Expert Systems with Applications 39 (2012) 6052–6060

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Expert Systems with Applications

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Neural network modeling of sorption of pharmaceuticals in engineered

floodplain filtration system
Shishir Kumar Behera a, Eldon R. Rene b, Hung-Suck Park a,⇑
a
Center for Clean Technology and Resource Recycling, University of Ulsan, Ulsan 680 749, South Korea
b
Chemical Engineering Laboratory, Faculty of Sciences, University of La Coruña, Rua da Fraga, 10, E-15008 La Coruña, Spain

a r t i c l e i n f o a b s t r a c t

Keywords: Engineered floodplain filtration (EFF) system is a versatile low-cost water treatment process wherein
Sorption water contaminants are removed, mainly by adsorption and–or degraded by microorganisms, as the infil-
Triclosan trating water moves from the wastewater treatment plants to any natural water stream. An artificial neu-
Ibuprofen ral network (ANN) based on multilayer perceptrons with back propagation algorithm was used to
Activated carbon
approximate and interpret the complex input/output relationship, essentially to understand the break-
EFF system
Artificial neural networks
through times in EFF system. Triclosan and ibuprofen were selected as the two model pollutants in this
study owing to their environmental significance. The input parameters to the ANN model were inlet con-
centration (ppm) and flow rate (m/d), and the output parameters were six concentration-time pairs (C, t).
These C, t pairs were the times in the breakthrough profile, when 1%, 5%, 25%, 50%, 75% and 95% of the
pollutant was present at the outlet of the system. The 10 set of experimental data points, 5 for each pol-
lutant, statistically investigated in the continuous column studies using the full-factorial design, were
divided into training (8  8) and testing (2  8) set. The most dependable condition for the network
was selected by a trial and error approach and by estimating the determination coefficient (R2) value
(>0.99) achieved during prediction of the testing set. The proposed ANN model for EFF system operation
could be used as a potential alternative for knowledge-based models through proper training and testing
of variables.
Ó 2011 Elsevier Ltd. All rights reserved.

1. Introduction
In the last several decades, the production of pharmaceuticals
and personal care products (PPCPs) has increased rapidly due to
the steadfast consumption by both humans and animals. A signif-
icant amount of these PPCPs discharged into the aquatic environ-
ment have been reportedly detected in wastewater and surface
water at ppb to ppm levels (Kim, Cho, Kim, Vanderford, & Snyder,
2007; Pedrouzo, Reverté, Borrull, Pocurull, & Marcé, 2007; Vander-
ford, Pearson, Rexing, & Snyder, 2003). Furthermore, PPCPs have
shown to pose severe risks and side-effects to the aquatic ecosys-
tem owing to their inherent biological effects (Clara et al., 2005;
Kasprzyk-Hordern, Dinsdale, & Guwy, 2008; Nakada et al., 2007;
Sanderson et al., 2004). Collectively, pollution of the aquatic eco-
system by PPCPs is becoming an emerging unmanageable environ-
mental problem worldwide.
The conventional treatment practices in wastewater treatment
plants by and large do not effectively eliminate and/or degrade
all the PPCPs. Ozonolysis and advanced oxidation techniques have
shown to remove higher amount of PPCPs, but these tertiary treat-
⇑ Corresponding author. Tel.: +82 52 259 1050; fax: +82 52 221 0152.
E-mail address: parkhs@ulsan.ac.kr (H.-S. Park).
ment systems can easily increase the costs several-fold (Ternes
et al., 2003). The partially eliminated as well as the residual quan-
tities of PPCPs emerging from secondary treatment systems usually
tend to accumulate in the aquatic environment (Hernando, Mez-
cua, Fernández-Alba, & Barceló, 2006). In this context, for waters
already treated to primary and secondary levels, land treatment
systems could be considered as a promising low-cost, eco-friendly
alternative. One such land treatment system is the floodplain filtra-
tion (FPF) system (Fig. 1). FPF is a low-cost water treatment tech-
nology that has shown to be efficient in eliminating organics and
nutrients from secondarily treated wastewater (Kunjikutty,
2006). Simultaneously, natural attenuation of emerging pollutants
including PPCPs discharged in the secondarily treated wastewater
effluents cannot also be ruled out during their infiltration and sub-
sequent emergence in the rivers. The degree of PPCP elimination in
FPF depends strongly on the proportion of clay, which has the abil-
ity to sorb the PPCPs in their matrix, present in the FPF and this va-
lue is typically 62% (Jeong et al., 2003; Kunjikutty, Prasher, Patel,
Barrington, & Kim, 2007). The removal of PPCPs from secondarily
treated wastewater can be enhanced if the floodplains available
nearby wastewater treatment facilities are supplemented with
adequate proportions of a suitable sorbent. This retro-fitted engi-
neered system, hereafter referred as engineered floodplain filtra-

0957-4174/$ - see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.eswa.2011.12.009
 S.K. Behera et al. / Expert Systems with Applications 39 (2012) 6052–6060
Fig. 1. Schematic of floodplain filtration system (MWWTF: municipal wastewater
treatment facility).
tion (EFF), can also easily exploit the prevailing natural conditions
leading to better performance at a low-cost. EFF is thus a modified
slow sand filter with a layer of sorbent sandwiched between two
sand layers. The EFF system can also be modified to act as a bio-
barrier in order to remove or degrade the PPCPs by combining
the adsorption and biodegradation steps within the same system.
Modeling of PPCP sorption behavior in environmental matrices
is especially very complex. To avoid excessive testing times and
experimental work expenses, numerous predictive mathematical
models describing the adsorption behavior have been proposed.
Mathematical models enable the prediction of breakthrough curve
from the basic kinetic and equilibrium data and these models vary
from linear and analytical ones to numerically based models that
can only be solved with the help of supercomputers. Recently,
the application of artificial neural networks (ANNs) in hydrology
and water-resource related problems have been gaining tremen-
dous momentum, as it has provided promising results for many
non-linear and complex systems. ANNs are non-linear mathemat-
ical models capable of learning the arbitrary and complex physico-
chemical process of a system from observed input variables and
desired outputs of the system. The primary advantage of ANN over
phenomenological/conceptual models is that, it does not require
information about the complex nature of the underlying process
to be explicitly described in mathematical form (Sahoo et al.,
2005).
In this study, column experiments were carried out in lab-scale
EFF systems, at different inlet concentration and flow rates of two
PPCP model compounds; namely triclosan and ibuprofen (Table 1).
Based on the collected experimental data, an ANN model was
developed. The input parameters for the ANN model were inlet
concentration and flow rate, while the output parameter was the
times corresponding to the six concentration levels (T1, T5, T25,
T50, T75 and T95) obtained at C/Co (exit concentration of the pollu-
Table 1
Structures and properties of triclosan and ibuprofen.a
Name Molecular structure MW
Triclosan 289.5
Ibuprofen 206.3
a
Adapted from Trenholm, Vanderford, Holady, Rexing, and Snyder (2006).
6053
tant/inlet concentration of the pollutant) values of 1%, 5%, 25%,
50%, 75% and 95%, respectively.
2. Materials and methods
2.1. Floodplain sediment and activated carbon
The sediment used in this experiment was collected from the
top 100 cm layer of an active floodplain, located upstream of Tae-
hwa River in Ulsan, South Korea. Particle separate characteristics of
sand, silt, and clay in the sediment were 91%, 8.9%, and 0.1%,
respectively, while the physicochemical properties of the sediment
such as pH, organic matter content, and cation exchange capacity
were 6.95, 0.8%, and 1.1 cmol/kg, respectively. Activated carbon
in granular form (particle size – 1.5 mm) was washed and dried
at 105 °C overnight and stored in a desiccator until use.
2.2. Chemical preparation
Triclosan (P97%) was obtained from Fluka (Steinheim, Ger-
many) and ibuprofen (99%) was obtained from Sigma–Aldrich
Co., St. Louis, MO, USA. The physico-chemical properties of these
two compounds are given in Table 1. The stock solutions of 1 g/L
were prepared by dissolving the compounds in HPLC grade meth-
anol (SK Chemical, Ulsan, South Korea) and stored at 4 °C. The stock
solution was spiked with ultra-pure water to achieve the concen-
tration levels of interest. All chemicals were used without further
purification.
2.3. Column experiment
Columns made up of borosilicate glass having the following
dimensions were used: 30 cm length  6.5 cm diameter (ID)
(Fig. 2). The conditions of the column experiments are based on
the experimental design specified by 2k-full factorial design (Ta-
ble 2) (Montgomery, 1991). To separately estimate the sorption
capacity of the EFF system, six columns each with the 6th column
acting as a replicate of the center-point condition (based on the
full-factorial design) was used under abiotic conditions. To ensure
abiotic condition, the floodplain sediment was sterilized at 100 °C
for 1 h and 100 ppm of sodium azide (NaN3) was added to the con-
taminated solution prepared by spiking desired compounds in
deionized water. The pH of that solution was maintained at 7.
The columns were filled with floodplain sediment, sandwiching a
1 cm layer (16 g) of activated carbon (as adsorbent), placed 14 cm
from the top of the column. Some glass wool and acid washed sand
were put at the bottom of the columns to hold the floodplain sedi-
ment and activated carbon in place and to prevent leaching of sed-
iment particles. All the columns were pre-wetted with double
Log Kow pKa Water solubility (ppm) Application
4.76 8.14 10 Anti-septic
3.97 4.91 21 Anti-inflammatory
6054 S.K. Behera et al. / Expert Systems with Applications 39 (2012) 6052–6060

Fig. 2. Experimental set-up of the EFF column. (Adapted from Behera (2010)).

tions. The neuron accepts input from single or multiple sources

Table 2
Experimental condition used in this study (based on the full- and produces output by a simple calculating process guarded by
factorial design). a non-linear transfer function. A simple three-layered network
with an input layer, hidden layer and output layer is shown in
Run no. Concentration (ppm) Flow rate (m/d)
Fig. 3. The input layer consists of a set of neurons NI, each repre-
1 0.1 1
senting an input parameter and propagates the raw information
2 1 1
3 0.1 5
to the neuron in the hidden layer (NH), which in turn transmits
4 1 5 them, to the neurons in the output layer (NO). Each layer consists
5 0.55 3 of several neurons and the layers are connected by the connection
6 0.55 3 weights (W 1ij and W 2ij ). The most commonly used transfer function
is the sigmoid function as described by

distilled water from the bottom to prevent the formation of air bub-
bles and to reduce the risk of channeling and then left to equilibrate
for 2 d. Experiments were performed at ambient room tempera-
tures (20 °C) and the entire unit used for column experiments,
including the tanks, was protected against exposure to light.
2.4. Chemical analysis
An HPLC system (UltimateÒ 3000) (Dionex, Sunnyville, CA, USA)
equipped with AcclaimÒ C-18 (4.6 mm  250 mm, 5 lm) and Dis-
covery RP-Amide C-16 (4.6 mm  150 mm, 5 lm) columns were
used to measure the triclosan and ibuprofen concentrations,
respectively. The UV–vis detection wavelengths were 220 and
230 nm, respectively for triclosan and ibuprofen. The mobile phase
used for elution was deionized water (30%) and acetonitrile (70%)
for triclosan and 25 mM KH2PO4 at pH 3.0 (40%) and acetonitrile
(60%) for ibuprofen, delivered at 1 mL/min through the columns.
A sample injection volume of 100 lL was used. The column tem-
peratures were maintained at 25 °C and 30 °C for triclosan and ibu-
profen, respectively.
2.5. ANN modeling
ANNs consists of a system of simple interconnected processing
element called neurons. This gives the ability to model any non-
linear process through a set of unidirectional weighted connec-
1
f ðxÞ ¼ ð1Þ
1 þ ex
This produces output in the range of 0–1 and introduces non-line-
arity into the network, which gives the power to capture non-linear
relationships. The back propagation network is the most prevalent
supervised ANN learning model (Rumelhart, Hinton, & Williams,
1986). It uses the gradient descent algorithm to correct the weights
between interconnected neurons (Maier & Dandy, 2001). During the
learning process of the network, the algorithm computes the error
between the predicted and specified target values at the output
layer. The error function at the output layer can be defined by
1X
E¼ ðOd  Op Þ2 ð2Þ
2
where E is the global error function, Od and Op are the desired out-
put and predicted output by the network, respectively.
2.5.1. Data pre-processing and division
The data points from all the EFF systems, operated at initial con-
centrations of 0.1, 0.55 and 1 ppm were normalized and scaled (Eq.
(3)) to the range of 0–1, so as to suit the transfer function in the
hidden (sigmoid) and output layer (linear). More comprehensible
and relevant information on the different types of transfer func-
tion, algorithms and internal parameter used for developing ANN
models are given elsewhere (Haykin, 1994; Hoskins & Himmelblau,
1988)
 S.K. Behera et al. / Expert Systems with Applications 39 (2012) 6052–6060
Fig. 3. Topology of an ANN model.
b ¼ X  X min
X ð3Þ
X max  X min
where X b is the normalized value, Xmin and Xmax are the minimum
and maximum values of X, respectively. This processed data was la-
ter divided into two sets; training and testing. 80% (8) of the data
points were used for training the network, while 20% (2) were used
for testing the developed network.
2.5.2. Model-inputs and outputs
The input vectors to the network were the easily monitored
parameters namely; input concentration (X1) and flow rate (X2).
The output of the ANN model was the times (day) corresponding
to the six concentration levels. The six concentration levels consid-
ered are those corresponding to the non-dimensional parameter
(C/Co) values of 1%, 5%, 25%, 50%, 75% and 95%. These outputs are
denoted as T1, T5, T25, T50, T75 and T95, respectively. Concentra-
tions below C = 0.01Co and the concentrations of C = Co are practi-
cally difficult to detect. The six-point method proposed here is
assumed to be sufficient to sketch an approximate, yet a close en-
ough breakthrough curve. Besides, breakpoints at 1% and 5% are
commonly used in water and wastewater treatment applications.
2.5.3. Internal network parameters
A good network architecture requires proper selection of sensi-
tive parameters like: number of hidden layers, the number of neu-
rons in the hidden layer (NH), the activation function f(x), the
learning rate of the network (g), epoch size (e), momentum term
(a) and training cycles (TC). The network architecture has to be
optimized to reduce computer processing, achieve good predict-
ability and avoid over fitting. The learning rate (g) and momentum
(a) can play an important role in the convergence of the network.
The g value of a network affects the size of steps taken in weight
space. If g is too small, the algorithm would take more time to con-
verge. The momentum term (a) accelerates the convergence of the
error during the learning process by adding a fraction to the pre-
cious weight update. The values of g and a varies between 0 and
1 and is normally estimated by trial and error. Initially, network
training based on a trial and error approach was used to identify
the best suitable range of these parameters. A detailed study on
the effect of internal network parameter on the performance of
back propagation neural network (BPNN) and the procedure in-
volved in selecting the best network topology has been described
elsewhere (Maier & Dandy, 1998).
6055
2.5.4. Selecting the best model architecture
The performance of the training and test data set were evalu-
ated in terms of the correlation coefficient values (R2), which sub-
stantially determines the closeness of prediction between the
desired and predicted output from the network. This is given by:
P P
P X Y
2 XY  N
R ¼ sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
 P  P  ð4Þ
P 2 ð X Þ2 P 2 ð Y Þ2
X  N Y  N
where X is the experimental value, Y is the model predicted value,
and N is the total number of observations. Furthermore, for the test-
ing data set, the total mean squared error (RMSE) was computed
according to the formulae given elsewhere (Elias, Berastegi, Arias,
& Barona, 2006).
2.5.5. Software used
ANN based predictive modeling was carried out using the
shareware version of the neural network and multivariable statis-
tical modeling software NNMODEL (version 1.4, neural fusion, NY).
The same software was also used to carry out the sensitivity
analysis.
3. Results and discussion
3.1. Column studies
Continuous tests were carried out under abiotic conditions at
three different initial concentrations and flow-rates (Table 2). The
inlet and outlet concentrations of both triclosan and ibuprofen
were measured every day, and the results were interpreted in
terms of the trend of C/Co, to achieve breakthrough. The time
course C/Co profile of triclosan and ibuprofen, at all the tested con-
ditions is illustrated in Fig. 4(a) and (b), respectively. It can be ob-
served clearly that, the onset of breakthrough condition differed
depending on the initial setting of flow rate (Q) and initial concen-
tration (Co), for both the compounds. It is also evident that the
breakthrough time in both cases decreased with an increase of Co
and Q. At lower Co and Q, breakthrough occurred slower and vice
versa. These results demonstrate that the change of concentration
and flow rate affects the saturation rate of sorbent and break-
through time, which are the typical characteristics of any adsorp-
tion process. With the increase of Co and Q, the loading rate of
the selected pharmaceuticals increased, and consequently the
6056 S.K. Behera et al. / Expert Systems with Applications 39 (2012) 6052–6060

both the saturation rate and breakthrough time (Knaebel, Ruthven,

Humphrey, & Carr, 1999). As Co increased, the loading rate of triclo-
san and ibuprofen increased, so does the driving force or mass
transfer, which results in a decrease in the adsorption zone length.
This result is in agreement with the works reported previously on
various fixed-bed adsorption systems, where a wide variety of
environmental chemicals were tested (Ahmad & Hameed, 2010;
Lua & Jia, 2009; Singh, Srivastava, & Mall, 2009).

3.2. ANN modeling

3.2.1. Data analysis and best network topology

The experimental data were divided into training (NTr-80%) and
test data (NTe-20%), leaving behind the steady-state data of C/Co,
after noticing breakthrough. The output variables, i.e., T1–T95,
was chosen based on a previous adsorption/predictive modeling
study using neural networks reported in the literature (Basheer &
Najjar, 1996). The basic statistics of the variables for the training
matrix are shown in Table 3. This table forms the database of the
training sets that embody a certain pattern and that the present
neural network has to be trained on to capture that pattern.
The number of neurons in the input layer (NI = 2) and output
layer (N0 = 6) were chosen based on the number of input and out-
put variables to the network. However, in order to get the best/
optimum network parameters, in most instances, literature sug-
gests the use of a trial and error approach where the performance
Fig. 4. Breakthrough curves; triclosan (a) and ibuprofen (b).
goal is set by the user. The best network architecture (Table 4) was
chosen based on the maximum predictability of the network for
fixed-bed EFF column became saturated with the pharmaceutical the test data by analyzing the correlation coefficient values (R2).
concentration as the effluent approached the Co. For both triclosan The model was trained using different combinations of these net-
and ibuprofen, high flow rate and high concentration (5 m/d and work parameters, viz., learning rate, momentum term and number
1 ppm) favored this phenomenon. of neurons in the hidden layer, so as to achieve maximum correla-
The breakthrough curves shifted to the origin at same Co (0.1 tion coefficient values (target value = 1, i.e., 100% correlation be-
and 1 ppm) with increasing Q, and earlier breakthrough time was tween measured and predicted variables). This was achieved by a
observed for the higher flow rate. In the interval of 70 d, the value vigorous trial and error approach by keeping some training param-
of C/Co for triclosan reached 0.51 and 0.85 at Co of 0.1 ppm and flow eters constant and by slowly moving the other parameters over a
rates 1 m/d and 5 m/d, respectively (Fig. 4a). Similarly, in the same wide range of values. Increasing the number of neurons from 2
interval of time and at the same Co, the value of C/Co for ibuprofen to 4 in the hidden layer (NH), increased the R2 value, while values
reached 0.43 and 0.99 when flow rates were 1 m/d and 5 m/d, larger than 4 did not show any improvement in the predictive abil-
respectively (Fig. 4b). Similar phenomena were also observed at ity of the developed model. Due to the high R2 observed under this
higher Co (1 ppm) and at different flow rates (1 m/d and 5 m/d). particular setting of network parameters (R2 > 0.95), this value of
For example, the values of C/Co reached at Co of 1 ppm and flow NH was kept constant at 4. Thus, by keeping the number of neurons
rates 1 m/d and 5 m/d were 0.33, and 0.79 and 0.16, and 0.98, in the hidden layer constant, the values of both learning rate and
respectively for triclosan and ibuprofen. momentum term was slowly changed from 0.1 to 0.95, through a
The variation in the adsorption capacity at various Co and Q can series of trial and errors, and by observing the changes of R2 in
be explained on the basis of mass transfer fundamentals. The the training data set. It was observed that, lower values of these
breakthrough time at Q = 1 m/d is longer than that at Q = 5 m/d be- parameters decreased the R2, from 0.98 to 0.87, while higher values
cause it takes a longer time to reach its effective bed load when the showed maximum predictive potential for the developed model.
other operating conditions are held at their respective constant Thus these values were then set at 0.9 and 0.8, respectively. The
values. Therefore, as Q increases, the breakthrough curve becomes R2 values achieved during training and testing are shown in
steeper, because of the shorter time required to attain its effective Table 5.
bed load. In other words, increasing Q decreases the effective bed
load or the effective adsorption capacity of the EFF column. This
Table 3
phenomenon is usually expected because the effective bed load re- Basic statistics of training data.
duces with increasing Q and hence requires a shorter time for
Variable N Mean Std. dev. Minimum Maximum Sum sq.
breakthrough of bed (Ruthven, 1984).
On the other hand, a close examination of Figs. 4a and b reveals C 8 0.55 0.48107 0.1 1 4.4
Q 8 3 2.13809 1 5 24
that at the same Q, the value of breakthrough time decreased with
T1 8 29.875 18.31812 10 55 239
an increase in Co values. The larger the Co, the steeper the slope of T5 8 34.375 19.84179 11 57 275
the breakthrough curve and smaller the breakthrough time. At low T25 8 45 15.63878 26 66 360
Co, breakthrough curves were dispersed and breakthrough oc- T50 8 51.125 15.06593 32 71 409
curred slower. As the value of Co increased, sharper breakthrough T75 8 57.375 14.39184 40 76 459
T95 8 61.875 15.30114 43 79 495
curves were obtained. This can be explained by the fact that more
adsorption sites were covered with increase in Co. These results Note: C: influent concentration (ppm), Q: flow rate (m/d), T1–T95: times corre-
demonstrated that the change in concentration gradient affected sponding to C/C0 (1–95%), respectively.
 S.K. Behera et al. / Expert Systems with Applications 39 (2012) 6052–6060
Table 4
Best values of network parameters used for training the network.
Training parameters Value
Training count (iterations) 20,000
Number of neurons in input layer 2 which was found to describe the system well. It was observed that
Number of neurons in hidden layer 4 with increase of bed height and decrease of influent dye concentra-
Number of neurons in output layer 6 tion, the breakthrough time was delayed. In that study, the authors
Learning rate 0.9
Momentum term 0.8
Error tolerance 0.00001
Training algorithm Gradient descent algorithm
Number of training data set 8 2010). Similarly, Oguz and Ersoy (2010) conducted continuous
Number of test data set 2
3.2.2. Predictive capability of the developed model
From Figs. 5 and 6, it can be seen that some data points show
deviancy between the measured and predicted C/Co profiles. This
is probably due to the fact that different conditions exhibited dif-
ferent onset times for reaching breakthrough. The delay in achiev-
ing breakthrough, i.e., at low flow rates and concentrations would
have caused an impact in the neural networks learning/generaliza-
tion pattern while predicting the performance parameter. The cor-
responding connection weights and bias terms for the developed
network are presented in Table 6. As observed in Fig. 5, the neural
network predicted breakthrough curves are very close to the corre-
sponding exact ones. Although the developed neural network is
specific, more general networks using wider ranges and variety
of input parameters can be developed using the procedure adopted
in this work.
The application of the BPNN to predict the filtrate water quality
parameters; temperature, turbidity, heterotrophic bacteria, and
coliform removal have been studied using riverbank filtration facil-
ities, wherein optimization of the ANN models’ structure was per-
formed on a trial and error basis. It was observed that the BPNN
model prediction result produced excellent agreement with the
measured data at a very high correlation coefficient (>0.99) in all
the cases (Sahoo et al., 2005). Experimental breakthrough curves
of pesticide in surface water were assessed in fixed-beds and mod-
eled using neural network approaches. Fifteen potentially influen-
tial parameters were identified in that study for the dynamic
adsorption of pesticides from surface water. For all breakthrough
curves, computations were performed for specific zones of the
breakthrough curves; breakthrough zone (C/C0 < 0.10), saturation
zone (C/C0 > 0.9), and the global breakthrough curve (0 < C/
C0 < 1). Neural networks provide quite satisfactory predictions for
pesticide dynamic adsorption onto activated carbon with R2 larger
than 0.981 (Faur, Cougnaud, Dreyfus, & Le Cloirec, 2008). ANN-
based models were also developed to predict the performance of
moving bed biofilm reactor for the treatment of a toxic and highly
refractory aromatic amine compound, aniline. For experiments
conducted over a period of 3 months, the reactor performance effi-
ciency was predicted at different retention times of 8, 24, 48 and
72 h, respectively with influent COD ranging from 100 to
4000 ppm. The proposed ANN model demonstrated the ability of
BPNN to predict the performance of moving bed biofilm reactor
with sufficient accuracy (Delnavaz, Ayati, & Ganjidoust, 2010).
For determining adsorption capability of two textile dyes in a
Table 5
Coefficient of regression (R2) values obtained during training and testing.
Triclosan
Run-1 Run-2 Run-3
Training 0.999 0.989 0.994
Testing 0.967
6057
fixed-bed system, packed with a tree bark as adsorbent, ANN mod-
el has been developed with bed depth, influent dye concentration
and volume of wastewater as the input parameters. The break-
through curves of adsorption were also exhibited by this model,
showed that neural networks can be used as an effective technique
to model, estimate state variables and predict the absorption
behavior with satisfactory results (Balci, Keskinkan, & Avci,
flow experiments in fixed-bed adsorption columns to remove
Cu2+ ions from aqueous solution using sunflower shells as adsor-
bent. They investigated the effects of flow rate, inlet concentration,
pH, bed depth and particle size on the breakthrough characteristics
of the adsorption system and subsequently developed an ANN
model to predict the Cu2+ concentration removed from aqueous
solution as a function of empirical parameters. The relationship be-
tween the predicted and observed data of the model yielded in a
correlation coefficient of 0.986. On the other hand, ANN models
have also been proposed to predict the performance of a continu-
ously operating immobilized-cell biofilter treating NH3 vapors.
The input parameters to the ANN model were inlet concentration,
loading rate, flow rate and pressure drop, and the output parame-
ters were removal efficiency and elimination capacity. The results
showed that a multilayer network (4–4–2) with a BPNN was able
to predict biofilter performance effectively with R2 values more
than 0.98 (Rene, Kim, & Park, 2009).
3.2.3. Sensitivity analysis of the developed model
Sensitivity analysis is a useful technique to assess the relative
contribution of the input variables to the performance of a neural
network by testing the neural network when each input variable
is unavailable. This is performed by varying the value of one
parameter over a certain range and by observing the associated ef-
fect on the desired outcome. For the problem studied in this work,
the two input parameters were checked for their sensitivity to the
breakthrough curve. The four-hidden nodes network was used for
this test. However, to avoid any bias, a representative set was se-
lected by taking the average of each input parameter from the
training and testing databases. The two parameters in the average
set are Co = 0.55 ppm and Q = 3 m/d. The value of each of these two
parameters is perturbed about its mean and the output break-
through curve is determined using the predictive network. It is
noteworthy to mention here that all perturbations were made
within the limits of the applicability of each input parameter.
The average absolute sensitivity matrix (Ski,abs) can be defined as
follows:
Pp  ðpÞ 
p¼1 ski 
Ski;abs ¼ ð5Þ
p
ðpÞ
where Ski is the sensitivity of the trained output and p is the num-
ber of training patterns presented to the network.
The higher average absolute sensitivity values (Table 7) for flow
rate rather than concentration suggest that flow change has a sig-
nificant and greater influence on the C/Co values than the initial
Ibuprofen
Run-4 Run-1 Run-2 Run-3 Run-4
0.999 0.999 0.984 0.993 0.999
0.993
6058 S.K. Behera et al. / Expert Systems with Applications 39 (2012) 6052–6060

Fig. 5. Training data for triclosan (a) and ibuprofen (b) (Run 1–4/p: model predicted; Run 1–4/e: experimentally observed).

70 Table 6
Ibuprofen - CP Hidden layer connection weights and bias term after network training.
60 Triclosan - CP Variable HID001 HID002 HID003 HID004
ANN Predicted

Input to hidden layer weights

50
C 2.016 4.799 4.1 3.18
Q 2.786 4.087 0.329 9.127
40 Bias 1.296 1.617 0.147 2.62
T1 T5 T25 T50 T75 T95
30
Hidden to output layer weights
HID001 1.556 0.946 0.441 0.638 0.598 0.382
20
HID002 4.297 2.768 2.718 1.937 1.389 0.836
HID003 1.302 0.172 0.326 0.815 1.161 1.562
10 HID004 0.901 1.5 0.922 0.865 0.924 1.211
Bias 0.731 0.108 0.147 0.414 0.429 0.213
0
Note. C: influent concentration (ppm), Q: flow rate (m/d), T1–T95: times corre-
0 10 20 30 40 50 60 70
sponding to C/C0 (1–95%), respectively.
Experimental

Fig. 6. Testing data for triclosan and ibuprofen.

Table 7
concentrations of both triclosan and ibuprofen. In general, the pre- Average absolute sensitivity values for the outputs.
dictive ability of the proposed model using the concepts of artificial
intelligence and the back propagation algorithm was high at the Variable T1 T5 T25 T50 T75 T95

95% confidence interval and meaningfully significant, as ascer- Q 0.7586 0.7934 0.7368 0.7214 0.7186 0.7585
tained from the correlation coefficient values between the mea- C 0.2414 0.2066 0.2632 0.2785 0.2814 0.2415

sured and predicted outputs in the training and test data. Note. Q: flow rate (m/d), C: concentration (ppm).

3.2.4. Practical implication

The behavior of the adsorption column (lysimeter) predicted by nal from a sensor coupled online to an auto-sampler connected to a
the ANN model can be compared by continuously monitoring the HPLC system. Thus, based on the information from the sensor, and
concentrations at the outlet. This can be done by acquiring the sig- based on the training made previously, the breakthrough times of
 S.K. Behera et al. / Expert Systems with Applications 39 (2012) 6052–6060
the column can be easily predicted. Consequently, the flow can be
diverted to a fresh column while this previously used column can
be regenerated separately. Furthermore, the column lysimeter data
can also be used to predict the performance of EFF system in real-
time applications. For example, Nema, Chelani, Ojha, Kumar, and
Khanna (2004) have shown that the ANN predicted results of their
column lysimeter experiment was in perfect agreement with ob-
served field data from their pilot soil aquifer treatment system
and indicated the utility of column lysimeter studies in evaluating
soil aquifer treatment systems. However, since the study period
was only about 3 months resulting in limited data collection, fur-
ther studies along similar lines over longer periods would add a
further degree of confidence in the translation of column lysimeter
results to the actual full-scale EFF system. Anew, in order to extrap-
olate the results obtained in this modeling work from lab-scale
experiments to practical situations, it is always possible to intro-
duce new inputs and new values to the already existing database
and the network can be trained whenever required. Apart from this
flexibility in updating the model as and when required, ANNs also
provide sufficient information to the plant operator about all pos-
sible interactions between predictor variables (T1–T95) and can
also signal/alarm the operator if unusual deviations in values are
noticed.
4. Conclusions
The following conclusions were made based on the perfor-
mance modeling of the EFF systems using neural networks:
1. The results from this ANN-based data-driven modeling strategy
shows that the EFF system performance, in terms of C/Co values,
can be predicted with high confidence level (95%) using easily
measurable operational parameters, namely, inlet concentra-
tion and flow rate. The model was adequately trained with
the laboratory-scale EFF column data and tested with a separate
data set.
2. A three-layered MLP was sufficient to describe the break-
through using connection weights and bias terms (thresholds).
The suitable network architecture of the model was determined
through a vigorous trial and error approach. The computed
determination coefficient (R2) values for the test data set show
high correlation between the predicted and measured perfor-
mance values. The best topology was found to be a simple
three-layered network, 2–4–6, achieved at the following set-
tings of internal network parameters: learning rate (0.9),
momentum (0.8) and a training count (epoch size) of 20,000.
3. From a practical application view point, if the pollutants and
their concentration are known in the inlet stream, they can be
added to the network and can be trained easily. Consequently,
the time for removing 1%, 5%, 25%, 50%, 75%, and 95% of the tar-
get pollutants in the EFF by adsorption can be evaluated, which
indicates the versatility of the model.
4. The robustness of the ANN was further explored with a sensitiv-
ity analysis of the input parameters, which showed that flow
rate was a more critical factor affecting EFF system perfor-
mance, than the inlet concentrations of triclosan and ibuprofen.
5. The models developed in this study can be extended to biotic
conditions by incorporating some easily measurable state
parameters such as oxygen utilization rate and specific activity
of the microorganisms to predict the breakthrough in a long
term assessment.
6. Although ANN models are not a substitute for a mechanistic
model, they were found to be promising for real-time use, in
predicting the breakthrough characteristics at different process
conditions.
6059
Acknowledgements
This research work was supported by the research funds from
University of Ulsan in South Korea. S.K.B. thankfully acknowledges
the Brain Korea 21 Post Doctoral fellowship from Ministry of Edu-
cation, Science and Technology through Environmental Engineer-
ing Program at University of Ulsan. E.R.R. thanks the Ministerio
de Ciencia e Innovación, Spain, for his ‘Juan de La Cierva’
fellowship.
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