International Journal of Environmental Science and Technology (2019) 16:5409–5420

https://doi.org/10.1007/s13762-018-1891-8

ORIGINAL PAPER

Electrocoagulation process for propiconazole elimination

from wastewater: experimental design for correlative modeling
and optimization
J. Shadmehr1 · S. M. Mirsoleimani‑azizi2 · S. Zeinali1 · P. Setoodeh2

Received: 21 November 2017 / Revised: 10 June 2018 / Accepted: 26 June 2018 / Published online: 16 July 2018
© Islamic Azad University (IAU) 2018

Abstract
Electrocoagulation process is an electrochemical method to remove variety of contaminants (i.e., pesticides) from water and
wastewater effluents. The current research examines the elimination of propiconazole by electrocoagulation technique. For
this aim, after the preliminary screening tests (using factorial design) for the identification of the significant and remarkable
factors, response surface methodology based on central composite design is employed to develop a correlative model for the
efficiency of the electrocoagulation process. Furthermore, simultaneous optimization of the operational process variables
[electrolysis duration (10–60 min), propiconazole initial concentration (10–50 mg/L), current density (2.5–12.5 mA/cm2),
and solution conductivity (0.5–2.5 mS/cm)], is carried out to find the most appropriate strategy. The screening of the prime
considered factors indicates that pH is not a significant variable and consequently is excluded from further deliberations. A
quadratic correlative model is prepared, and model-based optimization is further performed and experimentally verified. The
maximum removal efficiency (79.83%) is attained regarding the following process factors: the propiconazole initial concen-
tration of 25.93 mg/L, the time duration of 36.44 min, the current density of 10.95 mA/cm2, and the solution conductivity of
2.44 mS/cm. The results demonstrate that through electrocoagulation process with proper operational variables, the amounts
of propiconazole in wastewater effluents can adequately get lowered to acceptable levels.

Keywords  Electrocoagulation · Propiconazole · Removal efficiency · Design of experiments · Response surface

methodology

Introduction
Attributable to the contamination of freshwater supplies,
one of the major challenges facing human today is to pro-
vide clean water for the whole population around the world
(Ali 2002, 2009, 2012; Imran and Aboul-Enein 2006). With
increase in the world population, the need for clean water
is on an ascending trend. According to UNESCO (Singh
Editorial responsibility: Q. Aguilar-Virgen.
* S. Zeinali
zeinali@shirazu.ac.ir
1
Nanochemical Engineering Department, Faculty
of Advanced Technologies, Shiraz University, Shiraz 71345,
Iran
2 Propiconazole is a conazole fungicide that is used agricultur-
Department of Chemical Engineering, School of Chemical
and Petroleum Engineering, Shiraz University, Shiraz 71345,
Iran
2010), there are more than one billion people who do not
have access to freshwater and also two millions of children
under age of five die every year due to lack of clean drinking
water. However, the story is more tragic than these words.
Rapid industrialization, agricultural activities, and discharge
of industrial effluents to rivers and lakes contribute to the
generation of much more contaminated drinking water (Ali
and Jain 2004; Ali et al. 2012a, b, 2016a, b, c, d, e, f, 2017a,
b, 2018; Dehghani et al. 2016).
One of the main pollution sources of freshwater are pes-
ticides (Ali et al. 2016a, b, c, d, e, f; Cobas et al. 2016).
Pesticides involve all active components produced to control
insect pests, whiteflies, and aphids (Daneshvar et al. 2007;
Esfandian et al. 2016). Conazoles are a class of imidazole-
or triazole-containing antifungal agents commonly used in
agricultural and medicamental products (Tu et al. 2016).
ally to control pests on grasses, fruits, grains, seeds, hard-
woods, and conifers (Adam et al. 2005; Chen et al. 2008).

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5410 International Journal of Environmental Science and Technology (2019) 16:5409–5420
Table 1 shows the chemical structure and other character-
istics of propiconazole. It has been considered by the US
Environmental Protection Agency (EPA) as a carcinogenic
(group C) and robust toxic compound (Vialaton et al. 2001;
Wu et al. 2003). However, due to its wide applications in
agriculture, the elimination of this type of pesticides is too
low. Therefore, the aqueous solutions containing propicona-
zole must be treated before discharge to rivers or lakes.
Three major approaches have been developed for treatment
of agricultural and industrial effluents, namely physical (Rob-
inson et al. 2001; Liu et al. 2009; Sharma and Imran 2011;
Ali et al. 2012a, b, 2014, 2015; 2016a, b, c, d, e, f; 2017a,
b), chemical (Hench et al. 2003; Kurniawan et al. 2006), and
biological techniques (Grady Jr et al. 2011; Oller et al. 2011).
Regarding pesticide contamination, physical treatment is not
appropriate because of high associated residence time, side
reactions, disposal problems, and expensive procedure (Rob-
inson et al. 2001). Also, biological treatment is not suitable
except for the case of bacterial pollution. Moreover, it may
cause the production of colorless aromatic amines which
might be toxic, mutagenic, and possibly carcinogenic to ani-
mals (Robinson et al. 2001). Thus, the chemical treatment is
a more appropriate choice for this kind of pollutions.
The common chemical treatment approaches are oxidative
process (Colombo et al. 2016), ozonation (Ternes et al. 2003;
Zhang et al. 2017), photochemical (Suárez-Escobar et al. 2016),
and flocculation. These methods are applicable to remove dif-
ferent types of pollutants from waterways. For instance, floc-
culation is applicable to remove heavy metals where saline
seawaters mix with fresh river waters (Karbassi and Marefat
2017). Also, photochemical process has been applied to remove
diazinon from aqueous media (Jonidi-Jafari et al. 2015).
Electrochemical processes are a proper technique devel-
oped in the mid-1990s (Robinson et al. 2001). These meth-
ods can be applied to a wide range of wastewaters.
Table 1  Characteristics of
propiconazole fungicide IUPAC name
Chemical formula
Chemical structure
Molar mass (g/mol)
Class
Solubility in water (20 °C)
13
Electrocoagulation is one of the electrochemical approaches
that can be applied for treatment of wastewaters (Chianeh
and Parsa 2016). This process comprises the in situ genera-
tion of coagulants via dissolution of anode (Naje et al. 2016).
The dissolution of metal ions is taken out by an applied
electrical potential. Generally, the anode is made of iron and
aluminum. Regarding utilization of aluminum ) as anode,
firstly, aluminum ions are produced Al3+  , and subse-
(
(quently, they
) are transformed to( aluminum ) hydroxides
Al(OH)3(s) and aluminum oxides Al2 O3(s) (Guzmán et al.
2016):
Al(s) → Al3+ + 3e− (1)
Al3+ + 3H2 O → Al(OH)3(s) + 3H+ (2)
2Al3+ + 3H2 O → Al2 O3(s) + 6H+ . (3)
Also, at the aluminum cathode, hydrogen gas is released and
OH− ions are generated:
6H2 O + 6e− → 3H2 + 3OH− . (4)
This reaction produces insoluble hydroxides which adsorb
the contaminants and remove them from the solution through
complexation, electrostatic attraction, precipitation, and
chemical attachment to colloidal material (Naje et al. 2016;
Suárez-Escobar et al. 2016). Moreover, electrocoagulation
consists of various phenomena such as discharge, anodic
oxidation, cathodic reduction, coagulation, adsorption, and
precipitation (Suárez-Escobar et al. 2016). Also, the evolu-
tion of hydrogen gas bubbles beside the electrodes enhances
the floatation (Chen 2004). Electrocoagulation is charac-
terized by the following characteristics: compact sludge,
1-[[2-(2,4-dichlorophenyl)-4-propyl-
1,3-dioxolan-2-yl]methyl]-1,2,4-triazole
C15H17Cl2N3O2
342.22
Fungicide
100 mg/L
International Journal of Environmental Science and Technology (2019) 16:5409–5420 5411
environmental compatibility, rapid sedimentation, simple
equipment, low operating cost, and low retention time.
Furthermore, electrocoagulation has been widely used as a
credible approach for the treatment of industrial and agri-
cultural effluents including heavy metal ions (Heidmann and
Calmano 2008; Akbal and Camcı 2011; Fu and Wang 2011),
diazinon (Amooey et al. 2014), phenol (Uğurlu et al. 2008),
phosphor (Mores et al. 2016), hospital wastewater (Arsand
et al. 2013), oil refinery (Pérez et al. 2016), baker’s yeast
(Gengec et al. 2012), and textile (Kobya et al. 2003). In our
pervious study (Mirsoleimani-azizi et al. 2015), the impacts
of numerous variables on endosulfan removal from aqueous
solutions have been investigated. The results indicated that
electrocoagulation can be a reliable process for treatment
of this type of water pollutants. Additionally, Shafaei et al.
(Shafaei et al. 2011) studied the effectiveness of electroco-
agulation in removal of Co2+ and Mn2+ from wastewaters
using aluminum electrodes. Their examination revealed that
electrocoagulation eliminated about 99% of the contami-
nants from the solutions, and furthermore, the removal of
CO2+ was twice faster than the elimination of Mn2+ in the
same condition. Also, the elimination of Cr(VI) from real
wastewater by electrocoagulation process was reported in
Aber and coworkers research. The impacts of the electrolyte
and anode types, pH value, current density, and electrolysis
duration were additionally investigated (Aber et al. 2009).
Due to the variation of the reactions happen in the elec-
trocoagulation progression; this process is too complex to be
mathematically modeled (Mirsoleimani-azizi et al. 2015).
Moreover, numerous factors can affect the electrocoagulation
performance leading to more process complexity for mod-
eling considerations. To the best of authors’ knowledge, full-
mechanistic modeling of electrocoagulation process has not
yet been comprehensively examined. However, a few studies
have been performed considering development of correlative
Fig. 1  Experimental setup of
the electrocoagulation process
models for further analysis. For instance, Bhatti et al. (Bhatti
et al. 2011) applied multi-objective optimization using the
genetic algorithm over artificial neural networks (ANNs)
to maximize the copper removal by electrocoagulation pro-
cess. Hu et al. (Hu et al. 2007) used the Langmuir equation
to determine the kinetics of the fluoride removal reaction by
electrocoagulation. Recently, Andres et al. (Suárez-Escobar
et al. 2016) optimized the removal of total organic carbon
(TOC) with electrocoagulation using experimental design via
response surface methodology (RSM).
In the present study, the effects of numerous factors,
namely initial concentration, current density, initial pH value,
solution conductivity, and electrolysis duration on the removal
efficiency of propiconazole is examined. The approach of
RSM based on the central composite design (CCD) is applied
for correlative modeling due to prospect of simultaneous
model-based optimization of the significant operating factors.
Materials and methods
Experimental equipment and procedures
The schematic diagram of the electrocoagulation process is
illustrated in Fig. 1. As depicted in this figure, the appara-
tuses used are the electrocoagulation reactor, the DC power
supply, the stirrer, and the anode and cathode. The cylindri-
cal reactor was made of pyrex glass with overall length of
13 cm, outer diameter of 9.2 cm, wall thickness of 3 mm,
capacity of 600 ml of effluent, and a working volume of
400 ml of propiconazole solution. Moreover, four aluminum
electrodes with dimension of 12 × 5 × 1 cm3 were used as
cathode and anode. These electrodes were connected in par-
allel mode to a glass pipe, and the gap distance between
each electrode is 10 mm. As indicated in Fig. 1, the outer
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5412 International Journal of Environmental Science and Technology (2019) 16:5409–5420

electrodes were connected to DC power supply (0–30 V process. For this purpose, the full-factorial design (FFD)
and 0–5 A, Megatek MP3005, Taiwan), and there was an technique was applied. The factorial design not only reduces
inter-connection between the central electrodes. Also, a gap the total number of experiments but also offers the best over-
of 2 cm was maintained between the lowest point of the all process optimization by the consideration of all probable
electrodes and the bottom of the electrocoagulation reac- interactions between the operating factors (Brasil et al. 2005;
tor for easy circulation of the solution to maintain uniform Gottipati and Mishra 2010). A typical factorial design model
concentration in each point of the reactor. For this purpose, can be represented as:
the solution was agitated at 200 rpm by a magnetic stir-
Response = b0 + b1 A + b2 B + b3 C + b4 D + b12 AB + b13 AC …
rer (Heidolph, Germany). Additionally, the electrodes were
(5)
cleaned using sandpapers after washing with 0.5 M HCl
where bn is the coefficient associated with the nth factor,
solution (under ultrasonication in ultrasonic bath) to remove
and the letters, A, B, C,…, represent the factors in the model
any oxide or contaminant from their surface (Mirsoleimani-
(Abdul-Wahab and Abdo 2007). Other terms such as AC
azizi et al. 2015). All runs were carried out at atmospheric
indicate the interactions between the individual factors. A
pressure and room temperature. The pH of each test was
common screening experimental scheme is based on a two-
adjusted using 0.1 N HCl and 0.1 N NaOH. Each experiment
level factorial design. In this approach, two levels for each
was started when the current density reached the desired
factor are considered which are called the associated low
value. The main frequently used strategy in the experimen-
(− 1) and high (+ 1) values. Regarding two-level designs, if
tations was according to varying one factor and keeping the
there exist k factors, 2k experiments are required to perform
others constant. The aim of this kind of strategy was to find
a FFD (Gottipati and Mishra 2010).
the conditions under which the maximum propiconazole
In the present work, a five-factor two-level FFD (­ 25 runs)
removal efficiency occurred. A single-beam UV–Vis spec-
was employed for modeling of the removal efficiency of propi-
trophotometer (Thermo 53711, USA) was used to determine
conazole. These factors and their levels are given in Table 2.
propiconazole concentration regarding its corresponding
wavelength (λmax 205 nm).
Correlative model development

The second step of the statistical evaluation and experimen-

Experimental design and statistical evaluation
tal design is the development of the correlative model which
is performed through a three-step procedure, namely mod-
One-factor-at-a-time (OFAT) approach is one of the strate-
eling, optimization, and validation. In this section, the RSM
gies extensively used in experimentations. By means of OFAT
based on CCD was firstly employed for correlative modeling
method, there is a starting point for each factor, and each factor
and then applied to optimize the operating factors (electroly-
varies over its feasible range, while other factors are kept fixed
sis duration, initial concentration of propiconazole, current
(Czitrom 1999). However, the major defect of this method is its
density, and solution conductivity) in order to achieve the
failure to consider the probable interactions between the factors
highest propiconazole elimination efficiency. As given in
(Montgomery 2008; Abbasi and Habibi 2016). Consequently,
Table 3, five-level (− 2, − 1, 0, + 1, + 2) CCD was imple-
one should conduct a large number of experiments to identify
mented to evaluate the above-mentioned factors leading to
the interactions between the factors which is practically impos-
27 tests with three replicates at center point.
sible. To overcome the mentioned problem, more advanced
experimental design procedures have been employed.
Analysis of variance  Analysis of variance (ANOVA) is a sorely
A complete design of experiments (DoE) typically con-
powerful statistical technique that can be applied to estimate
sists of two main steps. The first one is to screen the prime
the source of variation (Miller and Miller 2010). The applica-
considered factors and select the significant ones, and the
second one is to develop a correlative model taking the Table 2  Considered levels for each factor in FFD
impacts of the selected factors as well as their interactions
Independent parameters Symbol Low level (− 1) High level (+ 1)
into account. In the current study, both of these steps were
performed using Design ­Expert® software version 10 (https​ Time (min) A 10 60
://www.state​ase.com). In the following subsection, the Initial concentration B 10 50
experimental design procedure will be completely described. (mg/L)
Current density (mA/ C 2.5 12.5
Screening cm2)
pH D 3 11
To start a new process, it is essential to identify which fac- Solution conductivity E 0.5 2.5
(mS/cm)
tors have significant influences on the final response of the

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International Journal of Environmental Science and Technology (2019) 16:5409–5420 5413

tion of ANOVA is to find the most important factors and inter- Table 4  ANOVA table for FFD tests
actions. Also, using ANOVA one can find whether the model Source Sum of squares DF Mean square F value P value
is reliable or not. The ANOVA table is given in Table  4. In
this table, the probability values less than 0.05 indicate the Model 11,215.02 5 2243.00 38.02 < 0.0001
statistical significance of a factor at its 95% confidence level A 5358.71 1 5358.71 90.84 < 0.0001
(Roosta et al. 2014). In other words, a term that has a P value B 3263.92 1 3263.92 55.33 < 0.0001
less than 0.05 would be considered as one with a significant C 1430.32 1 1430.32 24.25 < 0.0001
effect (Asfaram et al. 2015). Terms with P values greater than E 847.69 1 847.69 14.37 0.0008
0.10 are generally regarded as nonsignificant ones. Also, the AC 314.38 1 314.38 5.33 0.0292
calculated F value for a term is a criterion to compare its asso- Residual 1533.81 26 58.99
ciated variance with the residual one. It is defined as the mean Cor total 12,748.83 31
square for the term divided by the mean square for the residual. R2 = 0.879, adjusted R2 = 0.857, predicted R2 = 0.818
When the obtained F value is very large for one factor, it means
that the factor is extremely significant. and is not included in Table 4. Conversely, other factors
(A, B, C, and E) have sensible effects on electrocoagulation
process. Also, the contribution of the time duration and the
Results and discussion initial concentration factors in ANOVA table are 42.03%
and 25.66, respectively. It should be noted that the time
The removal efficiency (Re) was calculated according to duration factor has positive effect, while the initial con-
Eq. (6) gaining the data of different conditions: centration has negative impact on the removal efficiency.
( ) Moreover, the half-normal plot in which the effects
A of different factors on the process are shown is given in
Re = 1 − × 100 (6)
A0 Fig. 2b. In this figure, factors that lie along the line are
where A0 is the absorbance of the initial solution which negligible; however, other factors far from the line are
includes propiconazole while A is the absorbance of propi- significant (Abdul-Wahab and Abdo 2007). It is clear that
conazole at time t. A (time), C (current density), E (solution conductivity),
B (initial concentration), and AC are essential terms for
DoE results electrocoagulation, but there is not any trace of D (pH).
Figure 2a, b shows the results with identical outcomes.
Screening
Correlative model development
In order to determine which factors may have positive or
negative effects on electrocoagulation process removal After the completion of the tests listed in Table 3, the
efficiency, the Pareto chart (see Fig. 2a) and the half-nor- associated data were inserted in the response column of
mal plot (see Fig. 2b) were prepared and considered. the matrix of the experiments. To analyze the data, firstly,
In the Pareto chart, factors with the tallest bars have the it should be checked that whether the response need to
greatest effects on the process. As depicted in Fig. 2a, the be transformed or not. If the ratio of the maximum to the
Pareto chart have two lines, namely Bonferroni (3.519) and minimum values of the experimental data is greater than
t value limit lines (2.055). The factors with t values above 10, a transformation (by power, log, inverse or other trans-
the Bonferroni line are considerable; also, the factors with formers) is required. This ratio was equal to 4.208 for the
t values between the Bonferroni and t value lines are likely current study; hence, there is no need for any transforma-
to be significant. However, those ones with t values below tion of the experimental data.
t value line are not remarkable (Shah and Pathak 2010). The ANOVA for the correlative model development
Therefore, pH (D) is not an important factor in this study step is presented in Table 5. It was demonstrated that the

Table 3  Different selected Independent parameters Symbol Level

levels for the five-level CCD
− 2 − 1 0 1 2

Initial concentration (mg/L) A 10 20 30 40 50

Time (min) B 10 22.5 35 47.5 60
Current density (mA/cm2) C 2.5 5 7.5 10 12.5
Solution conductivity (mS/cm) D 0.5 1 1.5 2 2.5

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5414 International Journal of Environmental Science and Technology (2019) 16:5409–5420

Fig. 2  Diagnostic graphs for select effective parameters a Pareto chart and b half-normal plot

Table 5  ANOVA table for CCD tests curvature in the response function is not adequately modeled
Source Sum of squares DF Mean square F value P value
by a first-order model and can be approximated by a second-
order polynomial (Montgomery 2012; Roosta et al. 2014). In
Model 6501.66 6 1083.61 33.16 < 0.0001 such cases, a consistent model can be considered as:
A 1805.56 1 1805.56 55.25 < 0.0001
k k k
B 1190.03 1 1190.03 36.41 < 0.0001
∑ ∑ ∑∑
y = 𝛽0 + 𝛽j xj + 𝛽jj xj2 + xi xj 𝛽ij + ∈ (8)
C 133.13 1 133.13 4.07 0.0471 j=1 j=1 i j=2
D 2608.40 1 2608.40 79.81 < 0.0001
AC 124.07 1 124.07 3.80 0.0487
where xi xj 𝛽ij is the interaction term, while 𝛽jj represents the
A2 640.47 1 640.47 19.60 0.0003
pure second-order or quadratic effect (Dil et al. 2016).
Residual 653.63 20 58.99
The final correlative model in terms of the codec fac-
Cor total 7155.29 26
tors for the efficiency of the electrocoagulation process in
removal of propiconazole was found to be represented as the
R2-squared = 0.908, adjusted R2 = 0.881 l, predicted R2 = 0.834 following equation:
Removal efficiency
all aforementioned factors are significant and also the solu- = 54.98 − 8.67A + 7.04B + 2.36C + 10.43D + 2.78AC − 4.9A2
tion conductivity was an extremely remarkable variable. (9)
Furthermore, the ANOVA table displays supplementary According to Table 5, the P value of < 0.0001 and F value
pieces of beneficial information. For instance, the quantity of 33.16 were obtained for the model demonstrating the sig-
“R-squared” is defined as (Montgomery 2008): nificance of the developed correlation. Also, the predicted
model sum of squares and actual values for the removal efficiency of the CCD tests
R2 = (7) are given in Table 6.
total sum of squares
The second section in the correlative model development
In the present study, R2 = 0.908 was obtained which means step was the model-based optimization. The software cal-
that the model could describe 90.8% of the variations in culated the optimal conditions based on Eq. (9). The finest
the response. Also, the “Predicted R-squared” of 0.881 is in condition to attain the highest removal efficiency (79.83%)
reasonable agreement with the “Adjusted R-squared” value was achieved for the propiconazole initial concentration
of 0.834. The low difference between the adjusted R2 and the of 25.93 mg/L, the time duration of 36.44 min, the current
predicted one represents the proper adjustment of the data density of 10.95 mA/cm2, and the solution conductivity of
fitting (Sadeghi et al. 2014). 2.44 mS/cm. Figure 3 illustrates the optimal conditions.
As well, the software suggested a quadratic model for For scrutiny of the accuracy of the software predictions,
propiconazole removal efficiency. In some circumstances, the three additional tests were performed under the optimal

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International Journal of Environmental Science and Technology (2019) 16:5409–5420 5415

conditions introduced by Design Expert, and the removal
percentage values of 77.52, 77.2, and 78.6% were obtained.
Also, the mean square error (MSE) was attained to be 1.52
n �
� ��
ymi − yei 2
where ym is the measured and ye is the
∑
=
i=1
n
estimated values. Thus, the third section of the correlative
model development step was carried out comprehensively
and the predicted model was validated successfully.
Normal probability plot of residuals
The normal probability plot of the residuals was used to
investigate the model adequacy and also to check the normal
distribution of the experimental data (Sadeghi et al. 2014). If
the data points in the probability plot commonly fall close to a
straight line, the data are normally distributed (Antony 2004).
It can be dedicated from Fig. 4 that the current data points
approximately fell on a straight line. It demonstrates that the
experiments come from a normally distributed population.
The effect of current density
In the electrocoagulation process, the current density is an
important factor impacting the progress execution determin-
ing the coagulant generation rate. Also, the removal efficiency
depends on the aluminum concentration in the wastewater. The
theoretical amounts of Al dissolution (mtheo) in the electroco-
­ araday’s law as follows
agulation reactor can be expressed by F
(Amooey et al. 2014; Mirsoleimani-azizi et al. 2015):
ItM
mtheo = (10)
ZF
where I is the current density (A), t is the time of electrolysis
(s), mtheo is the amount of the dissolved aluminum (g), M is
the atomic weight of the aluminum (g/mol), Z is the metal
valance (3 for Al), and F is Faraday’s constant (F = 96,487 C/
mol). A number of experiments were performed applying
2.5, 5, 7.5, 10, and 12.5 mA/cm2, while the other operating
factors were kept constant in their center point to understand
the influence of the current density on the electrocoagulation
process. Figure 5a shows the effect of the current density

Table 6  CCD table with the Run no. Parameters Removal efficiency (%)
actual and predicted values of
removal efficiency (%) A B C D Actual Predicted

1 − 1 + 1 + 1 + 1 79.25 75.79

2 − 1 − 1 + 1 − 1 37.77 40.86
3 + 1 − 1 + 1 + 1 48.64 49.93
4 + 1 − 1 − 1 + 1 32.23 37.65
5 + 1 + 1 + 1 − 1 47.24 43.16
6 0 0 0 0 55.66 54.98
7 + 1 + 1 − 1 − 1 26.38 30.88
8 − 1 + 1 − 1 + 1 76.23 76.65
9 0 0 − 2 0 57.30 52.27
10 + 2 0 0 0 19.56 18.03
11 − 1 − 1 + 1 + 1 66.99 61.71
12 0 0 0 0 54.71 54.98
13 0 0 0 + 2 67.72 73.83
14 − 1 + 1 − 1 − 1 51.34 55.80
15 − 1 0 0 0 51.37 52.72
16 0 0 + 2 0 59.45 59.69
17 0 − 2 0 0 40.25 40.90
18 − 1 − 1 − 1 + 1 72.16 69.57
19 + 1 + 1 + 1 + 1 64.08 64.01
20 − 1 − 1 − 1 − 1 34.63 41.72
21 + 1 + 1 − 1 + 1 59.37 53.73
22 + 1 − 1 + 1 − 1 28.24 29.08
23 0 0 0 − 2 42.28 37.13
24 0 0 0 0 56.02 54.98
25 + 1 − 1 − 1 − 1 18.83 18.80
26 − 1 + 1 + 1 − 1 54.19 54.94
27 0 + 2 0 0 63.96 69.06

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5416 International Journal of Environmental Science and Technology (2019) 16:5409–5420
Fig. 3  Optimal condition obtained through CCD method
Fig. 4  Normal probability plot of residuals
on the propiconazole removal efficiency. It is evident that
the removal efficiency improved by increasing the current
density. As stated in Eq. 10, higher current density leads
to higher generation of Al ions, and consequently, it can
enhance the electrocoagulation removal efficiency.
13
The effect of the electrolysis duration
One of the essential factors affecting the removal efficiency
of the electrocoagulation progression is the electrolysis
duration. To explore the influence of this factor, a series
of experiments were conducted on propiconazole solution
regarding various time durations in the range of 10–60 min.
Logically, increasing the electrolysis time duration leads to
higher elimination efficiency. Indeed, according to Faraday’s
law, the quantity of aluminum released from anode depends
on the electrolysis time duration and current density. Thus,
by raising the time of reaction, more aluminum releases from
anode surface, and consequently, the propiconazole removal
enhances. As can be observed in Fig. 5b, with increase in the
electrolysis duration, the removal efficiency increases from
about 40% after 10 min to about 70% after 60 min. Hence,
the process time duration is an important factor with positive
effect on the response.
The effect of the solution conductivity
In order to evaluate the impact of the solution conductivity
on the propiconazole removal efficiency, all experiments
were carried out using NaCl as the supporting electrolyte
in the range of 0.5–2.5 mS/cm. As it is obvious in Fig. 5c,
International Journal of Environmental Science and Technology (2019) 16:5409–5420 5417
Fig. 5  Propiconazole removal efficiency versus. a the current density, b the time duration, c the solution conductivity and d the initial concentra-
tion of propiconazole
the solution conductivity had remarkable influence on the
removal percentage. Indeed, increasing the quantity of NaCl
in the solution led to higher conductivity and released more
chloride ions contributing to enhancement of the elimination
efficiency. It can be described by this fact that the presence of
propiconazole resulted in the construction of an impenetrable
passive film on the surfaces of the electrodes. However, the
presence of chloride ions omitted this passivation due to their
catalytic action and increased the availability of aluminum
hydroxide and consequently improved the removal efficiency
of the process (Lakshmipathiraj et al. 2008; Aber et al. 2009).
The effect of the initial concentration
The initial concentration is another remarkable factor in elec-
trocoagulation progression. The influence of this factor on the
removal efficiency is depicted in Fig. 5d. As demonstrated
in this figure, by increasing the initial concentration up to
20 mg/L, the removal efficiency increased. However, more
increment in initial concentration caused a descending trend
in the removal efficiency. This can be attributed to this fact
that there is a threshold limit for the elimination. Regarding
the cases with low initial concentrations, the removal easily
reached the threshold limit. In other words, the electrolysis
of water conquered these low amounts of contamination and
eliminated them from wastewater. By increasing the initial
concentration of propiconazole, water electrolysis could not
eliminate the whole contamination, and subsequently, the
removal efficiency effectually decreased. Moreover, according
to Faraday’s law, the amount of the produced Al ions remained
constant at the same constant current density and time duration
for the all initial concentrations of the contaminant. As a result,
13

5418 International Journal of Environmental Science and Technology (2019) 16:5409–5420

the Al ions produced at high initial concentrations of propi-
conazole are insufficient to reduce all of the contaminants.
The effect of the initial pH
As mentioned before, pH was not identified as an essential
factor for the electrocoagulation process in this study. As an
explanation, in high acidic media, the appearance of hydro-
nium ions ­(H3O+) increases significantly. Also, the water
hydrolysis which leads to the production of H ­ + and O
­ H− spe-
−
cies increases in these media. Moreover, ­OH is the principal
species for the decomposition and removal of pollutants in
aqueous solutions. However, the numerous ­H3O+ ions in the
solution play as a huge barrier in front of ­OH− ions. Besides,
the generation of ­Al3+ ions results in increment of ions inter-
ference. Therefore, there is no expectation of high removal
efficiency in high acidic media.
On the other hand, in basic media, according to the pres-
ence of ­OH− ions, high removal efficiencies are anticipated.
However, as mentioned above, the presence of ­Al3+ ions
causes ions interference and the generation of new species
which are not effectual in the removal of propiconazole due to
the following reactions (Amooey et al. 2014):
Al(OH)3 + OH− → Al(OH)−4 (11)
Al(OH)−4 + OH− → Al(OH)2−
5 (12)
Al(OH)−5 + OH− → Al(OH)3−
6 . (13)
Also, the negatively charged aluminate ions may be formed
according to the following reaction:
Al(OH)3 + OH− → AlO−2 + 2H2 O. (14)
Nevertheless, the removal efficiencies in high basic media
are similar to high acidic ones, and consequently, pH was
not recognized as an effective factor. By performing fur-
ther experiments, it was found that the maximum removal
efficiency is occurred at neutral pH. Moreover, it was dem-
onstrated that pH had no interactions with the other factors.
Thus, pH was ignored, and the process was carried out con-
sidering the other four factors.
concentrations, firstly, an ascending trend in removal effi-
ciency is sensible; however, by more increment in the ini-
tial concentration, a downward trend is observable. It can be
demonstrated that by increasing the current density, there is
no change in the maximum quantity of the removal efficiency;
however, this maximum occurred at a higher initial concentra-
tion of propiconazole (30 mg/L). This is due to the fact that
increasing the current density contributes to increment of the
hydrolysis rate.
Conclusion
In the present study, the efficiency of the electrocoagula-
tion process for propiconazole removal was examined, and
also, the effects of numerous factors such as the initial propi-
conazole concentration, the current density, the initial pH,
the solution conductivity, and the electrolysis duration were
considered. The RSM method based on CCD was used for
correlative modeling and simultaneous optimization of the
above-mentioned factors. The results demonstrated that:
(1) pH is not a significant factor for removal of propicona-
zole in electrocoagulation process and it was omitted.
(2) Neutral pH was an ideal pH condition to reach the
maximum removal efficiency.
(3) A quadratic correlative model was attained for propi-
conazole removal.
(4) Increasing in the current density, the solution conduc-
tivity and the electrolysis duration resulted in higher
elimination efficiency.
(5) An interaction between the initial concentration and the
current density was detected.

Investigation of the probable interactions

Interactions may significantly appear when the effect of one

factor depends on the level of another one. In this study, the
results indicated the interaction between the current den-
sity and the initial concentration of propiconazole. Figure 6
depicts this interaction in which the red and black lines are
related to the lowest (2.5 mA/cm2) and the highest (12.5 mA/
cm2) current density values. As it can be observed, regard- Fig. 6  Interaction between the initial concentration and the current
ing the lowest and the highest levels of propiconazole initial density

13
International Journal of Environmental Science and Technology (2019) 16:5409–5420 5419
(6) The highest propiconazole removal efficiency (79.83%)
was achieved by applying the initial concentration of
25.93 mg/L, the time duration of 36.44 min, the current
density of 10.95 mA/cm2, and the solution conductivity
of 2.44 mS/cm.
Acknowledgements  The authors wish to thank all who assisted in
conducting this work.
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