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Contents lists available at ScienceDirect

Process Safety and Environmental Protection

journal homepage: www.elsevier.com/locate/psep

The photocatalytic degradation of carbamazepine

and prediction by articial neural networks

Lipika Das, Uttam Maity, Jayanta Kumar Basu

Department of Chemical Engineering, Indian Institute of Technology Kharagpur, Kharagpur 721302, India

a b s t r a c t

The three layer articial neural network model was applied to predict the degradation efciency for carbamazepine in
photocatalytic oxidation under UV radiation. Titaniazirconia was employed as a catalyst for the photooxidation. The
catalyst was prepared using titanium isopropoxide and zirconium oxychloride by solgel method and characterized
by transmission electron microscopy and BET analysis. Different process parameters such as, initial concentration of
carbamazepine, pH of the solution, catalyst concentration and time of UV irradiation were employed as the input to
the articial neural network model and the output of the network was degradation efciency of carbamazepine. The
multilayer feed-forward networks with the LevenbergMarquardt (trainlm) backpropagation training algorithm was
used for the network training. The smallest mean square error was obtained for three-layer network with logsig
transfer function and ve neurons in the hidden layer gave optimal results. A comparison between the predicted
values and selective experimental data of degradation efciency showed a high correlation coefcient (R2 ) of 0.997.
2013 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

Keywords: Titainazirconia nanocomposite; Photocatalysis; Carbamazepine; Articial neural network; Sol-gel

method; Oxidation

1. Introduction composites (Martneza et al., 2011). Chong et al. (2011) have

Over the past few years, water pollution with pharmaceut-
icals is noticed as a rising aquatic environmental problem
due to their continuous input and persistency in the water
body even at low concentrations (Mige et al., 2009; Halling-
Sorensen et al., 1998; Giri and Pal, 2012). Carbamazepine
(5H-dibenzo [b,f]azepine-5-carboxamide) is one of such drugs,
used as an antieliptic and anticonvulsant for the treatment of
schizophrenia as well as bipolar disorder (Miao and Metcalfe,
2003). Carbamazepine (CBZ) has been found to be a persis-
tent drug in the environment and has a harmful effect on the
function of human embryonic cells (Pomati et al., 2006).
Advanced oxidation processes (AOPs) including photocat-
alytic oxidation have been found to be an efcient method
for the removal of pollutants in wastewaters (Pera-Titus et al.,
2004). Titania as a photocatalyst have been used for the degra-
dation of CBZ in its aquous solution by different researchers
(Chong and Jin, 2012; Doll and Frimmel, 2005).The degradation
kinetics of carabamazepine have been studied by nanocrys-
talline TiO2 , ZnO and multi-walled carbon nanotubesanatase
been studied the removal of carabamazepine by photocataytic
reaction using anatase titanate nanober catalyst. Photo-
catalytic treatment of high concentration carbamazepine in
synthetic hospital wastewater were investigated by Chong and
Jin. The degradation mechanism by photocatalytic route is a
quite complex phenomena and the process is inuenced by
the numerous factors. Due to complexity in mechanism of
the photocatalytic reactions and unknown behavior, the effect
of operational parameters on the reactions is very difcult to
describe. These produce several uncertainties in the design
and scale-up of chemical reactors at the industrial levels. It is
evident that this problem cannot be solved by simple linear
multivariate correlations. The kinetic modeling of the pro-
cess involves the solution to a complex set of equations of
energy including the all transport processes are trouble some
methods. Therefore, the conventional modeling can not be
successfully employed (Coti et al., 1995). The main advantage
of ANN compared to RSM are (i) ANN does not require a prior
specication of suitable tting function, (ii) ANN has univer-
sal approximation capability, i.e. it can approximate almost all

Corresponding author. Tel.: +91 3222 283914; fax: +91 3222 282250.
E-mail addresses: jkbosu@gmail.com, jkb@che.iitkgp.ernet.in (J.K. Basu).
Received 19 May 2013; Received in revised form 30 September 2013; Accepted 1 October 2013
0957-5820/$ see front matter 2013 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.psep.2013.10.001

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Table 1 Structure and characteristics of
carbamapazepine (CBZ).
Chemical structure
IUPAC name 5H-dibenzo[b,f]azepine-5-
carboxamide
Molecular mass 236.269 g/mol
Maximum wavelength of 276 nm
absorption spectrum
Formula C15 H12 N2 O
kinds of non-linear functions including quadratic functions,
whereas, RSM is useful only for quadratic approximations and
(iii) ANN requires limited number of experiments than RSM to
build an efcient model (Ting et al., 2009; Kana et al., 2012).
It has been surveyed that application of the articial neural
network (ANN) in the elds of engineering and science is a
promising tool because of their simplicity in simulation and
prediction (Prakash et al., 2008). The advantages of ANN are
the reduced time requirement for development of the model
than traditional mathematical models and limited number of
experiments is required in the prediction (Pareek et al., 2002).
The application of ANN has been reported in several wastewa-
ter problems (Jorjani et al., 2007; Shetty et al., 2003; Gb et al.,
1999; Oliveira-Esquerre et al., 2002; Ghanbary and Jafarian,
2011; Khataee, 2009; Aleboyeh et al., 2008). The prediction
of degradation of carabamazepine by ANN in photocatalytic
oxidation using nano crystalline titaniazirconia composite
catalyst is a new eld of study.
In this present work, titaniazirconia catalyst was prepared
by solgel method and characterized by transmission electron
microscopy (TEM) as well as BET analysis. The degradation
kinetics was studied for the degradation of CBZ in aquous
solution by the photocatalytic reaction using synthesized cat-
alyst. The effect of various process parameters such as initial
concentration, pH of the solution, reaction time and cata-
lyst concentration were studied. The ANN model was applied
for the prediction of CBZ degradation. The ANN model was
trained using 70 percent of experimental data and the model
was validated using the rest 30 percent of experimental data.
2. Materials and methods
2.1. Materials
Titanium isopropoxide (Ti[OCH(CH3 )2 ]4 ) was procured from
Alfa Aeser, UK and zirconium oxychloride octahydrate
(ZrOCl2 , 8H2 O) was obtained from Loba Chemic Pvt. Ltd., Mum-
bai, India and ethanol (C2 H5 OH) was procured from Hong
Kong Chemical Corporation, China. Carbamazepine (CBZ) was
obtained from SigmaAldrich, India. The structure and char-
acteristics of CBZ are presented in Table 1.
2.2. Catalyst preparation and characterization
The titaniazirconia (TiO2 /ZrO2 ) nano composite catalyst was
prepared by solgel method using titanium isopropoxide and
zirconium oxychloride octahydrate as raw materials. Desired
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quantities of titanium isopropoxide and anhydrous ethanol
were premixed together and stirred by a magnetic stirrer for
45 min and this mixture is designated as A. The solution B
was prepared by dissolving a measured quantity of zirconium
oxychloride octahydrate in distilled water. The solution B was
then added drop-wise into mixture A to form a slurry. The
pH of the slurry was maintained at 2 by adding an appropriate
amount of diluted hydrochloric acid. The resultant slurry was
dried at 120 C and was calcined at 500 C in a mufe furnace
for 3 h (Jung and Park, 2004). Thus, a composite titaniazirconia
composite catalyst was prepared.
The surface morphology and particle size of synthesized
catalyst were analyzed by transmission electron microscopy
(TEM) (JEOL, JEM-2100, Japan). Specic surface area and pore
volume of the catalyst were determined by BET analyzer
(Quantachrome, AUTOSORB-1C, USA). Chemical composition
of the catalyst was also measured.
2.3. Experimental procedure
The photo catalytic degradation was studied in 500 mL cylin-
drical batch reactor (length: 29 cm, inside diameter: 6 cm) tted
with an ultraviolet C lamp (8 W, 218 nm, Philips, Holland),
which was placed axially inside a quartz tube and the annular
space surrounding the quartz tube was used as reactor. The
solution containing 10 mg/L of CBZ of volume 250 mL with a
require amount of catalyst was taken in the annular space. Air
was dispersed at a ow rate of 0.25 LPM through a sparger at
the bottom of the reactor and the temperature was maintained
at 30 C with a variation of 1 C. The samples were withdrawn
at the specic time intervals and analyzed by UVvis spec-
trophotometer (Chemito, India, Model 2600). The effects of
different process parameters were observed by varying the ini-
tial concentration of CBZ from 5 to 60 mg/L, pH of the solution
from 3 to 12 and catalyst concentration from 50 to 800 mg/L.
2.4. Application of articial neural network for the
prediction of degradation of CBZ
The formulation of articial neural network in prediction of
several problems is originally came from the biology of human
brain (Daneshvar et al., 2006; Durn et al., 2006; Yao et al.,
2005). The main advantage of ANN model over traditional
mathematical models is that, they do not require the com-
plex nature of the fundamental process (Nayak et al., 2006).
The analysis was performed using neural network toolbox of
MATLAB 7.9.0. In the present study, a three layer feed-forward
backpropagation network model was developed. This model
consists of an input layer, a hidden layer and an output layer
as shown in Fig. 1 which is linked by weighted connections.
In this network, the information ow is in forward direction
only from the input nodes, through the hidden nodes (if any),
and to the output nodes without any feedback connections. A
neural network is dened as a system of simple processing ele-
ments called neurons, which consists of a set of weights and
commonly interconnected nodes in a variety of structures. In
ANN, each intermediate node receives input signals from the
preceding layer through neurons, multiplied by connection
weight and the collective products are processed through a
transfer function to generate output (Li and Bridgwater, 2000).
So, the proper selections of algorithm and transfer function are
important for designing an ANN model to obtain a reliable out-
put. The commonly supported transfer functions are sigmoid,
sine, logistic, hyperbolic tangent, linear etc. are available build
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Fig. 1 Schematic diagram of the three layers ANN model
with four input and one output layer.
in functions inside MATLAB software. The details of the avail-
able algorithms of ve transfer functions are shown in Table 2.
The development of neural network need to learn about the
problem under study and this learning is commonly termed as
training process. ANNs can learn correlated patterns between
input data sets and corresponding target values, which is
called the training. After training, ANNs can be used to predict
the outcome from a new set of independent input data. During
the training process, the connection weights are adjusted from
the experience of the previous training in order to minimize
the error on the calculated output. The process is repeated
until the stop criteria such as, error tolerance limit, specied
number of iterations etc. are attained. The method by which
weights are adjusted depends on the training algorithm.
The design of an ANN model includes (a) the selection of
train and test data sets, (b) determination of most appropri-
ate architecture of the network. One of the most well-known
ANN is the feed-forward multi-layer network which uses
back-propagation learning algorithm. This type of network
generally contains an input layer, hidden layer(s) and an
output layer. This network consists of the unidirectional infor-
mation ow from the input nodes, through the hidden nodes
(if any), and to the output nodes without any feedback con-
nections. The feed-forward backpropagation network is a
feed-forward network in which training of the network has
performed by updating the weights according to the delta
values of the hidden layer to the output layer and the input
layer. Different algorithms were tested to train the transfer
function and the back propagation algorithm used for the net-
work training by updating the weights according to the delta
values of the hidden layer to the output layer and the input
Table 2 Algorithms of the transfer function used for
developing ANN model.
Name of the transfer Algorithm
function
purelin purelin(n) = n, for all n
tansig tansig(n) = 2(1 + exp (2n)) 1
satlin satlin(n) = 0, if n 0
= n, if 0 n 1
= 1, if 1 n
poslin poslin(n) = n, if n 0
= 0, if n 0
logsig logsig(n) = 1(1 + exp (n))
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3
Fig. 2 TEM image of titaniazirconia nano composite
catalyst.
layer to the hidden layer. Training of the neural network is also
dependable to the number of neurons in the hidden layer and
the optimum number of neurons in the hidden layer was to be
determined during the network design. The number of neu-
rons was optimized by trial and error method. In this present
study three layered (input layer, one hidden layer and output
layer) feed-forward backpropagation network was developed
for modeling the data. Experimental data were divided into
two sets such as, input matrix and target matrix. The four reac-
tion parameters (catalyst concentration, pH, reaction time and
initial concentration of CBZ) are the four nodes in the input
layer of the network and the output layer consists of only one
node, percentage removal of CBZ.
3. Results and discussion
3.1. Catalyst characterization
The morphology of titaniazirconia nanocomposite particles
are analyzed by TEM analysis and shown in the Fig. 2. It is
found from the gure that the particles are roughly spheri-
cal in shape and almost uniform in size with a narrow size
distribution. The presence of macro voids and agglomera-
tion of particles are clearly observed in the gure. The TEM
micrograph shows that the materials are partly composed
of clusters containing composite nano particles adhering to
each other with a mean size of about 20 nm. It suggests that
the incorporation of ZrO2 within TiO2 nanoparticles inhibits
the growth of crystallites which leads to smaller particle size.
The N2 adsorptiondesorption experiment with the catalyst is
undertaken in a BET apparatus. The surface area and pore vol-
ume are found to be 190 m2 /g and 0.72 mL/g, respectively. The
quantitative analysis of the catalyst shows that Ti: 46.37 wt%,
Zr: 5.49 wt% and O: 48.14 wt%.
3.2. ANN model development
Experimental data set at different operating condition was
used to train and test the neural network model. The ranges
of different operating parameters are given in Table 3.
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0.1
Table 3 The ranges of various process parameters used
for experiment.
0.08
Input parameters Range of the
parameter value
0.06

MSE
pH 312
Catalyst concentration (mg/L) 50800 0.04
Initial CBZ concentration (mg/L) 540
Time (min) 0150 0.02

3.3. Preprocessing of experimental data set for ANN 0

0 5 10 15 20
model development
Number of neurons

In this present study, a three layered (an input layer, single hid- Fig. 3 Relationship between number of neurons and MSE.
den layer and an output layer) feed-forward backpropagation
network was considered for modeling the data. The reaction 100
parameters (pH of the experimental solution, catalyst concen-
tration, reaction time and initial concentration of CBZ) are the y = 0.9937x + 0.3293
R = 0.9975
four nodes in input layer of the network and the output layer 80
consists of only one node, percentage removal of CBZ. Total
130 data sets that were obtained by varying different reac-

Predicted value
tion parameters were used for the neural network model. The 60
data sets were randomly divided into training (70%), validation
(10%) and test (20%) subsets. The initial rate data (at time = 0)
was not considered while developing the model to reduce the 40
o Data points
error. Best linear fit
- - - - y=x
3.4. Selection of backpropagation algorithm and 20
hidden layer transfer function

The selection of appropriate training algorithm and trans- 0

0 20 40 60 80 100
fer function is an important step for the design of ANN. The
Experimental value
number of neurons in the hidden layer initially was selected
as 2. In this present study, ve different backpropagation Fig. 4 Comparison between predicted and experimental
training algorithms such as, traincgp, trainlm, traingdx, values of the output.
trainrp, and trainscg were tested as all the algorithms may
not be applicable for all problems. The output layer transfer
of the system, the optimum neurons chosen is ve. Thus, the
function was purelin and in the hidden layer ve various
ANN is a three-layer ANN, with a logsig transfer function in the
transfer function were tested to nd out the best combina-
hidden layer with ve neurons and a linear transfer function
tion of training algorithm and hidden layer transfer function
(Purelin) in the output layer.
that will result the best coefcient of correlation (R2 ). The
comparison of different combination of training algorithms
3.6. Test and validation of the ANN model
and hidden layer transfer functions is shown in Table 4.
The LevenbergMarquardt training algorithm (trainlm) with
The data sets were provided as input parameters to the
logsig transfer function in hidden layer with ve neurons has
designed ANN model and the output from the model was
higher correlation coefcient (R2 ) value of 0.99 compared to
other combinations. In the present study Trainlm was con-
sidered as training algorithm and logsig transfer function was 20 20
nally applied in the hidden layer.
15 15
3.5. Optimization of neurons number
10 10
The optimum number of neurons was determined based on 5 5
correlation coefcient and the minimum value of MSE of the
RE (%)

training and prediction set (Yetilmezsoy and Demirel, 2008) 0 0

which is shown in Fig. 3. Too few neurons causes undertting
and too many neurons in hidden layer leads to overtting the -5 -5
model by raising the complexity of the model (Karsoliya, 2012;
-10 -10
Villiers and Barnard, 1992; Dutta et al., 2010). The network
optimization was performed by using LevenbergMarquardt -15 -15
backpropagation algorithm and Logsig transfer function was
used in the hidden layer and the number of neurons was var- -20 -20
ied from 1 to 20. The values of R2 for ve and twelve neurons
are 0.999 and 0.994 which are very close. So, to avoid overtting Fig. 5 Plot of percentage residual error.

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Table 4 Selection of Back propagation Algorithm and transfer function.

Algorithm Function Transfer function Transfer function R2 (correlation
for hidden layer for output layer factor) value

1. Conjugate gradient arbitrary backpropagation traincgp tansig purelin Arbitrary

with Polak-Ribiere updates logsig purelin 0.62
purelin purelin 0.52
satlin purelin 0.47
poslin purelin Arbitrary
2. Scaled conjugate purelin gradient trainscg tansig purelin 0.98
backpropagation logsig purelin 0.93
purelin purelin 0.81
satlin purelin 0.93
poslin purelin 0.96
3. Resillient backpropagation trainrp tansig purelin 0.93
logsig purelin 0.95
purelin purelin 0.98
satlin purelin 0.91
poslin purelin 0.94
4. Gradient descent with momentum and traingdx tansig purelin 0.92
adaptive learning rate backpropagation logsig purelin Arbitrary
purelin Purelin 0.91
satlin Purelin 0.95
poslin purelin 0.97
5. LevenbergMarquardt backpropagation trainlm tansig purelin 0.98
logsig purelin 0.99
purelin purelin 0.93
satlin purelin 0.85
poslin purelin 0.94

compared with the experimental data to assess the accuracy represents the best tted line with a good correlation coef-
of the model. In order to validate the neural network model, cient of 0.997 (Oguz et al., 2008; Giroto et al., 2006; Salari et al.,
the simulated values from the model is plotted as a func- 2005). Fig. 5 indicates a signicant correlation with percentage
tion of experimental values as shown in Fig. 4. The solid line residual error varying in the range of 12% to 14%.

Fig. 6 Comparison between actual and ANN model rends in training, validation, test and all.

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3.7. Overall results of ANN model

The results for the tting in different stages such as train-

ing, validation, test and overall data by using 45 degree lines
are presented in Fig. 6 of the ANN analysis. It can be seen
that the ANN model makes accurate predictions in the train-
ing and testing stages. The percentage removal of CBZ trends
predicted by the ANN completely follows the observed trends
in the training and testing stages, the 45 degree lines are tted
with good R2 values. Therefore, the ANN model is capable of
simulating and predicting the photocatalytic efciency with
titaniazirconia nano composite catalyst.

3.8. Effect of reactant concentration

To observe the effect of initial concentration of CBZ, experi-

ments were conducted by varying the initial concentration of
Fig. 7 Comparison between experimental and predicted
CBZ from 5 to 40 mg/L using 250 mg/L catalyst concentration at
values at various initial concentration of CBZ.
an air ow rate of 0.25 LPM. The pH of the experimental solu-
tion was maintained 7 and reactions were carried out at room
temperature. Fig. 7 shows that the percentage removal of CBZ
decreases as concentration of CBZ increases from 5 to 40 mg/L
and also shows that the experimental values and predicted
values by ANN are almost same. At 5 mg/L concentration of
CBZ, the removal rate was 90.78% at 150 min and it was found
to be 57.28% for 20 mg/L concentration of CBZ. It was further
reduced to 33.13% for 40 mg/L CBZ for the same time of degra-
dation. With the increase in concentration of CBZ, there will be
less availability of catalyst surface as assess the large number
of CBZ molecules on the surface will reduces.

3.9. Effect of catalyst concentration

The effect of catalyst concentration on degradation of CBZ,

reactions were studied at various catalyst concentration from
50 to 500 mg/L for 10 mg/L initial concentration of CBZ, at a
pH 7, an air ow rate of 0.25 LPM and at constant temper-
ature (30 C). It is seen from Fig. 8 that degradation of CBZ
increases from 48.9% to 89.9% up to 500 mg/L with increase
in catalyst concentration from 50 to 500 mg/L. Whereas, the Fig. 8 Comparison between experimental and ANN
degradation decreases above 500 mg/L of catalyst concentra- output results at various loading of catalyst.
tion. The degradation is found to be 78.62% for 800 mg/L. The
photocatalytic rate initially increases due to availability of
sufcient catalyst active sites and for higher catalyst con-
centration, there may be the light scattering and screening
effects. At the same time, a tendency toward agglomeration
(particleparticle interaction) may increase at high catalyst
concentration, which may reduce the surface area for light
absorption with decreasing photocatalytic reaction. Fig. 7 also
shows as the catalyst concentration is more sensitive to the
output parameter, the predicted results from the model is
compared in terms of experimental data for various catalyst
concentrations. The gure shows a good agreement between
the model predicted values with experimental values of the
percentage degradation of CBZ.

3.10. Effect of pH

The pH is also an important parameter in photocatalytic reac-

tion. Here, the reactions were carried out at various pH from
3 to 12 at 250 mg/L catalyst concentration, initial concentra-
tion of CBZ 10 mg/L at an air ow rate of 0.25 LPM and room Fig. 9 Comparison between experimental and ANN
temperature was maintained. The variation of the CBZ degra- output results at pH of experimental solution.
dation with the change in pH is shown Fig. 9. It is seen that

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the percentage degradation of CBZ decreases from 91.7% to
62.2% with increasing pH of the solution from 3 to 12. The
possible explanation of this is the amphoteric behavior of
semiconducting material and the change of surface charge of
the catalyst with change in pH. It also may be explained that
the induced force of attraction between negatively charged
lone pair of CBZ molecules and positively charged catalyst
increases under acidic condition and vice versa. Fig. 8 also
shows the comparison between predicted and experimental
values of CBZ degradation at various pH and the predicted
values are found to be almost similar to the experimental data.
4. Conclusions
The titaniazirconia nano cryatalline catalyst was prepared
and characterized by various methods. The catalyst was
applied for degradation of CBZ by photocatalytic reaction
under the inuence of UV radiation. The percentage degra-
dation of CBZ was successfully predicted by a three-layered
neural network analysis with ve neurons in the hidden layer
using a trainlm back propagation training algorithm. The
effect of various parameters such as, effect the initial concen-
tration of CBZ, catalyst concentration, reaction time and pH of
the solution were investigated for the degradation efciency of
CBZ through comparison with predicted results than obtained
for ANN degradation. The results conrmed that the neural
network modeling could effectively reproduce the experimen-
tal data for the photocatalytic degradation of pharmaceutical
like carabamazepine.
References
Aleboyeh, A., Kasiri, M.B., Olya, M.E., Aleboyeh, H., 2008.
Prediction of azo dye decolorization by UV/H2 O2 using
articial neural networks. Dyes and Pigments 77, 288294.
Chong, M.N., Jin, B., 2012. Photocatalytic treatment of high
concentration carbamazepine in synthetic hospital
wastewater. Journal of Hazardous Materials 199200, 135142.
Chong, M.N., Jin, B., Laera, G., Saint, C.P., 2011. Evaluating the
photodegradation of Carbamazepine in a sequential batch
photoreactor system: impacts of efuent organic matter and
inorganic ions. Chemical Engineering Journal 174, 595602.
Coti, M., Grand Jean, B.P.A., Lessard, P., Thibault, J., 1995. Dynamic
modelling of the activated sludge process: improving
prediction using neural networks. Water Research 29 (995),
1004.
Daneshvar, N., Khataee, A.R., Djafarzadeh, N., 2006. The use of
articial neural networks (ANN) for modeling of
decolorization of textile dye solution containing C. I. Basic
Yellow 28 by electrocoagulation process. Journal of Hazardous
Materials B137, 17881795.
Doll, T.E., Frimmel, F.H., 2005. Photocatalytic degradation of
carbamazepine, clobric acid and iomeprol with P25 and
Hombikat UV100 in the presence of natural organic matter
(NOM) and other organic water constituents. Water Research
39, 403411.
Durn, A., Monteagudo, J.M., Mohedano, M., 2006. Neural
networks simulation of photo-Fenton degradation of reactive
Blue 4. Applied Catalysis B: Environmental 65, 127134.
Dutta, S., Parsons, S.A., Bhattacharjee, C., Bandhyopadhyay, S.,
Datta, S., 2010. Development of an articial neural network
model for adsorption and photocatalysis of reactive dye on
TiO2 surface. Expert Systems with Applications 37, 86348638.
Ghanbary, F., Jafarian, A., 2011. Preparation and photocatalytic
properties of silver doped titanium dioxide nanoparticles and
using articial neural network for modeling of photocatalytic
activity. Australian Journal of Basic and Applied Sciences 5,
21932202.
Please cite this article in press as: Das, L., et al., The photocatalytic degradation of carbamazepine and prediction by articial neural networks.
Process Safety and Environmental Protection (2013), http://dx.doi.org/10.1016/j.psep.2013.10.001
7
Giri, P., Pal, C., 2012. Pharmaceuticals in the environment: a brief
review. Advances in Pure and Applied Chemistry 1, 7376.
Giroto, J.A., Guardani, R., Teixeira, A.C.S.C., Nascimento, C.A.O.,
2006. Study on the photo-Fenton degradation of polyvinyl
alcohol in aqueous solution. Chemical Engineering and
Processing 45, 523532.
Gb, S., Oliveros, E., Bossmann, S.H., Braun, A.M., Guardani, R.,
Nascimento, C.A.O., 1999. Modeling the kinetics of a
photochemical water treatment process by means of articial
neural networks. Chemical Engineering and Processing 38,
373382.
Halling-Sorensen, B., Nors Nielsen, S., Lanzky, P.F., Ingerslev, F.,
Holten Liitzho, H.C., Jorgensen, S.E., 1998. Occurrence, fate
and effects of pharmaceutical substances in the environment
a review. Chemosphere 36, 357393.
Jorjani, E., Chehreh Chelgani, S., Mesroghli, Sh., 2007. Prediction
of microbial desulfurization of coal using articial neural
networks. Minerals Engineering 20, 12851292.
Jung, K.Y., Park, S.B., 2004. Photoactivity of SiO2 /TiO2 and
ZrO2 /TiO2 mixed oxides prepared by solgel method.
Materials Letters 58, 28972900.
Kana, E.B.G., Oloke, J.K., Lateef, A., Oyebanji, A., 2012.
Comparative evaluation of articial neural network coupled
genetic algorithm and response surface methodology for
modeling and optimization of citric acid production by
Aspergillus niger mcbn297. The Italian Association of Chemical
Engineering 27, 397402.
Karsoliya, S., 2012. Approximating number of hidden layer
neurons in multiple hidden layer BPNN architecture.
International Journal of Engineering Trends and Technology 3,
714717.
Khataee, A.R., 2009. Photocatalytic removal of C.I. Basic Red 46 on
immobilized TiO2 nanoparticles: articial neural network
modelling. Environmental Technology 30, 11551168.
Li, Y.Y., Bridgwater, J., 2000. Prediction of extrusion pressure using
an articial neural network. Powder Technology 108, 6573.
Martneza, C., Canle, L.M., Fernndez, M.I., Santaballa, J.A., Faria,
J., 2011. Kinetics and mechanism of aqueous degradation of
carbamazepine by heterogeneous photocatalysis using
nanocrystalline TiO2 , ZnO and multi-walled carbon
nanotubesanatase composites. Applied Catalysis B:
Environmental 102, 563571.
Miao, X., Metcalfe, C.D., 2003. Determination of carbamazepine
and its metabolites in aqueous samples using liquid
chromatography-electrospray tandem mass spectrometry.
Analytical Chemistry 75, 37313738.
Mige, C., Choubert, J.M., Ribeiro, L., Eusbe, M., Coquery, M.,
2009. Fate of pharmaceuticals and personal care products in
wastewater treatment plants conception of a database and
rst results. Environmental Pollution 157, 17211726.
Nayak, P.C., Satyaji Rao, Y.R., Sudheer, K.P., 2006. Groundwater
level forecasting in a shallow aquifer using articial neural
network approach. Water Resources Management 20, 7790.
Oguz, E., Tortum, A., Keskinler, B., 2008. Determination of the
apparent rate constants of the degradation of humic
substances by ozonation and modeling of the removal of
humic substances from the aqueous solutions with neural
network. Journal of Hazardous Materials 157, 455463.
Oliveira-Esquerre, K.P., Mori, M., Bruns, R.E., 2002. Simulation of
an industrial wastewater treatment plant using articial
neural networks and principal components analysis. Brazilian
Journal of Chemical Engineering 19, 365370.
Pareek, V.K., Brungs, M.P., Adesina, A.A., Sharma, R., 2002.
Articial neural network modeling of a multiphase
photodegradation system. Journal of Photochemistry and
Photobiology A: Chemistry 149, 139146.
Pera-Titus, M., Garc a-Molina, V., Banos, M.A., Gimneza, J.,
Esplugas, S., 2004. Degradation of chlorophenols by means of
advanced oxidation processes: a general review. Applied
Catalysis B: Environmental 47, 219256.
Pomati, F., Castiglioni, S., Zuccato, E., Fanelli, R., Vigetti, D., Ssetti,
C., Calamari, D., 2006. Effects of a complex mixture of
therapeutic drugs at environmental levels on human
PSEP-375; No. of Pages 8
ARTICLE IN PRESS
8 Process Safety and Environmental Protection x x x ( 2 0 1 3 ) xxxxxx

embryonic cells. Environmental Science and Technology 40,
24422447.
Prakash, N., Manikandan, S.A., Govindarajan, L., Vijayagopal, V.,
2008. Prediction of biosorption efciency for the removal of
copper(II) using articial neural networks. Journal of
Hazardous Materials 152, 12681275.
Salari, D., Daneshvar, N., Aghazadeh, F., Khataee, A.R., 2005.
Application of articial neural networks for modeling of the
treatment of wastewater contaminated with methyl tert-butyl
ether (MTBE) by UV/H2 O2 process. Journal of Hazardous
Materials B125, 205210.
Shetty, G.R., Malki, H., Chellam, S., 2003. Predicting contaminant
removal during municipal drinking water nanoltration using
articial neural networks. Journal of Membrane Science 212,
99112.
Ting, H.T., Abou-El-Hossein, K.A., Chua, H.B., 2009.
Prediction of etching rate of alumino-silicate glass by RSM
and ANN. Journal of Scientic & Industrial Research 68,
920924.
Yao, H.M., Vuthaluru, H.B., Tade, M.O., Djukanovic, D., 2005.
Articial neural network-based prediction of hydrogen
content of coal in power station boilers. Fuel 84,
15351542.
Yetilmezsoy, K., Demirel, S., 2008. Articial neural network (ANN)
approach for modeling of Pb(II) adsorption from aqueous
solution by Antep pistachio (Pistacia vera L.) shells. Journal of
Hazardous Materials 153, 12881300.
Villiers, J.D., Barnard, E., 1992. Backpropagation neural nets with
one and two hidden layers. IEEE Transactions on Neural
Networks 4, 137141.

Please cite this article in press as: Das, L., et al., The photocatalytic degradation of carbamazepine and prediction by articial neural networks.
Process Safety and Environmental Protection (2013), http://dx.doi.org/10.1016/j.psep.2013.10.001