes were well understood, this is would require very
extensive computational time making the modelling tasks extremely difficult
to undertake.

CONCLUSION
The general methodology outlined above and its application to the Mersey
Estuary is similar to many other heavy metal modelling studies. The main difference in approach has been the manner in which the partitioning coefficient
has been developed; this has significance for future heavy metal modelling
studies. As in many previous studies, KD is expressed as a function of salinity
that reflects total water chemistry. The KD -salinity relationship developed for
Ni is based on direct sampling of the estuary waters and subsequent chemical
analysis. Having developed this relationship, it is quite easy to incorporate it
into a numerical model, requiring only to compute salinity before calculating
the value of KD . The metal model developed for the Mersey has been proven
to predict Ni concentrations that are quite close to measured data, proving the
approach is promising in this case.
The authors are developing KD -salinity relationships for other metals
in the Mersey Estuary and elsewhere using the same approach. For some
metals the application of Equation 6 to data results in an exponential type
of KD -salinity relationship, for other metals the approach does not result in an
exponentially decreasing relationship. Thus one of the advantages of this approach is that the form of the KD -salinity relationship is not overly prescribed.
Through the application of the above approach, the authors are in the
process of developing a series of KD -salinity relationships for various metals
and in different estuaries. The completion of this work will shed more light
on how KD -salinity relationships vary between metals and between estuaries.
The authors will publish this work on its completion. This will provide other
researchers with useful initial relationships for heavy metal modelling in the
absence of data for the system of interest.

ACKNOWLEDGMENTS
This work was funded by the UK Environment Agency under Contract No.
12153: Development of a Water Quality Model for the Mersey Estuary. The
authors wish to thanks the UK Environment Agency for permission to publish
this paper.

Modelling the Fate and Transport of Nickel

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