Desalination 284 (2012) 2231

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Desalination
journal homepage: www.elsevier.com/locate/desal

Modeling of nitrate removal for ion exchange resin in batch and xed
bed experiments
A.A. Hekmatzadeh a, A. Karimi-Jashani a,, N. Talebbeydokhti a, b, B. Klve c
a
b
c

Department of Civil and Environmental Engineering, Shiraz University, P.O. Box 7134851156 Shiraz, Iran
Environmental Research and Sustainable Development Center, Shiraz University, Shiraz, Iran
Water Resources and Environmental Engineering Laboratory, Department of Process and Environmental Engineering, University of Oulu, Oulu, Finland

a r t i c l e

i n f o

Article history:
Received 30 June 2011
Received in revised form 14 August 2011
Accepted 16 August 2011
Available online 14 September 2011
Keywords:
Advectiondispersion equation
CrankNicholson scheme
Mass action law model
Nitrate selective resin

a b s t r a c t
In this study, nitrate removal from aqueous solutions was studied using a nitrate selective ion exchange resin
in both batch and xed bed experiments. Nitrate retention experiments were carried out using nitrate-rich
groundwater and several synthetic waters with different initial nitrate concentrations and the presence of
competitive ions, such as sulfate. The equilibrium data were modeled and compared using the Langmuir adsorption isotherm and the mass action law and both models described the experimental data well. However,
different values of Langmuir coefcients were obtained for different operating conditions, whereas it is possible to state all equilibrium data with a simple general equation obtained by applying the mass action law. A
mathematical model (advectiondispersion equation) was solved numerically to predict the dynamic behavior of the columns. The experimental breakthrough curves from column experiments were in good agreement with the model predictions. The mass action isotherm parameters obtained from these column
experiments were conrmed by the results of the batch experiments. Consequently, column behavior can
be predicted from the batch equilibrium data by using the mass action isotherm. Finally, sensitivity analysis
showed that the variation of dispersion coefcient between two times higher and two times lower than the
base value was negligible.
2011 Elsevier B.V. All rights reserved.

1. Introduction
Nitrate is one of the most widespread pollutants of groundwater
in many developed and developing countries. Intensive use of chemical fertilizers, manure in crop production, and poor wastewater
treatment and collection systems are the main sources of nitrate contamination in groundwater [13]. Additionally, the existence of
nitrate in drinking water is a potential hazard to human health, the
reason being that nitrate is reduced to nitrite in the digestion system
and then absorbed by blood, which in turn is combined with hemoglobin, preventing the oxygen uptake of blood. This can lead to methemoglobinemia (also called blue baby syndrome) in infants. Moreover,
the formation of nitrate compounds in the stomach has been shown to
be carcinogenic [4,5]. Groundwater is extensively used as one of the
main sources of drinking water in many areas around the world
[1,6]. About 75% of potable water for drinking purposes in Shiraz, the
biggest city in the south of Iran, is supplied by groundwater [7]. In this
city, the wastewater collection system is currently under construction

Corresponding author. Tel.: +98 7116473499, +98 9173007901(mobile); fax: +98

711 6473161.
E-mail addresses: hekmatz@shirazu.ac.ir (A.A. Hekmatzadeh),
akarimi@shirazu.ac.ir, ajashni@yahoo.ca (A. Karimi-Jashani), taleb@shirazu.ac.ir
(N. Talebbeydokhti), bjorn.klove@oulu. (B. Klve).
0011-9164/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.desal.2011.08.033

and many houses use adsorption wells for their sewage, which causes
the groundwater to become polluted with nitrate.
Nitrate is a highly stable and soluble ion that is difcult to remove
using traditional water treatment methods [8]. Therefore, several
techniques for nitrate removal have been presented, such as biological denitrication, reverse osmosis, electro dialysis, ion exchange,
adsorption, chemical reduction using zero valent iron, and catalytic
reduction [919]. Ion exchange is considered to be one of the best
and most feasible methods for nitrate removal of water supplies
due to its high efciency, simple operation and relatively low cost
[5,2023]. The conventional anion exchange resins usually have an
ion selectivity sequence of SO4 N NO3 N CL N HCO3 [8]. As a result,
nitrate removal of water with high sulfate concentration can be difcult, since resin capacity is reduced by sulfate. Moreover, nitrate
peaking or nitrate dumping might occur with these types of resin if
sulfate replaces nitrate [5,20,24,25]. Amberlite IRA 410 [26], Amberlite IRA 900 [27], Amberlite IRN-78 [28], Amberlite IRA 400 [29], and
Amberlite IRN 9766 [22] are examples of conventional anion exchange resins used in the studies on nitrate removal. However,
nitrate-to-sulfate selective resins can operate successfully for nitrate
removal without any nitrate peaking in the presence of sulfate [8,20].
Imac HP555 [21], Amberlite IRA 996 [25], Purolite A520E [5,14], and
Indion NSSR [23] are examples of nitrate selective resins that have
been used previously in nitrate removal studies.

A.A. Hekmatzadeh et al. / Desalination 284 (2012) 2231

To the best of our knowledge, most studies on nitrate removal by ion

exchange resins have been performed in batch experiments and only a
few have been reported in xed bed systems [19,21,22,2529]. In general, batch experiments are used to determine the equilibrium isotherm
and kinetic of nitrate removal onto resin particles. One disadvantage of
these experiments is that they do not give information about the hydrodynamic parameters of xed bed columns such as the dispersion coefcient [30]. Another drawback of batch processes is their discontinuity
and the need to perform complicated phase separation operations
[31]. Furthermore, little attention has been paid to the numerical solution of nitrate removal models in a xed bed column packed with ion
exchange resins, even though a suitable numerical solution can help
to reduce the number of experiments associated with new operating
conditions. A novel and well-researched model can be used as a reliable
solution to design, optimize and predict the breakthrough curves of
xed bed columns in real water treatment processes.
Both empirical and more theoretical isotherm models have been
developed to describe ion exchange equilibrium [3234]. Several empirical and semi-empirical isotherm models can be found in the literature, such as the Langmuir and Freundlich equations to explain ion
exchange equilibrium [35,36]. Several researchers have used these
methods to illustrate the equilibrium of the ion exchange process
[5,29,3741]. Theoretical isotherm models are basically based on the
law of mass action. In these methods, the ion exchange process is
treated as a chemical reaction, while the concept of membrane theory
and thermodynamic description are used to illustrate the real behavior of ions in both the solution and resin phases [31,32]. It is important
to note that few comparisons have been done between empirical and
theoretical equilibrium models for ion exchange resins.
The aim of the present research is to study and model the removal
of nitrate from synthetic solutions and groundwater through the use
of a selective ion exchange resin called IND NSSR in both batch and
xed bed systems. The effects of ow rate, initial nitrate concentration and the existence of competitive ions such as sulfate on nitrate
removal were also investigated. Afterwards, the equilibrium data
were simulated by an adsorption isotherm and the mass action law,
and the results were compared to each other under different operating conditions. Then, a numerical model was developed to solve the
advection dispersion equation with adsorption in columns. The adsorption term was simulated using the mass action law isotherm.
Model parameters were estimated and compared to those obtained
in equilibrium experiments. Finally, sensitivity analysis was performed to determine the effect of model parameters on breakthrough
curve shape.
2. Experimental
2.1. Materials
A nitrate selective ion exchange resin named IND NSSR was
obtained from Ion Exchange India LTD. This material is a macroporous
strongly basic anion resin that is suitable for the removal of nitrate
from water. The effective sizes of the particles range from 0.4 to
0.5 mm containing exchangeable chloride ions. The unique advantage
of this resin is that it has more afnity for nitrate ions in comparison
with other existing anions. Before use, the resin particles were
washed with distilled water in order to remove any adhering dirt.
The resin was dried at an oven temperature of 60 C for the batch experiments. Synthetic solutions were prepared by dissolving different
amounts of NaNO3, Na2SO4 and NaCl in distilled water in order to
reach the desired concentrations. The groundwater was obtained
from one of the drinking wells of Shiraz, Iran. The characteristics of
this water are summarized in Table 1.
Nitrate ions were analyzed using a UV spectrophotometer instrument (HACH DR/5000) at a wavelength of 220 nm. Before measurement, 50 ml of samples was acidied with 1 ml of 1.0 N HCl in order

23

Table 1
Composition of Shiraz groundwater.
Species

Concentration (mg/l)

F
Cl
SO4
HCO3
NO2
NO3
NH3
Ca++
Mg++
Na+
K+
TDS
pH

0.76 0.007
100.3 0.518
236 0.323
360.3 2.24
0.012 0.005
63.3 0.24
0.08 .01
118.7 2.71
68.1 0.763
80.4 0.844
2.8 0.128
884 5.25
7.53 0.08

to eliminate the interface of hydroxide and bicarbonate ions. The pH

of the analyzed solution was 2 0.1. Sulfate and chloride ions were
analyzed using Ion Chromatography (Metrohm 761).
2.2. Batch mode equilibrium experiments
In order to obtain the ion exchange equilibrium data, batch experiments were carried out in duplicate with respect to Shiraz
groundwater and various synthetic solutions, including solutions
with different initial nitrate concentrations and solutions containing
sulfate and chloride ions. A specied amount of resin (0.025 to 0.8 g)
was added to glass bottles containing 200 ml of nitrate solution. The
bottles were sealed and placed in a temperature-controlled rotating
shaker for 24 h to reach equilibrium. The temperature was kept at a
constant 20 C with a maximum tolerance of 0.1 C. The ion concentration uptake to solid phase was computed using the following mass
balance equation:
qe

C0 Ce V
m

where qe (mg/g) is the solid phase equilibrium adsorption concentration, C0 and Ce (mg/l) are the initial and equilibrium liquid phase ion
concentrations, and V (l) and m (g) are the volume and the resin
mass, respectively.
2.3. Column mode experiments
Column tests were performed using glass columns with an internal diameter of 3.6 cm. A schematic diagram of the column setup
used for the xed bed studies is shown in Fig. 1. All experiments
were conducted at a constant temperature of 20 1 C. The nitrate
solution was passed through the resin bed in an upward direction
to ensure a completely saturated bed [42]. A peristaltic pump was
used to maintain a constant ow rate during the experiments. The experiments were carried out at different conditions of ow rates, inuent concentrations and the presence of sulfate and chloride ions. The
resin bed height for all tests was set at 20.5 cm with a tolerance of
0.15 cm. The column experiments were continued until the complete
saturation of the resins was achieved. The column void portion, i.e.
bed porosity, was estimated through rst moment analysis of pulse
loading experiments using NaCl as a tracer. The effect of ow rate on
nitrate adsorption was investigated by varying the ow rate from 0.69
to 2.11 l/h at a constant inuent nitrate concentration of 120 mg/l
(Runs 1 to 3). Moreover, the effect of the inuent nitrate concentration
on the sorption performance of nitrate was examined at the values of
89.5 and 60.4 mg/l (Runs 4 and 5). Run 6 and Run 7 were arranged in
order to inspect the inuence of sulfate and chloride ions on the removal of nitrate. Finally, column tests were performed to investigate nitrate
removal from Shiraz groundwater (Runs 8 and 9).

24

A.A. Hekmatzadeh et al. / Desalination 284 (2012) 2231

It is important to note that this equation has been extracted from binary systems where only nitrate and chloride are present in the initial
solution. When the system contains more anions such as sulfate, additional terms should be included in the nominator of Eq. (6) [32].
Eq. (6) can be put to a linear form (Eq. (7)) in order to determine k
and qT coefcients through linear regression.
1
1
C0
k1

:
qeNO3 k qT CeNO3
k qT

3.2. Column numerical modeling

The column breakthrough curve or the concentrationtime prole
can be modeled by the differential mass balance of solute transport in
a segment of the column. The governing transport equation that includes the adsorption of solute in the column is described by the following one dimensional advection dispersion equation [43]:
Fig. 1. Experimental setup for column tests.

C
2 C
C q
D 2 u b
n t
t
x
x

3. Modeling
3.1. Equilibrium modeling
The Langmuir isotherm model is a well-known and widely used
model in the literature [35]. The model assumes monolayer adsorption onto surfaces that take place at the nite number of identical
sites. There are no lateral interactions between neighboring adsorbed
molecules [35]. The Langmuir relation is stated as Eq. (2):
qeNO3

Q 0 b CeNO3
1 b CeNO3

where Q 0 and b are known as the Langmuir constants and CeNO3 and
qeNO3 are the pollution concentrations of the liquid and solid phases, respectively. Q 0 is the maximum adsorption capacity and b is a constant
related to adsorption energy. In order to calculate Q 0 and b parameters,
Eq. (2) can be rearranged to give the following linear equation:
1
1
1
1

:
qeNO3 Q 0 b CeNO3 Q 0

In the mass action law approach, the ion uptake by resin particles
can be treated as chemical reactions. The following expression represents the chemical reaction between nitrate ions and resin particles:
RCl

NO3 RNO3 Cl :

CeCl qeNO3
qeCl CeNO3

where qeNO3, qeCl, CeNO3 and CeCl represent concentrations of nitrate

and chloride ions in the resin and liquid phases at equilibrium condition, respectively. Applying mass balance to the resin and liquid
phases leads to the following isotherm equation:
qeNO3

k qT C eNO3

C0 k1CeNO3

Here, C and q are the nitrate concentrations in the liquid and solid
phases, respectively. u represents the interstitial velocity of the solution through the bed. D, b, and n stand for the axial dispersion coefcient, bulk density and bed porosity of resin particles, respectively.
In solving Eq. (8), one more relationship is needed as it contains
two unknown variables: C and q. Therefore, assuming local equilibrium, the mass action law isotherm model was used to explain the relationship between C and q. The last term on the right hand side of
Eq. (8) can be replaced with relation 9:
q q C

:
t C t

The transport Eq. (8), the mass action isotherm Eqs. (6) and (9)
were combined to obtain the following one dependent variable partial differential equation:
R

C
2 C
C
D 2 u
t
x
x

10

where R is the retardation factor, dened as:

R

!
b
kC0 qT
:
n C0 k1C 2

11

In this expression, NO3 and Cl represent nitrate and chloride

concentrations in the liquid phase and R NO3 and R Cl are the
ion concentrations in the solid phase. The apparent equilibrium constant of reaction 4 is:
k

where qT (qT = qeNO3 + qeCl) denotes the maximum ion exchange capacity of resin and C0 is the total anion concentration. Eq. (6) is
known as the competitive Langmuir isotherm in the literature [33].

Eq. (10) can be transformed to dimensionless form as Eq. (12):

C
D 2 C C

T uL X 2 X

12

where X (X xL) and T (T tuL) are dimensionless length and time variable, respectively and L is the resin bed length. The initial and boundary
conditions of the above equation in the present experimental set-up are
as follows:
C T 0 0

0X1

13

C X 0 C0 NO3

0T

14

C X 1
0
X

0T:

15

A computer code was developed and run in the MATLAB software

using nite difference techniques to solve Eq. (12). The general form

A.A. Hekmatzadeh et al. / Desalination 284 (2012) 2231

25

Table 2
Batch experiments data with synthetic solutions.
Synthetic
solution

W/V
g/l

C0
meq/l

Ce
meq/l

qe
meq/g

Synthetic
solution

W/V
g/l

C0
meq/l

Ce
meq/l

qe
meq/g

1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
3
3
3
3
3

0.101
0.180
0.219
0.332
0.5
1
1.5
2
2.5
3
0.1
0.15
0.25
0.5
1
1.5
2
2.5
3
0.1
0.15
0.25
0.5
1

1.902
1.902
1.902
1.902
1.902
1.902
1.902
1.902
1.902
1.902
1.407
1.407
1.407
1.407
1.407
1.407
1.407
1.407
1.407
0.897
0.897
0.897
0.897
0.897

1.596
1.407
1.345
1.147
0.833
0.357
0.200
0.136
0.102
0.086
1.157
1.049
0.835
0.485
0.193
0.114
0.079
0.071
0.057
0.685
0.604
0.428
0.214
0.086

3.032
2.757
2.549
2.275
2.139
1.545
1.140
0.892
0.731
0.618
2.506
2.385
2.288
1.843
1.214
0.862
0.664
0.537
0.455
2.113
1.951
1.873
1.365
0.811

3
3
4
4
4
4
4
4
4
5
5
5
5
5
5
5
6
6
6
6
6
6
6

1.5
2
0.127
0.253
0.501
1.0065
1.753
2.501
4.003
0.126
0.250
0.502
1.003
1.752
2.501
4.002
0.207
0.376
0.753
1.504
2
2.5
3.25

0.897
0.897
4.873
4.873
4.873
4.873
4.873
4.873
4.873
6.795
6.795
6.795
6.795
6.795
6.795
6.795
9.871
9.871
9.871
9.871
9.871
9.871
9.871

0.050
0.036
1.658
1.454
1.114
0.664
0.357
0.243
0.150
1.739
1.579
1.264
0.857
0.518
0.357
0.221
1.683
1.478
1.157
0.750
0.600
0.469
0.364

0.564
0.431
1.998
1.807
1.590
1.238
0.886
0.667
0.440
1.604
1.448
1.350
1.081
0.812
0.633
0.430
1.546
1.398
1.124
0.833
0.701
0.613
0.504

of the nite difference approximation of Eq. (10) is in the form of

Eq. (16):
(
 n
C n1 Cin
D
n
n 
1
Ri i
Ci1 2Ci Ci1
2
T
uLX

function can be stated as root mean square of errors (RMSE) between

experimental data and model estimations.

RMSE

)
n

1 
n
n
n
1Ci Ci1 1Ci1 Ci
X
(


D
n1
n1
n1

Ci1 2Ci Ci1

2
uLX

)
i
1 h
n1
n1
n1
n1
1Ci Ci1 1Ci1 Ci
:
X
16

Here, i and n are the time and length indices, respectively. Also,
and denote temporal and spatial weighting parameters. Discretization of rst order derivatives in Eq. (16) ends up in a truncation error
in algebraic form which is proportional to the second derivative term
2 C
of X
2 . This error forms a second order numerical dispersion which
should be represented in Eq. (16). Eq. (16) is reduced to the Crank
Nicolson approximation, centered in space, when = = 0.5. In
this scheme, numerical dispersion will be zero [44]. In order to
achieve a reliable numerical solution, articial oscillation (also
known as overshoots and undershoots) should be avoided. It was
found in this research that when grid spacing is such that the grid
Peclet number, Peg (dened by Eq. (17)), is less than 2, these overshoots and undershoots are reduced considerably.
Peg

uLX
:
D

17

The governing Eq. (10) contains two groups of model parameters.

The rst group can be measured directly as velocity and bulk density.
These parameters were considered as xed values in modeling. The second ones need to be estimated, such as the dispersion coefcient, maximum adsorption capacity and apparent equilibrium constant. The later
parameters are obtained by minimizing an objective function. This

v
u n 
2
u
u C exp;i C model;i
t i1
n

18

where Cexp and Cmodel are the experimental and model predictions of
nitrate concentration obtained at the column outlet. The lsqnonlin
function in the optimization toolbox of MATLAB software was used
to optimize the values of the aforementioned parameters. This function uses non-linear least square techniques to minimize the objective function.
4. Results and discussion
4.1. Batch equilibrium results
The isotherm experimental data of the batch experiments with
different synthetic solutions and Shiraz groundwater are reported in
Tables 2 and 3, respectively. The initial nitrate, sulfate, and chloride
concentrations of the different synthetic solutions are given in
Table 4. Regression analysis was performed on the data using the linear form of the Langmuir and the mass action law isotherm models
(Eqs. (3) and (7)). The estimated constants of both models and related correlation coefcients (R 2) and root mean square errors (RMSE)
for different batch experiments are provided in Table 4. Root mean
square errors (RMSE) were calculated between experimental nitrate
solid phase concentration measurements, i.e., qeNO3, and the predictions of Langmuir and mass action isotherms. The values of correlation coefcients (R 2) are higher than 0.94, which indicates a
satisfactory description of each set of equilibrium data by both isotherm models. However, the estimated values of Langmuir constant
b varied, ranging from 0.47 to 2.83 l/meq for different cases of batch
experiments. This shows that Langmuir constant b depends on the solution environment and changes with nitrate, sulfate, and chloride
concentrations in solutions. Consequently, the Langmuir equation is
not fully accurate to be used in predicting the dynamic behavior of

26

A.A. Hekmatzadeh et al. / Desalination 284 (2012) 2231

Table 3
Batch experiments data with Shiraz groundwater.
C0
meq/l

Ce
meq/l

qe
meq/l

0.125
0.2085
0.25
0.3755
0.5
0.751
1
1.502
2.0055
2.5
2.5025
3.252
4

8.870
8.870
8.870
8.870
8.870
8.870
8.870
8.870
8.870
8.870
8.870
8.870
8.870

0.908
0.814
0.814
0.707
0.688
0.501
0.465
0.307
0.243
0.236
0.200
0.164
0.168

1.073
1.099
0.913
0.896
0.708
0.722
0.577
0.490
0.399
0.323
0.337
0.270
0.219

R = 0.999
RMSE=0.044 meq/g

1/qe NO3

W/V
g/l

2.5

R = 0.997
RMSE=0.157 meq/g

1.5

1
Nitrate solution (sol.

0.5

Nitrate+chloride solution (sol.

0
0

10

12

14

1/Ce

B
2.5

1/qe NO3

columns packed with ion exchange resin. In contrast, the estimated

constants of the mass action law isotherm (k and qT) for all cases
are close to each other. The model constants, qT and k, are in the
range of 2.13 to 2.81 meq/g and 5.20 to 7.23, respectively. Therefore,
it is possible to state ion exchange equilibrium with the unique isotherm equation using the mass action law. These results show that
the mass action law isotherm is more efcacious for describing ion
exchange equilibrium in comparison with adsorption models such
as the Langmuir isotherm. Although the Langmuir model can describe
equilibrium data adequately, its parameters such as b depend on solution conditions.
Another important difference between the Langmuir and the mass
action law isotherm models is related to the estimation of maximum
adsorption capacity (Q0 and qT). As shown in Table 4, the Langmuir
equation overestimates the value of maximum adsorption capacity
in comparison with the mass action law equation. Also, the range of
estimation of the Langmuir model is noticeably wider than the second
model. The estimated values of Q0 are between 2.46 and 3.50 meq/g,
while the values of qT range from 2.13 to 2.81 meq/g. This shows that
the mass action law model is more reliable than the Langmuir model.
The results showed that the Langmuir coefcient b changed considerably when chloride, sulfate, or both were present in nitrate solutions,
while the mass action law constants remained nearly constant in these
conditions. The linear form of the Langmuir and the mass action law isotherms (Eqs. (3) and (7)) were compared for synthetic solutions 1 and 4
(Fig. 2). The difference between these two solutions was the existence
of chloride in the latter. Nitrate concentration was the same in both solutions. Although both solutions follow the Langmuir isotherm model
individually, the predicted value of b for synthetic solution 4 is less
than half of the b constant obtained for solution 1. Therefore, it is not accurate to express both equilibrium data with the same Langmuir equation. However, as Fig. 2(B) shows, not only are both data sets described
well by the mass action law model, but also they can be shown with

1.5

Nitrate solution (sol.1)

R = 0.997 RMSE=0.157 meq/g

Nitrate+chloride solution (sol.4)

0.5

R = 0.999 RMSE=0.044 meq/g

0
0

10

20

30

40

C0/Ce
Fig. 2. Comparison of Langmuir and mass action law models using batch experiments
data of solutions 1 and 4 for (A) linear form of Langmuir model, and (B) linear form
of the mass action law model.

almost a single line. Similar gures were obtained for the other solutions which they are not shown here for the sake of brevity.
The Langmuir constant b is related to adsorption energy and does
not give any information about the chemical mechanism. Previously,
the Langmuir and the mass action law models were compared by
Misak (2000) [45]. According to his argument, if the Langmuir model
is used in the ion exchange equilibrium description, the Langmuir constant b should be equal to k/CCl, where CCl is chloride concentration in an
equilibrium state. This means that b is a function of CCl and is therefore
not constant. On the other hand, the estimated value of b is inuenced
by the value of C0, i.e. the total initial anions concentration. Although
the Langmuir model is a simple and excellent representative of isotherm data, this ion exchange equilibrium cannot be represented by

Table 4
Isotherm parameters obtained for removal of nitrate by IND NSSR resin.
Solutions

Sol. 1
Sol. 2
Sol. 3
Sol. 4
Sol. 5
Sol. 6
Groundwater
All data

Langmuir isotherm parameters

Mass action law isotherm parameters

Initial nitrate sulfate and

chloride concentrations

Q0
meq/g

b
l/meq

R2

RMSE
meq/g

qT
meq/g

R2

RMSE
meq/g

NO3
mg/l

SO4
mg/l

Cl
mg/l

3.223
3.351
2.549
2.848
2.455
3.082
3.495
1.028

2.801
2.834
5.669
1.230
0.961
0.521
0.472
13.51

0.997
0.991
0.998
0.999
0.992
0.985
0.940
0.190

0.157
0.066
0.045
0.044
0.030
0.051
0.078
0.691

2.713
2.679
2.130
2.441
2.129
2.579
2.814
2.548

6.322
5.001
6.082
6.991
7.529
6.156
5.196
5.893

0.997
0.991
0.999
0.999
0.999
0.986
0.941
0.962

0.157
0.066
0.045
0.044
0.030
0.051
0.078
0.141

118
87
56
120
120
126
63

0
0
0
0
236
240
235

0
0
0
100
0
0
100

A.A. Hekmatzadeh et al. / Desalination 284 (2012) 2231

27

concentration was not included in C0. This conclusion will be veried

again later in a column test using Shiraz groundwater.
R = 0.9619
RMSE = 0.1406 meq/g

1/qe NO3

4.2. Column test results

3

0
0

10

20

30

40

50

60

C0/Ce
Nitrate solution (sol. 1 to 3)
Nitrate+chloride (sol. 4)
Nitrate+sulfate (sol. 5)
Nitrate+sulfate+chloride (sol. 6)
Shiraz groundwater

Fig. 3. Linear form of mass action isotherm model for all equilibrium data obtained
from batch experiments.

such an adsorption system. Thus, the mass action law model is a better
representative of ion exchange equilibrium data.
Even though Eq. (6) has been obtained for binary (nitrate and chloride) systems, it also works well in cases where there is sulfate in the nitrate solution. In the conducted experiments, solutions 5 and 6 and
Shiraz groundwater contained sulfate and nitrate. As Fig. 3 shows, all
data points (i.e., synthetic solutions 1 to 6 and Shiraz groundwater) follow the mass action model line very well. This also can be underscored
by the obtained correlation coefcient of 0.96, conrming satisfactory
agreement between the isotherm data and the isotherm model. Thus,
it may be concluded that Eq. (6), which is obtained by applying the
mass action law to binary systems, can be applied to various initial nitrate concentrations and with or without the presence of chloride, sulfate, and bicarbonate in nitrate solutions. The calculated average
values of k and qT for all equilibrium data in the experiments were computed to be 5.89 and 2.55 meq/l, respectively.
The term C0 in Eq. (6) is equal to the sum of the nitrate, sulfate and
chloride ion concentrations. In the case of Shiraz groundwater, which
also contains bicarbonate ion, the preliminary results of adsorption
experiments showed that the existence of bicarbonate has a negligible effect on nitrate uptake by this resin. Therefore, bicarbonate

4.2.1. Continuous modeling

The results of columns tests were used to determine the mathematical model (Eqs. (10) and (11)) parameters. The characteristics
of column experiments and their results are listed in Table 5. The experimental data and the model prediction are also provided in Fig. 4.
There was a close agreement between the simulated and experimental breakthrough curves in several column experiments, including
those with different ow rates, initial nitrate concentrations, and
the presence of sulfate and chloride ions in the inuent. All computed
correlation coefcients are above 0.96, indicating a high level of
agreement (Table 5).This shows that the presented mathematical
model, including axial dispersion and the mass action law isotherm,
successfully describes the adsorption process of an ion exchange column packed with this resin, i.e., nitrate selective resin IND NSSR
under diverse operating conditions.
The tted isotherm parameters for all cases of column experiments (qT and k), reported in Table 5, are in good agreement with
the batch experiment results. The estimated values of maximum ion
exchange capacity, qT, and the apparent equilibrium constant, k,
range from 2.3 to 2.75 meq/g and from 4.9 to 6.2, respectively.
These estimations are close to each other and are also in good agreement with those obtained from the batch experiments. This conrms
that the mass action law isotherm is a suitable model when dealing
with ion exchange processes in a packed bed column. In fact, a simple
mass action isotherm equation obtained from equilibrium data can be
used in dynamic modeling to predict breakthrough curves in diverse
operating conditions. The optimized isotherm parameters and the
dispersion coefcients obtained using nonlinear least square, as
explained before, are presented in Table 5.

4.2.2. Effect of ow rate

The breakthrough curves of column tests of different ow rates
(Runs 1 to 3) can be found in Fig. 4(A). This gure shows that the
breakthrough time generally occurred faster with higher ow rates
(i.e. higher velocity). Moreover, the adsorption capacity remains nearly constant when the ow rate changes from 2.11 to 0.69 l/h (Table 5).
The total adsorption capacity and breakthrough adsorption capacity of
these experiments are all between 55.1 to 56.0 mg nitrate/ml resin
and 45.5 to 46.9 mg nitrate/ml resin, respectively. It seems that the nitrate adsorption capacity is not very sensitive to variations in ow velocity. This may signify that the rate of chemical reaction or selectivity
and the sorption process are high and the assumption of local equilibrium is correct.

Table 5
Measured characteristics of column experiments and model parameter predictions.
Continuous no.

Run 1

Run 2

Run 3

Run 4

Run 5

Run 6

Run 7

Run 8

Flow rate (l/h)

NO3 (mg/l)
SO4 (mg/l)
Cl (mg/l)
Breakthrough time (h)
Breakthrough capacity (mg nitrate/ml resin)
Total capacity (mg nitrate/ml resin)
Breakthrough bed volume (l)
qT (meq nitrate/g resin)
K
D (m2/s) 105

2.114
119.4
0
0
36.2
45.5
55.1
76.7
2.61
5.0
1.603

1.401
119.1
0
0
54.6
45.8
55.7
76.6
2.61
5.4
1.071

0.693
120.4
0
0
111.6
45.9
56.0
77.4
2.63
6.0
0.5453

2.101
89.5
0
0
53.1
48.3
56.2
111.6
2.71
6.2
1.585

2.091
60.4
0
0
82.9
50.0
56.8
173.5
2.75
4.9
1.597

2.108
119.1
237
0
21.6
24.9
30.8
45.6
2.30
5.5
0.8878

2.095
120.2
0
102
30.5
36.3
41.8
63.8
2.68
6.1
0.965

2.164
63.7
236
100.5
27.2
17.0
21.4
58.9
2.40
5.8
0.6688

28

A.A. Hekmatzadeh et al. / Desalination 284 (2012) 2231

Here, Dm is the molecular diffusion coefcient, u is the interstitial

ow velocity, and is the dispersivity coefcient. The molecular diffusion can be ignored in comparison with u in these ow velocities
[46]. Therefore, the value of was calculated to be 1.47 cm by liner
plot of D versus u, which is not shown here.

1.2
1

C/C0

0.8

4.2.3. Effect of initial nitrate concentration

The effect of inuent nitrate concentration on adsorption capacity was
investigated using Column tests Run 1, Run 4, and Run 5 (Fig. 4(B)).
The breakthrough time and the treated volume of water decreased
with the rise in inuent concentration (Table 5). This indicates that
the resin bed was saturated faster by nitrate at higher concentrations
due to higher nitrate loading rates. As reported in Table 5, the total
amount of adsorbed nitrate obtained from these experiments was
in the range of 55.1 to 56.8 mg nitrate/ml resin as initial nitrate concentration decreased from 119.4 to 60.4 mg/l. It can be deduced that initial
nitrate concentration has a negligible effect on the total adsorption
capacity.
Table 5 shows that the estimated values of D for different inuent
concentrations are between 1.585 10 5 to 1.603 10 5 m 2/s, which
are nearly the same. The average value of this coefcient for different
nitrate concentrations is equal to 1.595 10 5 m 2/s. Therefore, the
dispersion coefcient is not inuenced by initial nitrate concentration. The calculated dispersion coefcient in this research is comparable to those reported by other researcher [42].

0.6
2.11 l/h Mod.
2.11 l/h Exp. (run1)
1.40 l/h Mod.
1.40 l/h Exp. (run2)
0.69 l/h Mod.
0.69 l/h Exp. (run3)

0.4
0.2
0
0

40

80

120

160

200

240

time (h)

1.2
1

C/C0

0.8
0.6

4.2.4. Effect of competitive ions (chloride and sulfate)

Fig. 4(C) shows the effect of competitive ions on nitrate adsorption (Runs 1, 6, and 7). The presence of both sulfate and chloride
inuenced the nitrate breakthrough curve and reduced the break
time and adsorption capacity (Table 5).The total adsorption capacity
of this resin was found to be between 55.1 and 56.8 mg nitrate/ml
resin when only nitrate is present in the solution (Runs 1 to 5). In
the cases where there was sulfate (Run 6) or chloride (Run 7) along
with nitrate in the solution, the adsorption capacity was reduced to
30.8 and 41.8 mg nitrate/ml resin, respectively. Thus, it can be concluded that a portion of resin capacity is occupied by sulfate and chloride ions. In addition, no nitrate peak was observed during these tests,
lending credence to the superior selectivity of nitrate in comparison
with sulfate.
According to Table 5, the dispersion coefcient of nitrate was
inuenced by the presence of chloride and sulfate in the aqueous solution. In these cases, smaller values were obtained for this coefcient. Dispersion coefcient was computed to be 0.965 10 5 m 2/s
and 0.8878 10 5 m 2/s for Run 6 and Run 7 which contained chloride and sulfate in nitrate solutions, respectively.

119.4 mg/l Mod.

119.4 mg/l Exp. (run1)
89.5 mg/l Mod.
89.5 mg/l Exp. (run4)
60.4 mg/l Mod.
60.4 mg/l Exp. (run5)

0.4
0.2
0
0

40

80

120

160

180

time (h)

1.2
1

C/C0

0.8
0.6
NO 3 - Mod.
NO 3 - Exp. (run1)
NO 3 -+Cl - Mod.
NO 3 -+Cl - Exp. (run7)
NO 3 -+SO 4- Mod.
NO 3 -+SO 4- Exp. (run6)

0.4
0.2

1.2

0
0

20

40

60

80

90
0.8

Fig. 4. Measured and modeled nitrate breakthrough curves for (A) different ow rate
(B) different inuent concentration, and (C) presence of sulfate and chloride.

C/C0

time (h)

0.6

0.4

The dispersion coefcient was estimated for each column experiment, the results appearing in Table 5. An increase in the value of D
(dispersion coefcient) was observed alongside a rise in the ow
velocity. It is known that the dispersion coefcient is described as
follows [46]:
D Dm u:

19

60.4 mg/l Mod.

60.4 mg/l Exp. (run5)
Groundwater Mod.
Groundwater Exp. (run8)

0.2

0
0

40

80

120

160

185

time (h)
Fig. 5. Measured and modeled nitrate breakthrough curves for Shiraz groundwater
(Run 8) and synthetic solution which contained only nitrate ions (Run 5).

A.A. Hekmatzadeh et al. / Desalination 284 (2012) 2231

4.2.5. Nitrate removal from Shiraz groundwater

The results of nitrate removal from Shiraz groundwater (Run 8)
and the synthetic solution which contained only nitrate ions (Run
5) are compared in Fig. 5. Nitrate inuent concentration and the
ow rate in both experiments were the same. The column experiment
using Shiraz groundwater was saturated much faster than the column
test with the synthetic solution. The breakthrough time of Shiraz
groundwater column tests was 27.2 h, while this time was 82.9 h for
the column test with the synthetic solution (Run 5). Also, a smaller
slope (smaller dispersion coefcient) was observed for the breakthrough curve of the column test using Shiraz groundwater. In the
case of the groundwater, the dispersion coefcient was computed to
be 0.6688 10 5 m 2/s, in comparison with 1.597 10 5 m 2/s for the
synthetic solution. The presence of competitive ions in Shiraz groundwater decreased the nitrate adsorption capacity from 56.8 to 21.4 mg
nitrate/ml resin (Table 5).
Fig. 6 shows the breakthrough curves of nitrate, sulfate, chloride
and bicarbonate, in a second column test using Shiraz groundwater
with a ow rate of 0.69 l/h. At rst, both nitrate and sulfate were
adsorbed onto the resin particles, and chloride was released due to
the higher selectivity of the former anions in comparison with chloride. As more water passed through the resin bed, sulfate ions suddenly appeared in the efuent at higher concentrations than that of
the inuent water. The maximum efuent concentration of sulfate
was 1.12 times that of the inuent concentration. In fact, the adsorbed
sulfate ions were released, with the nitrate ions being replaced. This
phenomenon shows that nitrate was preferentially bound to this
resin with a sufciently high selectivity compared to sulfate. Also, a
small amount of bicarbonate was adsorbed at the beginning of the
run because of the high number of exchangeable sites at that time.
However, after a few minutes, the bicarbonate concentration at the
column outlet was equal to the inlet concentration. This indicates
that resin capacity is not reduced as a result of the presence of
bicarbonate.

4.2.6. Sensitivity analysis

Sensitivity analysis was performed on the results of the column
test (Run 1) with a nitrate inuent concentration of 120 mg/l, a bed
depth of 20.5 cm, and a ow discharge of 2.11 l/h. The effect of axial
dispersion coefcient, D, on the shape of the breakthrough curve is
presented in Fig. 7(A). The value of D varied between 8 times lower
and 8 times higher than the optimized value (1.603 10 5 m 2/s). Although the reduction in D caused a steeper slope in the breakthrough
curve, the break time was only slightly changed. On the other hand,
the increase in D reduced the break point and the slope of

1.2
D=1.603x10-5 m2/s
D=12.817x10-5 m2/s
D=6.408x10-5 m2/s
D=3.205x10-5 m2/s
D=0.801x10-5 m2/s
D=0.200x10-5 m2/s

C/C0

0.8
0.6
0.4
0.2
0
0

20

40

60

80

60

80

60

80

time (h)

1.2
1
k=1.5
k=2
k=3
k=5
k=10

C/C0

0.8
0.6
0.4
0.2
0
0

20

40

time (h)

1.2
1

qT=2.2 meq/l
qT=2.4 meq/l
qT=2.6 meq/l
qT=2.8 meq/l
qT=3.0 meq/l

C/C0

0.8
0.6
0.4
0.2

400

concentration (mg/l)

29

300

20

40

time (h)

Sulfate
Chloride
Bicarbonate
Nitrate

200

100

0
0

40

80

120

160

time (h)
Fig. 6. Column breakthrough proles for nitrate, sulfate, and bicarbonate using Shiraz
groundwater (Run 9).

Fig. 7. Effect of variation in model parameters values on breakthrough prole based on

column test Run 1: (A) dispersion coefcient, D. (B) apparent equilibrium constant, k.
(C) Maximum adsorption capacity, qT.

breakthrough curve. Therefore, a rise in D has a greater impact on

the sensitivity of the model than does a decrease in the value of this
variable. It is worth mentioning that a variation in D between two
times higher and 2 times lower than the base value has a negligible
effect on the breakthrough curve.
The effects of change in the isotherm parameters, k and qT, are
shown in Fig. 7(B) and (C), respectively. It was found that values of
k exceeding three had an insignicant effect on the shape of the
breakthrough curve, while values below three inuenced the slope
of the breakthrough curve noticeably. Any change applied to qT led

30

A.A. Hekmatzadeh et al. / Desalination 284 (2012) 2231

to a shift in the obtained values for breakthrough time, whereas its

impact on the slope of the breakthrough curve was not signicant.
Among these three parameters, the selected mathematical model
had the lowest sensitivity to variations in the values of k, i.e., the
value of chemical reaction.
5. Conclusions
Nitrate removal from different aqueous solutions in both batch
and continuous systems was studied using a nitrate selective ion exchange resin called IND NSSR. The results showed that this resin is an
effective adsorbent for nitrate removal from both synthetic solutions
and Shiraz groundwater, specically in the presence of sulfate. The
average maximum adsorption capacity obtained during the tests
was 2.55 meq/g. The variations in ow rate and initial nitrate concentration had a negligible effect on the total nitrate adsorption capacity.
However, resin capacity was reduced in the presence of chloride and
sulfate. Moreover, the computed dispersion coefcient was not inuenced by the initial nitrate concentration. Nonetheless, comparatively
smaller values were obtained for this coefcient in the presence of
competitive ions.
The equilibrium distribution of nitrate ions between resin and liquid phases was modeled by both an adsorption isotherm (the Langmuir isotherm) and the mass action law isotherm. It was found that
equilibrium data can be described well with both models. However,
Langmuir parameters especially b constant depend on the solution
condition, such as nitrate, sulfate and chloride concentrations in solutions. On the other hand, it was found that a simple general model
based on the mass action law model can be used to simulate ion exchange equilibrium under diverse operating conditions.
The advection dispersion equation including the adsorption term
(Eq. (8)) was considered as a mathematical model to simulate the ion
exchange process in columns packed with ion exchange resins. The
mass action law isotherm was used to simulate the nitrate adsorption
term in this equation. The nite difference method, reduced to the
CrankNicholson scheme, was used to numerically solve the above
equation. The isotherm parameters and dispersion coefcient were
computed by minimizing an error function (Eq. (18)). The model predictions of the breakthrough curves were in a very good agreement
with the experimental data at different ow rates, inuent nitrate concentrations, and the presence of sulfate and chloride ions in the inuent.
The mass action isotherm parameters obtained from column experiments were conrmed with those obtained from batch experiments.
Consequently, the column behavior can be predicted from the batch
equilibrium data by using the mass action isotherm.
Sensitivity analysis was performed on the mathematical model
parameters. It was obtained that the variation of D, i.e. dispersion coefcient, between two times higher and lower than the base value
was negligible. Among the parameters optimized in the modeling,
the selected mathematical model has the lowest sensitivity to the
values of k, i.e., the value of apparent chemical reaction.
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