Trans Indian Inst Met
DOI 10.1007/s12666-014-0507-3
TECHNICAL PAPER
Modeling on Transition of Heavy Metals from NiCd Zinc Plant
Residue Using Artificial Neural Network
Hossein Kamran Haghighi Meraj Rafie
Davood Moradkhani Behzad Sedaghat
Aliakbar Abdollahzadeh
Received: 2 October 2014 / Accepted: 24 December 2014
 The Indian Institute of Metals - IIM 2015
Abstract The assessment of heavy metal transition from
NiCd zinc plant residue (filtercake), as concentrations of
zinc, nickel, cadmium and lead, requires quantification and
a mathematical model that predicts their relative concen-
trations. Variability of filtercake characteristics may
change the availability of heavy metals to the leachate or
environment. In this study, a novel artificial neural network
(ANN) model was constructed to predict Zn, Ni, Cd and Pb
concentration leached from NiCd filtercake in the leach-
ing column. A three-layer backpropagation neural network
was optimized and developed based on the Bayesian
training algorithm. The inputs of this network are pH, flow
rate of acidic influent, particle size and time. The geometry
of the network giving the minimized mean square error
(MSE) and sum of squared error (SSE) was a three-layer
network having 18 neurons in the hidden layer (4:18:4)
with a tangent sigmoid transfer function (tansig) at the
hidden layer and linear transfer function (purelin) at the
output layer. The fitting, regression, error and histogram
plots for each response illustrate that there is a good
agreement between the experimental data and the predicted
H. Kamran Haghighi (&)
A. Abdollahzadeh
Department of Mining and Metallurgical Engineering,
Amirkabir University of Technology, Tehran, Iran
e-mail: h.kamran.h@aut.ac.ir
H. Kamran Haghighi
University of Applied Science and Technology, Calcimin
Branch, Zanjan, Iran
M. Rafie
D. Moradkhani
Faculty of Engineering, Zanjan University, Zanjan, Iran
B. Sedaghat
Research and Engineering Company for Non-ferrous Metals
(RECo), P.O. Box 45195-1445, Zanjan, Iran
TP 2899
values. Finally, a generalization of the developed model
was carried out as 3D plots to evaluate the interactions of
the input parameters on the transition of heavy metals to
the leachate. With respect to these results, the effect of
particle size on concentrations of zinc, nickel and lead are
less (\3 mg/L) than that of cadmium (\3 mg/L). Further-
more, it was found that, at low flow rate, the concentrations
of extracted metals are high due to enhancement of expo-
sure residence time (between particles and leach solution).
Keywords Artificial neural networks (ANN)

Column leaching
NickelCadmium filtercake

Zinc
Lead
1 Introduction
The behavior of wastes, soils and materials are attractive
for different fields such as environmental science, mineral
processing engineering, chemistry, agricultural and biolo-
gical sciences, and chemical engineering. In the field of
mineral processing (i.e., especially zinc minerals process-
ing), the term filtercake is attributed to the waste produced
during the leach-purification-electrolysis line. In zinc
mineral processing plants, a number of filtercakes are
generated daily as by products. Located in the north-
western province of Zanjan, Iran, in NILZ electrolytic zinc
plant, with a capacity of 20,000 t-Zn/y, a major amount of
CdNi filtercake has been stockpiled during the years [1,
2]. Existence of heavy metals in zinc plant filtercake is
potentially a risk to the environment. Rainfall water with
various conditions i.e. pH and flow rate can wash the
wastes. The chemical composition of the escaped water
may be dangerous from the environmental point of view.
The acidic water leaches hazardous metals from the
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materials. Acid mine drainage is known to have very high
concentrations of heavy metals. Acid drainage may con-
taminate both surface and ground water [3, 4]. Once acid
mine drainage begins to form it is usually impossible to
stop and is difficult and costly to remedy [4, 5]. Therefore,
control of the transfer of heavy metals to water and plants
is vital in environmental risk management. Many heavy
metals (e.g., Fe, Mn, Cu, and Zn) are vital to the nutritional
budget of plants and animals, but in high concentrations
they can be toxic and may enter the food chain through
contaminated leachate entering water supplies [6]. Deter-
mining dissolution of metals from residues of a plant is
experimentally expensive and time consuming [7]. Esti-
mating dissolution of heavy metals from these residues is a
significant stage towards evaluating the risk. Mathematical
modeling is one of the required steps before risk assess-
ment. Many mathematical or physiochemical transport
models of different chemical pollutants in solid matrices
have been described in the literature [814]. Bianchi
Janetti et al. [13] investigated the mobility and interaction
of heavy metals in a natural soil by isothermal models.
Altin et al. [14] proposed a mathematical model and
compared it with experimental data for the migration of
heavy metal ions (Pb and Cd) during the flow of aqueous
solutions through calcium-saturated montmorillonite
packing. Hinz and Selim [9] assessed the transport of zinc
and cadmium in soil using experimental evidence and
physiochemical transport models. Modeling the influence
of variable pH on the transport of zinc in a contaminated
aquifer using semi empirical surface complexation mod-
els was studied by Kent et al. [10]. Assessing the appli-
cability of Burns-type model (simple model) and
LEACHM (complex model) for describing potassium (K?)
leaching in soil was the objective of Kolahchiet et al.s
research [11]. Van der Zee and van Riemsdijk [15] have
developed a model to predict the sorption of heavy metals
based on the Freundlich isotherm for Cd in soil. The same
researches by Springob and Bottcher [16], Wilkins et al.
[17], Kookana and Naidu [18], and Streck and Richter [19]
and many others have used the Freundlich isotherm to
model the elements transition. A number of studies have
been carried out on the modeling behavior of heavy metal
sorption in soil using the artificial neural network (ANN)
[6, 7, 20]. In addition, few studies have investigated
leaching behavior of wastes using the back-propagation
neural network. Among these modeling procedures, ANN
could be used to ease the complexity of the ion transition
behavior used by means of a mechanism called training or
learning [21]. Bayar et al. [21] used ANN analysis to
construct models of column leaching behavior as a function
of mix composition. Furthermore, it was used to simulate
nitrate leaching in the agricultural drainage effluent under
various management systems [22]. It is noteworthy that
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Trans Indian Inst Met
the leaching tests categorized as extraction tests, leach tests
and column leach tests are used to study the leaching be-
havior of the wastes. They are used by regulatory agencies
for classifying hazardous waste as well as by waste dis-
posal contractors to compare the leaching performance of
different waste forms [20, 23]. Despite the significant
deviation in leachate chemistry among replicate columns
over time [24, 25], column leaching was still thought to be
a valuable approach to assess the medium- to long-term
dynamics of mine tailings toxicity and hydrogeochem-
istry [26].
With respect to the aforementioned discussions, despite
the increasing use of mathematical algorithms in sorption
and transition of metals in soils by various leaching pro-
cedures, no attempts have been carried out on the simulated
column leaching behavior using ANN in the literature.
Therefore, the state of the art of this study is the effort
towards the modeling transition and leachability of heavy
metals conducted in the simulated column leaching using
the artificial neural network.
ANNs are algorithms used to perform nonlinear statis-
tical modeling. They provide a new alternative to logistic
regression and are the most commonly used method for
developing predictive models for dichotomous outcomes
[27, 28]. ANN could be used to ease the complexity of the
ion transition behavior used by means of a mechanism
called training or learning. After a training process, ANNs
are able to give estimation by using the relationship be-
tween variables and ion transition developed during the
learning phase [21].
The present work investigated the application of ANN
for the prediction of Ni, Cd, Pb and Zn transition in terms
of heavy metal removal from NiCd filtercake by the
column leaching process. The ANN modeling outputs were
compared with the experimental data and generalized in the
experimental design space. The input parameters of this
work were selected with respect to the company condition.
The ranges of rainfall pH and rainfall flow rate were
adopted from rainfall condition of the region. Using the
results of ANN, we could predict the composition of
rainwater escaping from filtercakes on various days of a
year (i.e. various condition of this work) and the further
possible control of the hazardous metals.
Table 1 Experimental parameter variation intervals for the NiCd
filtercake leaching
Parameter Value
Particle size (mesh) ?18 -18 ? 30 Mixed particle
Flow rate (cc/min) 0.5 1 2
Input pH 7 6 5
Trans Indian Inst Met

Table 2 Comparison between outputs and targets values obtained for the concentrations of zinc, nickel, cadmium and lead
Inputs Targets (ion concentration mg/L) Outputs (ion concentration mg/L) Hazardous

No. of pH Q (mL/ Particle Time Zn Ni Cd Pb Zn Ni Cd Pb Zn Ni Cd Pb

ANN runs min) size (day)
(ASTM
mesh)

1 7 1 1 1 1.301 1.400 38.080 1.305 1.305 1.389 38.114 1.343 No Yes Yes Yes
2 7 1 1 3 1.471 0.620 18.840 0.700 1.467 0.637 18.854 0.670 No Yes Yes Yes
3 7 1 1 7 1.210 0.240 14.180 0.185 1.197 0.227 14.098 0.219 No No Yes No
4 7 1 1 13 0.880 0.020 11.750 0.270 0.881 0.014 11.814 0.255 No No Yes No
5 7 1 1 20 0.740 0.290 9.330 0.000 0.738 0.297 9.262 0.000 No No Yes No
6 7 1 1 30 0.530 0.170 8.110 0.000 0.532 0.178 8.193 0.000 No No Yes No
7 7 1 2 1 1.310 0.870 31.400 0.810 1.302 0.865 31.395 0.807 No Yes Yes Yes
8 7 1 2 3 1.520 0.410 13.940 0.100 1.528 0.413 13.930 0.120 No Yes Yes No
9 7 1 2 7 1.540 0.240 7.130 0.050 1.541 0.234 7.139 0.034 No No Yes No
10 7 1 2 13 1.240 0.010 3.680 0.180 1.242 0.033 3.874 0.181 No No Yes No
11 7 1 2 20 0.710 0.230 2.470 0.000 0.709 0.214 2.430 0.000 No No Yes No
12 7 1 2 30 0.460 0.170 3.715 0.000 0.460 0.174 3.714 0.000 No No Yes No
13 7 1 3 1 0.790 0.640 18.910 0.770 0.788 0.633 18.889 0.784 No Yes Yes Yes
14 7 1 3 3 1.360 0.290 6.790 0.100 1.361 0.304 6.798 0.063 No No Yes No
15 7 1 3 7 1.250 0.180 4.840 0.050 1.249 0.168 4.873 0.075 No No Yes No
16 7 1 3 13 0.660 0.010 4.120 0.150 0.662 0.008 4.116 0.137 No No Yes No
17 7 1 3 20 0.570 0.220 3.450 0.000 0.568 0.247 3.426 0.013 No No Yes No
18 7 1 3 30 0.430 0.170 1.910 0.000 0.433 0.132 1.943 0.000 No No Yes No
19 7 1 1 1 1.301 1.410 38.084 1.341 1.312 1.395 38.075 1.337 No Yes Yes Yes
20 7 1 1 3 1.473 0.621 18.842 0.709 1.476 0.623 18.830 0.720 No Yes Yes Yes
21 7 1 1 7 1.205 0.244 14.181 0.188 1.202 0.234 14.189 0.169 No No Yes No
22 7 1 1 13 0.882 0.025 11.754 0.271 0.882 0.043 11.544 0.271 No No Yes No
23 7 1 1 20 0.744 0.293 9.335 0.033 0.740 0.274 9.290 0.000 No No Yes No
24 7 1 1 30 0.532 0.171 8.111 0.021 0.530 0.174 8.109 0.000 No No Yes No
25 6 1 1 1 6.270 1.320 54.200 0.300 6.299 1.328 54.161 0.308 Yes Yes Yes No
26 6 1 1 3 5.500 0.285 19.360 0.210 5.466 0.291 19.349 0.167 Yes No Yes No
27 6 1 1 7 1.770 0.400 6.665 0.302 1.774 0.431 6.677 0.335 No No Yes No
28 6 1 1 13 2.790 0.090 6.335 0.362 2.792 0.052 6.213 0.345 Yes No Yes No
29 6 1 1 20 3.030 0.120 2.795 0.196 3.019 0.093 2.777 0.247 Yes No Yes No
30 6 1 1 30 1.660 0.310 3.825 0.308 1.663 0.322 3.830 0.325 No No Yes No
31 5 1 1 1 8.370 1.335 56.000 0.320 8.361 1.321 56.087 0.357 Yes Yes Yes No
32 5 1 1 3 6.390 0.375 21.860 0.260 6.403 0.382 21.815 0.219 Yes No Yes No
33 5 1 1 7 5.010 0.155 10.490 0.260 5.010 0.143 10.484 0.285 Yes No Yes No
34 5 1 1 13 2.530 0.230 9.040 0.232 2.523 0.225 9.042 0.226 Yes No Yes No
35 5 1 1 20 3.470 0.260 7.615 0.220 3.480 0.286 7.647 0.199 Yes No Yes No
36 5 1 1 30 1.380 0.160 2.445 0.148 1.378 0.164 2.454 0.153 No No Yes No
37 7 0.5 1 1 9.080 1.520 40.280 0.300 9.072 1.515 40.275 0.297 Yes Yes Yes No
38 7 0.5 1 3 1.880 1.130 24.300 0.000 1.888 1.133 24.290 0.020 No Yes Yes No
39 7 0.5 1 7 0.380 0.400 16.700 0.000 0.381 0.394 16.709 0.000 No No Yes No
40 7 0.5 1 13 1.020 0.000 13.560 0.190 1.022 0.023 13.754 0.191 No No Yes No
41 7 0.5 1 20 1.050 0.090 9.620 0.000 1.049 0.074 9.580 0.000 No No Yes No
42 7 0.5 1 30 1.400 0.160 7.840 0.000 1.400 0.164 7.839 0.000 No No Yes No
43 7 1 1 1 1.309 1.409 38.090 1.342 1.307 1.435 38.147 1.317 No Yes Yes Yes
44 7 1 1 3 1.475 0.621 18.844 0.709 1.463 0.559 18.783 0.727 No Yes Yes Yes
45 7 1 1 7 1.201 0.248 14.182 0.180 1.201 0.283 14.248 0.158 No No Yes No
46 7 1 1 13 0.882 0.026 11.750 0.209 0.881 0.000 11.677 0.320 No No Yes No
47 7 1 1 20 0.740 0.295 9.332 0.065 0.740 0.285 9.336 0.000 No No Yes No

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Table 2 continued
Inputs Targets (ion concentration mg/L) Outputs (ion concentration mg/L) Hazardous

No. of pH Q (mL/ Particle Time Zn Ni Cd Pb Zn Ni Cd Pb Zn Ni Cd Pb

ANN runs min) size (day)
(ASTM
mesh)

48 7 1 1 30 0.530 0.174 8.111 0.057 0.528 0.178 8.082 0.036 No No Yes No

49 7 2 1 1 1.050 0.700 11.790 0.103 1.059 0.730 11.749 0.115 No Yes Yes No
50 7 2 1 3 0.885 0.530 10.430 0.000 0.867 0.479 10.401 0.000 No Yes Yes No
51 7 2 1 7 0.685 0.065 6.995 0.000 0.698 0.102 7.039 0.000 No No Yes No
52 7 2 1 13 1.090 0.000 4.030 0.085 1.083 0.000 4.018 0.097 No No Yes No
53 7 2 1 20 0.543 0.080 4.580 0.000 0.546 0.096 4.603 0.000 No No Yes No
54 7 2 1 30 0.500 0.075 4.050 0.000 0.500 0.082 4.062 0.000 No No Yes No

The hazardous condition of each experiment has been specified by Yes or No with respect to DIN standard

Fig. 1 The neural network

structure of this study

2 Materials and Methods
2.1 Material Preparation
NiCd filtercake for the leaching study was obtained from
National Lead and Zinc Co., Zanjan, Iran. The composition
of the filtercake was analyzed by Atomic Absorption
Spectroscopy (AAS) and the following result was obtained:
Zn 44.16 %, Ni 3.9 %, Co 0.02 %, Cd 15.15 % and Pb
1.05 %. Also, X-ray diffractometry (XRD) results showed
that Zn, ZnSO4, ZnSO3
2.5H2O, CdO and ZnO were the
major phases in the filtercake [2].
In order to prepare a desired sample for the experiments,
the following steps were pursued: drying, crushing and
sieving. Based on these steps, before crushing, the filter-
cake was dried at 100 C. In order to obtain three fractions
of samples i.e., 18 ASTM mesh (first level). -18 ? 30
mesh and mixed fraction size (third level), the dried fil-
tercake was comminuted in a jaw crusher followed by
sieving. H2SO4 from Merck, with a purity of 9598 %, was
used in column leaching experiments.
2.2 Experimental Procedures
In order to model the transition of heavy metals using
ANN, a series of experiments were conducted to collect
appropriate data. Based on the natural conditions that oc-
curred during rainfall, time, particle size, pH and flow rate

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of the leaching column influent as the four input parameters
and the concentration of Ni, Cd, Zn and Pb as the outputs
of the neural network were chosen to be investigated.
Table 1 shows the aforementioned parameters and the
ranges of their levels considered in the structure of ANN.
The experiments were carried out in the cylindrical glass
columns with a diameter of 6 cm and height of 50 cm. In
Fig. 2 Curve of SSE to training subset
the experiments, each column was filled with 1,270 gr of
dried filtercake and a layer of washed and dried sand along
with a Whatman filter paper with a thickness of 24 cm
were put on the top of the filled filtercake. A droplet system
was set to add the acid solution with different pH and flow
rates at the top of the columns.
In this column, a series of classical approaches was
carried out to determine the optimum conditions of particle
size, Q and pH, respectively (see Table 2). In the first step
pH and Q were fixed at 7 and 1 (mL/min) and the max-
imum dissolution condition of particle size was determined
with respect to the experiment row numbers of 118 (i.e.
the optimum condition of particle size was found to be 1).
Then, the overall maximum dissolution condition of Q was
selected to be 1 (i.e. when the pH and particle size were
fixed at 7 and 1) with regard to the experiment row num-
bers of 3754. Finally, the effects of pHs (5 and 6) in
optimum conditions of particle size and Q (i.e. mixed
fraction (1) and Q = 1) were investigated as experiment
row numbers of 1936 illustrated in Table 2. The detailed
discussion about how the experiments were conducted was
published elsewhere [29]. All the experiments were carried
out for 30 days and sampling of the leachate was per-
formed on the 1st, 3rd, 7th, 13th, 20th and 30th days. The
diluted clear leach sample was analyzed for Ni, Cd, Zn, and
Pb using an AA-300 Perkin-Elmer model Atomic
Absorption Spectrometer.

Table 3 Weight matrix, weights between input and hidden layers (W1) and weights between hidden and output layers (W2)
Neuron W1 (input layer to hidden layer) W2 (hidden layer to output layer)
Inputs Outputs
pH Q Particle size time Zn conc. Ni conc. Cd conc. Pb conc.

1 -2.92 -0.92 0.12 -2.61 -3.83 -0.38 -2.6 4.4

2 0.12 -0.5 0.34 0.47 1.88 0.08 -2.75 -0.16
3 -2.67 1.35 -0.09 -2.58 -0.14 -0.24 0.04 0.65
4 -1.9 1.84 2.25 -4.42 -1.21 0.68 2.63 -1.03
5 -1.39 1.38 1.93 -4.37 1.15 -0.45 -1.09 1.07
6 -0.37 0.11 -0.23 -4.81 -0.15 0.55 -0.11 -0.39
7 0.15 0.78 0.05 6.04 -1.73 -1.52 -2.52 0.14
8 -1.64 0.81 0.19 3.9 1.35 -1.23 -0.52 -1.36
9 0.83 -1.08 -0.19 -2.12 2.13 -3.15 -0.83 -2.03
10 2.99 1.79 0.57 2.52 -3.03 -0.69 -2.07 4.32
11 -1.76 0.32 -0.95 -0.58 0.55 0.27 -0.28 -0.51
12 -0.55 1.77 -0.21 -0.84 1.21 -0.88 -2.43 -0.34
13 -0.01 1.47 0.79 0.44 0.5 0.33 -0.47 -0.82
14 1.75 -1.17 0.95 2.91 1.06 -0.25 1.01 -1.94
15 -0.14 -6.33 -2.64 6.41 1.05 -0.77 0.41 -0.3
16 -0.47 1.5 0.24 1.84 0.27 -1.98 0.01 0
17 3.31 1.1 -3.79 7.38 -0.83 0.8 1.02 0.19
18 2.76 -2.58 -0.1 3.35 -1.78 0.57 -1.03 1.49

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Table 4 Bias matrix, biases applied to the hidden layer (b1) and training epoch, the network compares the target result with
biases applied to the output layer (b2) the actual result and calculates the error [21].
Neuron b1 b2 In this study, the following actions were performed to
Hidden layer Output layer construct an appropriate structure for ANN: (i) data selection
and pre-processing, (ii) dividing the sample to three series:
1 -0.2 -0.12
training, validation and test, (iii) selection of model geometry.
2 1.02 0.35
Based on this process, MATLAB software was used for
3 3.29 1.22
training and validating the neural network models. Four
4 0.07 -0.55
input and four output (Multiple Input-Multiple Output)
5 -0.47
network models were developed for the initial pH, the flow
6 -2.47
rate of acidic influent (mL/min), the particle size, and time
7 6.58
and for the concentrations of zinc, nickel, cadmium and
8 0.4
lead as the responses. The standard Bayesian regularization
9 -0.38
back propagation training algorithm, trainbr function, was
10 1.38 used for training the network. The LevenbergMarquardt
11 0.92 algorithm was used to optimize the weights and biases in
12 -1.5 this training method. The Bayesian training algorithm is
13 1.4 one of the best ways to improve generalization perfor-
14 1.24 mance of the network for function approximation problems
15 1.56 [32]. This is because it does not require that a validation
16 0.28 data set be separated out of the training data set. This is
17 1.28 especially noticeable for small sizes of the data set.
18 -1.22 Minimization of a linear combination of squared errors
and weights followed by determination of the correct
combination to produce the network and well generaliza-
Table 5 Safe limit concentrations of heavy metals and DIN standard
tion are the other advantageous of this algorithm [32, 33].
leaching levels A three-layered back propagation neural network formed
the structure of the present work. Figure 1 shows the afore-
Element Max concentration WHO Safe DIN leaching
in current column limit (mg/L) level (mg/L) mentioned structure. 54 experimental data sets were used to
leaching (mg/L) [35] [36] develop the structure of ANN. The inputs and output data
collected from experimental results were divided into the
Zn 9.08 2.00 2.00
input matrix [P] and target matrix [T]. The 54 data sets were
Pb 1.34 0.5 0.4
divided into training (48) and test (6) subsets. It is noteworthy
Cd 56 0.01 0.1
that the Bayesian approach permits to control the problem of
Ni 1.52 0.4 overfitting because of the automatic penalization of highly
complex model. Furthermore, Bayesian algorithms per-
2.3 Artificial Neural Network (ANN) mit the values of regularization coefficients to be selected
using only the training data. Because of these reasons,
ANNs are computational models in which the mode of during Bayesian learning, a separate set of cross-validation
data processing replicates the mode of synaptic dynamics data is not required given that there is no need to stop training
in the biological neural networks. ANNs consist of closely in order to avoid overfitting [34]. The number of neurons
interconnected numerical processing units called neurons, was examined in different networks and a number, which had
which offer a rich structure exhibiting some properties of the least mean square value (MSE) and sum squared error
biological neural networks [28, 30]. (SSE), was selected as the optimum neurons number.
The strength of these interconnections is determined by
the weight associated with neurons [31]. Various structures
based on some algorithms are used in ANN. One of these 3 Results and Discussion
structures is the multilayer feed-forward perceptron. Appli-
cation of this kind of network is common in engineering and 3.1 Determination Process of Neural Network
environmental science. This network learns by experimental Structure
data, that is, a repeatedly processing training epoch con-
taining a series of input matrices and the target output matrix As mentioned, a network based on trainbr was applied
for each case should be provided. During each run of the to predict the transition process of heavy metals from Ni

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Zn Leachate conc.-DIN conc>2

6
Concentration (mg/L)

0
1 3 5 7 9 11 13 15 17 19 21 23 25 27 29 31 33 35 37 39 41 43 45 47 49 51 53
Condition number

Fig. 3 The concentration of zinc in the leachate of experiments with respect to the DIN limited levels. The concentrations of the conditions
being more than DIN concentration have been illustrated with red color (light color in black and white prints)

Ni Leachate conc.-DIN conc>0.4

1.6

1.2
Concentration (mg/L)

0.8

0.4

0
1 3 5 7 9 11 13 15 17 19 21 23 25 27 29 31 33 35 37 39 41 43 45 47 49 51 53
Condion number

Fig. 4 The concentration of nickel in the leachate of experiments with respect to the DIN limited levels. The concentrations of the conditions
being more than DIN concentration have been illustrated with red color (light color in black and white prints)

Cd filtercake. A three-layered network was selected to form inputs at the hidden layer and output layer, respectively. In
the structure of the present study. Tangent sigmoid (tansig) order to determine the optimal artificial neural network
and linear (purelin) functions were chosen to transfer structure, several numbers of epochs were evaluated with

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Cd Leachate conc. -DIN conc.>0.1

55

50

45

40
Concentration (mg/L)

35

30

25

20

15

10

0
1 3 5 7 9 11 13 15 17 19 21 23 25 27 29 31 33 35 37 39 41 43 45 47 49 51 53
Condition number

Fig. 5 The concentration of cadmium in the leachate of experiments with respect to the DIN limited levels. The concentrations of the conditions
being more than DIN concentration have been illustrated with red color (light color in black and white prints)

Pb Leachate conc.-DIN conc.>0.4

1.2
Concentration (mg/L)

0.8

0.4

0
1 3 5 7 9 11 13 15 17 19 21 23 25 27 29 31 33 35 37 39 41 43 45 47 49 51 53
Sample number

Fig. 6 The concentration of lead in the leachate of experiments with respect to the DIN limited levels. The concentrations of the conditions
being more than DIN concentration have been illustrated with red color (light color in black and white prints)

different numbers of neurons in the hidden layer. The de-
termination process started with two neurons and increased
the number of neurons up to eighteen. The minimized
value of the sum squared error performance function (SSE)
was obtained at 0.00738336 in one hidden layer with
eighteen neurons (Fig. 2).
The artificial neural network tries each example in turn
using the inputs to calculate answers, which is compared to
the target provided. If it is wrong, the ANN corrects the
network by making changes to interconnections (weights
and biases) [32, 35]. In this study, the trial and error pro-
cess was used to obtain the optimized weights and biases.
In this condition, the network outputs were in good
agreement with targets. Tables 3 and 4 show the weight
and bias matrixes between neurons of layers made by the
ANN model used in this study.

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Fig. 7 a Comparison of measured zinc transition from NiCd filtercake (concentration) in leaching column with predicted values, b correlation
between calculated and observed values, c prediction error values and d relative frequency histograms of data set output errors by NN for zinc
Outputs and targets as the concentrations of zinc, nickel,
cadmium and lead, respectively, obtained from ex-
perimental data and the neural network model, are illus-
trated in Table 2. As illustrated in this table, the slight
differences between network outputs and experimental
values (targets) indicated a good agreement between the
results of ANN and the empirical experiments.
3.2 Classification of Hazardous Conditions
In order to classify the hazardous condition, the DIN
standard limit and WHO were used. Table 5 shows safe
limit concentrations of heavy metals and DIN standard
leaching levels. If concentration values of heavy metals in
a condition are more than the value of this table, it will be
classified as a hazardous condition.
Figures 3 to 6 show the concentrations of heavy metals
obtained from the 54 conditions. As seen in these figures,
the concentration of each metal has been illustrated as
columns. In order to determine the hazardous condition,
each concentration was compared with DIN standard
leaching level, so that if a concentration of an element was
more than DIN level, the related condition would be
classified as a hazardous condition. In these figures, the
concentrations being more than the DIN levels are haz-
ardous and have been seen in columns with red (light)
color.
According to the DIN level, the standard concentration
of Zn in environment is 2.00 mg/L. Therefore, the con-
centration being more than this level is hazardous. As
Fig. 3 and Table 2, the condition numbers 2537 except
27, 30 and 36 were found to be hazardous conditions. As
seen, these conditions often occurred at pHs of 5 and 6.
This is because of high dissolution of zinc and elements at
acidic pHs. Similarly, as seen in Fig. 4, the concentration
of nickel in conditions being 1, 2, 7, 8, 13, 19, 20, 25, 31,
37. 38, 43, 44, 49 and 50 were more than DIN standard (i.e.
0.4) and classified as hazardous conditions. These results
showed that in early days of leaching (i.e. 13 days), the
concentration of nickel are not safe. Furthermore, as shown
123

Fig. 8 a Comparison of measured nickel transition from NiCd filtercake (concentration) in leaching column with estimated values,
b correlation between calculated and observed values, c prediction error values and d relative frequency histograms of data set output errors by
NN for nickel
in Fig. 5, the concentration of cadmium in all conditions of
experiments was classified as hazardous conditions. Fi-
nally, as shown in Fig. 6, the concentration of lead in the
conditions being 1, 2, 7, 13, 19, 20, 43 and 44 were more
than 0.4 and classified as hazardous conditions. As a result,
the conditions performed in the early days of leaching (i.e.
13 days) were unsafe. With respect to the results, the
leaching of the filtercakes in all conditions produces a
leachate with a hazardous cadmium concentration. There-
fore, the filtercakes used in this study can be identified as a
hazardous material.
3.3 ANN Predictability
In order to determine the accuracy of the model, a number
of values, namely the R2, mean square error (MSE),
standard error of the regression error (RMSE) and per-
centage relative error was determined for both training and
testing sets. Using these values, the selection of the
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produced neural network model could be possible. There-
fore, training was proceeded until over-training occurred.
Correlation values were calculated for the evaluation data
set after training. The best network geometry is selected
according to the highest R2 and the lowest MSE and
RMSE error value. These values along with percentage
relative error value for one hidden layered network with
eighteen numbers of neurons in the hidden layer are shown
in Figs. 7 to 10 for the zinc, nickel, cadmium and lead
concentration of leachate.
3.3.1 Predictability of Zinc Concentration (Transition)
In order to evaluate the predictability of the model for the
metal transition, the following plots were achieved: (a) fit-
ting, (b) regression, (c) error and (d) histogram plots. The
results of agreement between measured and predicted
values (targets and outputs) and prediction error values are
shown in Fig. 7ad. As seen in Fig. 7a, the output and
Trans Indian Inst Met
Fig. 9 a Comparison of measured cadmium transition from NiCd filtercake (concentration) in leaching column with estimated values,
b correlation between calculated and observed values, c prediction error values and d relative frequency histograms of data set output errors by
NN for cadmium
target curves are exactly fitted together. According to the
prediction results, shown in Fig. 7b, the high R squared
value shows that the performance of the selected network
(4:18:4) is high. Figure 7c shows that the error is between
-0.01 and 0.01 % (i.e., with a confidence interval of 95 %)
which is an acceptable error interval. The values of MSE
and RMSE for these output sets of the NN model were
calculated to be 6.27 9 10-6 and 0.0025, respectively. An
analysis of error histograms is shown to be an effective
means for investigating and resolving inconsistent perfor-
mance measures. In order to explore the inconsistences in
errors, the histograms of the output errors were plotted for
the network (Fig. 7d). The large center peak indicates
very small errors or output that is very close to the targeted
values. The smaller endpoint spikes denote clearly
incorrect responses [36]. As seen in Fig. 7d, the error
histogram has focused on the zero error, with high fre-
quency. Therefore, the histogram plot shows that the pre-
dicted values together with the observed values are in good
agreement.
3.3.2 Predictability of Nickel Concentration (Transition)
As mentioned for predictability of zinc transition, the
predictability of nickel concentration in the leachate was
evaluated using fitting, regression, error and histogram
plots. The result of agreement between predicted values of
output neurons and experimental values for nickel transi-
tion is shown in Fig. 8a. Figure 8b illustrates the correla-
tion between the outputs of the ANN model and the target
values for the data set. As shown in this figure, the R
squared value is 0.999 showing good agreement between
the model prediction and the experimental targets. The
prediction error distribution of nickel concentration for the
54 data by ANN is shown in Fig. 8c. As seen in this plot,
the tolerances of the relative error are approximately be-
tween -0.01 and 0.01 % showing the acceptable pre-
dictability of the model for nickel concentration in the
leachate. The values of MSE and RMSE for these output
sets of the NN model (5.43 9 10-5 and 0.0007, respec-
tively) confirm the aforementioned result. The histogram of
123

Fig. 10 a Comparison of measured lead transition from NiCd filtercake (concentration) in leaching column with estimated values, b correlation
between calculated and observed values, c prediction error values and d relative frequency histograms of data set output errors by NN for
cadmium
the output errors was plotted for the nickel concentration
(mg/L) in Fig. 8d. As shown in this plot, the relative error
range for nickel concentration occurring within 2 9 10-2
indicates that there is no significant difference between
target and output values.
3.3.3 Predictability of Cadmium Concentration
(Transition)
The predictability of the network for the cadmium concen-
tration in the leachate can be shown by the trends between
the outputs and targets (actual and predicted values) in
Fig. 9a. As seen in this figure, the neural network is found to
be very effective in predicting the transition of cadmium
species from the NiCd filtercake within the range of the
data set. Figure 9b shows a comparison between ex-
perimental cadmium concentration values and predicted
values using the neural network model. The figure contains
the points, being placed with respect to the experimental
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result (x-axis) and predicted values (y-axis), on the plot and
a line, showing how the model predicts the process. The
slope of this line shows a correlation coefficient (R2) of 1.
Figure 9c illustrates the percentage relative error between
ANN training and testing (54 runs) and experimental data.
The mean square error (MSE) and standard error of the
regression error (RMSE) are found to be 1.3682 9 10-7 and
0.000036289, which is within the 0.1 % error range.
Figure 9d shows the histogram of the relative error of the
cadmium concentration versus the cumulative occurrence.
As seen in this plot, the relative error range within
2 9 10-2 indicates that there is a good fit between the
outputs of the model and results of experiments.
3.3.4 Predictability of Lead Concentration (Transition)
Figure 10a shows a comparison between ANN outputs and
experimental target data. As seen in this plot, the results
obtained from the ANN model have a close trend to the
Trans Indian Inst Met
Fig. 11 Generalization performances of optimal ANN, effect of particle size (ASTM mesh) and time (days) on the concentration of a zinc,
b nickel, c cadmium and d lead at the flow rate of 1 mL/min and pH of 7
result of experiments. Figure 10b shows the comparison of
experimental measured data versus the outputs predicted
by ANN. A perfect prediction would fall along a 45o line,
so a deviation from this line represents an error in the
prediction [37]. As can be seen, the R2 of 0.999 shows
that the prediction of the lead concentration in the leachate
is good by the aforementioned NN model.
The prediction error distribution of lead transition from
the NiCd filtercake to the leachate is shown in Fig. 10c. As
seen in this plot, the percentage relative error between ?0.02
and -0.02 depicts that the model of ANN has a very accurate
representation of the experimental results. The values of
MSE and RMSE calculated for the outputs of the NN model
(7.5961 9 10-5 and 0.0087156, respectively) confirm this
result. In addition, the error histogram indicates the error
values focusing on zero (Fig. 7d). This high frequency of
errors on the zero point shows that the predicted values to-
gether with the experimental values are in good agreement.
3.4 ANN Generalization
After selection of appropriate neural network architecture,
it is possible to predict heavy metal transition from the Ni
Cd filtercake for different inputs in the area of training
data. Having predicted the metal transition as the concen-
tration of zinc, nickel, cadmium and lead by the produced
model by ANN, the 3D plots for the four responses were
constructed and shown in Figs. 11 to 13. With respect to
these plots, the interaction between time and the other input
parameters on the concentration of heavy metals in the
leachate can be found. In these figures, the surfaces show
the results of the network with the structure of 4:18:4 for
comparison. Note that the experimental data have been
illustrated with bold points to show the differences of the
ANN and experiment results. With respect to these points,
it can be seen that the selected network can accurately
predict the metal transition from filtercake.
3.4.1 Effect of Particle Size
In order to predict the effect of particle size and time on the
concentration of heavy metals, the 3D plots were con-
structed for the responses by ANN (Fig. 11ad). With re-
spect to Fig. 11a, the interval changes of zinc
concentration vary between 0.5 to 3 mg/L. As seen in
Fig. 11b and d, the effect of particle size on the transition
123

Fig. 12 Generalization performances of optimal ANN, effect of flow rate (mL/min) and time (days) on the concentration of a zinc, b nickel,
c cadmium and d lead at the pH of 7 and mixed particle size
of nickel and lead is \1 mg/L. In contrast, Fig. 11c shows
the considerable effect of particle size on the transition of
cadmium to the leachate. As seen in this plot, the transition
of cadmium is increasing when the particle size changes
from ?18 (3), -18 ? 30 (2) (ASTM mesh) to the mixed
particle (3). With regard to this result, the leaching kinetic
of cadmium is faster for the finer than the coarser particles.
The fact that the mixed particle size fraction leaches faster
than the other particle size categories indicates that
heterogeneity may be a factor. The high recovery leaching
of the metals in the mixed particle size fraction is due to the
association of two properties: the high exposure due to the
existence of the fine particle and appropriate percolation of
the coarse particle existing in this fraction [38].
3.4.2 Effect of Flow Rate
The effect of the time and flow rate on the transition of
heavy metals, in the flow rate range of 0.52 mL/min in
30 days was investigated in 3D ANN plots (Fig. 12ad).
As shown in this figure, the high concentrations have been
concluded at the low flow rate of the influent due to the
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sufficient time of the solution to react with the exposed
particles. Furthermore, the concentrations of the metals
decreased with prolonging time due to the depletion of
leachable species to the leachate. In other words, the steady
state occurs during the last days. When the steady state
conditions prevail, the hydraulic conductivity of the fil-
tercake bulk in the column will be equal to the superficial
infiltration velocity. Consequently, the mass flow rate at
the inlet and outlet will be the same [39].
3.4.3 Effect of pH
To estimate the effect of time and pH on the concentration
of metal species in the leachate, the initial pH and time
varied in the range of 57 and 030 days, respectively
(Fig. 13ad). As can be seen, the significance of the low
pH appeared in the earlier times when the kinetic of
leaching is faster. This kinetic behavior was seen in the
literate [40, 41]. This effect is more significant for nickel
and cadmium. With increased time, the effect of pH is
decreasing due to depletion of leachable species to the
leachate.
Trans Indian Inst Met

Fig. 13 Generalization performances of optimal ANN, effect of pH and time (days) on the concentration of a zinc, b nickel, c cadmium and
d lead at the flow rate of 1 mL/min and mixed particle size

4 Conclusion the structure and geometry of the network were

investigated.
The present work investigated the hazardous conditions of With respect to the results, the geometry of a network
NiCd filtercake, the application of ANN for the prediction giving the minimized mean square error (MSE) and
of Ni, Cd, Pb and Zn transition from the filtercake in a sum squared error (SSE) was a three-layer network
simulated column leaching and the effects of various pa- having 18 neurons with a tangent sigmoid transfer
rameters on this transition. The detailed conclusions were: function (tansig) at the hidden layer and linear transfer
function (purelin) at the output layer based on the
The classification of the hazardous conditions of
Bayesian training algorithm. This geometry could be
filtercake was carried out using the DIN standard limit.
effectively used to study the effects of the selected
According to the results, the leaching of the filtercakes
input parameters on the concentrations of heavy metals
in all conditions produced a leachate with the hazardous
leached from NiCd zinc plant residue.
cadmium concentration. Therefore, the filtercakes used
The generalization results of the constructed model as
in this study can be identified as a hazardous material.
the 3D plots were used to evaluate the interactions and
With respect to the high risk of this material, artificial
effects of the input parameters on the transition of
neural network (ANN) was used to obtain a simplified
current study heavy metals to the leachate. With respect
model for predicting Zn, Ni, Cd and Pb concentrations
to the results, the effect of particle size on nickel, lead
in the leachate as a function of pH, the flow rate of the
and zinc transition is less 3 mg/L; however, this effect
acidic influent, particle size and time.
on cadmium transition is less than 20 mg/L.
The main aim of this study was to construct a simplified
The generalization results showed that with decreasing
and accurate network by which the effects of the
flow rate increased residence time of the acidic solution
parameters on the metal concentrations could be
and therefore, increased the leaching of heavy metals.
obtained. To construct an appropriate ANN model,

123

According to these results, high transition of heavy
metals occurred at the acidic pH, the mixed particle size
and the low flow rates.
Using these results, we could predict the composition of
rainwater escaping from filtercakes on various days of a
year and control the hazardous metals.
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