Chemosphere 207 (2018) 690e698

Contents lists available at ScienceDirect

Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

Transformation products and degradation pathway of textile industry

wastewater pollutants in Electro-Fenton process
Parminder Kaur, Jai Prakash Kushwaha*, Vikas Kumar Sangal
Department of Chemical Engineering, Thapar Institute of Engineering & Technology, Patiala, Punjab, India

h i g h l i g h t s

Continuous electrocatalytic treatment of real textile wastewater was performed.

Most of originally present organic compounds were completely mineralized/degraded.



Chlorine based oxidants and OH radicals mineralized/transformed the pollutants.

Optimum steady state time was found to be 137 min with 142 min retention time.

Toxicity bioassay test showed increased exposure from 1 h to 96 h for 100% mortality.

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

Article history: In this study, pollutants from textile industry wastewater were transformed/oxidized using Ti/RuO2
Received 11 March 2018 electrode by Electro-Fenton (EF) method in a continuous reactor. The performance was evaluated in
Received in revised form terms of % COD removal, % color removal and energy consumed. Electrolysis time, retention time, current,
18 May 2018
and ferrous sulphate concentration as Fenton catalyst were selected as EF process parameters. To
Accepted 19 May 2018
Available online 24 May 2018
determine the optimum operating conditions multiple response optimization with desirability approach
based on central composite design under response surface methodology was used. Spectrophotometric
Handling Editor: E. Brillas and GC-MS analysis were performed to identify the degraded/transformation compounds, and on this
basis degradation mechanism during EF process as well as disposability of treated wastewater was
Keywords: analyzed. Further, bioassay test of treated textile wastewater was conducted for toxicity analysis in view
Textile industry wastewater of its disposal quality.
Electro-Fenton Results showed that all the components of textile wastewater were totally eliminated/transformed in
COD removal lower molecular weight compounds after EF treatment of textile effluent. Further, bioassay test analysis
Color removal
confirmed the nontoxic nature of treated wastewater.
TiRuO2 anode
© 2018 Elsevier Ltd. All rights reserved.
Transformation products

1. Introduction stability of dyes and other chemicals in textile wastewater, make it

Water contamination is a huge issue that the world is con-
fronting today. It is expanding with each passing year, making grave
and hopeless harm to the earth and environment. Textile industries
are considered to be a major containment to the fresh water
because of high toxicity and non-biodegradability of dye stuff and
other chemicals. Direct discharge of textile wastewater is restricted
to the environment by various environmental/pollution regulatory
agencies. Unfortunately, due to biological resistance and chemical
* Corresponding author.
E-mail addresses: jps_kag@yahoo.co.in (J.P. Kushwaha), vksangal@gmail.com
(V.K. Sangal).
hardly treated by the conventional treatment methods (Georgiou
et al., 2002; Meric et al., 2004; Izares et al., 2006; Chen and Liu.,
2012; Bansal et al., 2013; Kaur et al., 2017), however, if treated
huge volume of secondary pollutants are generated. Therefore,
researchers have focused toward the treatment without generating
secondary pollutants. Among all promising techniques, electro-
oxidation is efficient to degrade toxic compounds in an aqueous
phase, and demonstrated their great performance for the treatment
of textile wastewater. However, generation of chloro-organic
compounds during the treatment process is major drawback of
electro-oxidation process. This drawback can be overcome by
Electro-Fenton process (EF) (Brillas et al., 2009). The efficiency of
the EF process predominantly depends on H2O2 production rate, O2
solubility, pH, anode material, Fenton catalyst and current intensity.

https://doi.org/10.1016/j.chemosphere.2018.05.114
0045-6535/© 2018 Elsevier Ltd. All rights reserved.
 P. Kaur et al. / Chemosphere 207 (2018) 690e698
Fenton catalyst concentration and type significantly affect the EF
treatment efficiency. Various catalyst are reported in literature but
Fe2þ or Fe3þ proved good catalytic characteristics even at lower
concentrations (Sire
s and Brillas, 2012). EF is based on the degra-
dation of pollutants by the action of both Fenton's reaction Eq. (2) in
the bulk and anodic oxidation at the anode surface Eq. (4). H2O2 is
continuously generated in the solution during electrolysis in EF
process due to two electron oxygen reduction at cathode (Brillas
et al., 2009; Sire
s et al., 2014) in an acidic medium Eq. (1), and


ferrous ion added into the system analogously generates the OH
radicals in the classical Fenton's reaction Eq. (2). At the same time,
in this process, the ferrous ion is regenerated at the cathode Eq. (3).
Ferric ions generated during EF process for monomeric and poly-
meric hydroxyl complexes.
O2 þ 2Hþ þ 2e / H2O2 (1)
Fe2þ þ H2O2 / Fe3þ þ OH þ OH


(2)
Fe3þ þ e / Fe2þ (3)
M(H2O) / M( OH) þ Hþ þ e


(4)
Dimensionally stable anodes (DSAs) are stable during electrol-
ysis, have high oxygen overvoltage and does not produce secondary
pollutants (Brillas and Casado, 2002; Nasr et al., 2005). There are
number of DSAs i.e titanium coated RuO2, IrO2, SnO2, PbO2; boron
doped diamond electrodes; Pt/Ti etc. used by various researchers
for electrochemical treatment processes (Wang et al., 2005; Zhou
and He, 2007; Martinez-Huitle and Brillas., 2009; Salazar et al.,
2012; Oturan et al., 2012; Pajootan et al., 2014; Mukimin et al.,
2015; Mukimin et al., 2017). Fenton's reaction is applied in acidic


pH of 2.8e3.0 (Sun and Pignatello, 1993) to efficiently produce OH.
Ti/RuO2 electrodes are highly stable in acidic medium and it is an
active DSAs electrode, provide large surface area for the adsorption
of pollutants (Santos et al., 2010). Ti/RuO2 anode also favours the
chlorine species-mediated oxidation in bulk. Due to this carcino-
genic/toxic chlorinated organic compounds may be generated


during the EF process. OH radical generation is prominent in EF
process, which can mineralized chlorinated organic compounds by


OH mediated oxidation. Various investigations prove that EF is
well able to reduce the strong nature, carcinogenic and toxic
behaviour of textile wastewater (Santos et al., 2010; Salazar et al.,
2012; Nidheesh and Gandhimathi, 2014; Lin et al., 2014; Pajootan
et al., 2014; Ghanbari and Moradi, 2015; Asghar et al., 2015;
Garcia-Segura and Brillas, 2016). In literature, no study has been
reported on the textile industry wastewater treatment by contin-
uous EF method. Researchers just examined about the treatment of
simulated/model textile wastewater. Textile industry wastewater
has number of components, which can advance or thwart the
treatment process. Subsequently, execution examination and
appropriateness of EF process require more investigation on textile
industry wastewater.
In the present study, treatment of textile industry wastewater
was performed by EF method in continuous mode using Ti/RuO2
electrodes. The EF process was optimized for various process pa-
rameters i.e. elapsed time (t), retention time (RT), current (i) and
concentration of ferrous sulphate (CFe) (Fenton catalyst) for %
chemical oxidation demand (COD) removal (X1), % color removal
(X2) and energy consumed (X3). Spectrophotometric and GC-MS
analysis at optimum conditions was performed to identify the
degraded/transformation compounds for degradation mechanism
during EF process as well as disposability of treated wastewater.
Further, bioassay test was performed for toxicity analysis of treated
691
textile wastewater in view of disposal quality. The persuasive
mechanism of the treatment process was also purposed by GC-MS
analysis. Moreover, degradation kinetics in terms of COD removal
and color removal were investigated. Operating cost analysis of the
continuous mode for per Kg of COD removal was also performed to
determine the economic feasibility.
2. Materials and methods
2.1. Wastewater and experimental setup
Textile industry wastewater was collected from Mink Blanket
industry (Ludhiana, Punjab). Textile effluent contains high strength
of dyes that were used in mink blanket industry. The character-
ization of textile wastewater for various water quality parameters is
given in Table SM-1. The Cl content of the textile wastewater was
also analyzed and found to be 1682.50 mgL1 with standard Vol-
hard method. Cubical shape EF continuous reactor was fabricated of
plexi glass sheet. The working volume of the continuous reactor
was 1.5 L. Two electrodes of Ti/RuO2 having dimension of
100 mm  85 mm x 1.5 mm were used as anode (supplied by Tita-
nium Tantalum Products Limited, Chennai, India), whereas two
aluminum electrodes of same dimension were used as cathode.
Electrical power to the electrochemical reactor was supplied by
DIGITECH DC power supply (Model: 4818A10; 0e20 V, 0e5 A;
Roorkee, India). Continuous and steady aeration to the wastewater
was maintained by using air diffusers at the bottom of reactor. The
pH of the textile wastewater was adjusted using AR grade HCl.
Magnetic stirrer was used to for homogenization of the wastewater
during the electro-catalytic reaction. The schematic diagram of the
experimental setup is shown in Fig. SM-1.
2.2. Experimental procedure
The statistical Design-Expert software version 6.06 (STAT-EASE
Inc., Minneapolis, US) was used to design the experiments with
RSM five level central composite design. RSM is a factual strategy
for outlining experimental runs and assessing the impacts of
different parameters on the selected reaction responses. In present
study, the range of selected parameters i.e. t (15e175 min), RT
(50e230 min), i (0.25e3 A) and CFe (0.20e1 mM) were determined
from preliminary experiments (Table SM-2). Anticipated responses
(X) were in terms of X1, X2 and X3. Experiments were conducted, as
per the design matrix (Table 1). Ideal pH for EF process has been
reported to be 3 (Sun and Pignatello, 1993). Therefore, pH of the
textile industry wastewater was adjusted to 3, before the start of
experimental run. Power supply was switched on, and t was
measured from this moment to the withdrawal of the sample. i was
maintained constant during the EF experimental run. Textile in-
dustry wastewater was continuously stirred and agitated with air
and magnetic stirrer. After the desired t power supply was switched
off and sample was drawn from the reactor for further analysis.
2.3. Analysis and optimization
Double beam UV visible spectrophotometer (HACH, DR 5000,
USA) at COD program 1500 mgL1 was used to analyze COD of the
samples. Energy consumption (Z) during the EF treatment was
calculated by the following equation:
ðV  t  iÞ 3
Z¼ 10 (5)
CODf
where, i ¼ current (A); V ¼ voltage (volt); t ¼ elapsed time (h);
CODf ¼ COD removed (mgL-1)
692 P. Kaur et al. / Chemosphere 207 (2018) 690e698

Table 1
Design of Experiment matrix for the Electro-Fenton of textile industry wastewater.

Run t(min) RT (min) i (A) CFe (mM) % COD removal (X1) % Color removal (X2) Energy consumed (X3)

1 95 150 1.25 0.6 73.58 94.13 0.015

2 95 150 1.25 0.2 57 79 0.015
3 135 200 0.75 0.4 69.53 79.14 0.0164
4 55 200 1.75 0.4 53.15 52.42 0.013
5 135 100 1.75 0.8 70.32 80.1 0.0199
6 55 200 0.75 0.8 33.04 62.42 0.014
7 95 150 1.25 0.6 73.58 94.13 0.0175
8 95 150 1.25 0.6 73.58 94.13 0.0175
9 55 100 1.75 0.8 45.42 68.34 0.014
10 175 150 1.25 0.6 85.41 76 0.015
11 55 200 0.75 0.4 43 51 0.0049
12 135 100 0.75 0.4 81.78 99.15 0.0197
13 135 100 0.75 0.8 60.05 72.52 0.01
14 135 100 1.75 0.4 80.63 89.33 0.0219
15 135 200 1.75 0.4 73.18 77.17 0.02
16 95 150 0.25 0.6 27 68.82 0.003
17 95 250 1.25 0.6 57.12 70.8 0.0189
18 135 200 0.75 0.8 54.07 78.54 0.0094
19 95 150 1.25 0.6 73.58 94.13 0.015
20 15 150 1.25 0.6 45.54 49.05 0.0009
21 95 150 2.25 0.6 52.14 83.67 0.018
22 95 50 1.25 0.6 60.61 73.34 0.0175
23 135 200 1.75 0.8 63.19 92.36 0.0188
24 55 100 0.75 0.8 28.22 54.32 0.0056
25 95 150 1.25 0.6 70.58 94.13 0.0175
26 95 150 1.25 1 42.72 79.49 0.0198
27 55 100 1.75 0.4 59.19 68.74 0.01
28 95 150 1.25 0.6 66.03 84.54 0.0198
29 55 100 0.75 0.4 40 75.42 0.007
30 55 200 1.75 0.8 50 70.22 0.023

GC-MS of treated textile wastewater (at optimum conditions)
and untreated textile wastewater was carried out to identify
various transformation products formed during EF degradation and
for disposal study. PerkinElmer Clarus 500 MS instrument with
fused silica capillary columns (25 m  0.20 mm internal diameter)
coated with a 5% diphenyl/95% dimethyl polysiloxane was used for
GC-MS analysis. The split/split less injector mode was used at
injector temperature 350  C. Helium was used as carrier gas with a
flow rate of 1 mL min1. The temperatures corresponding to the
inlet line and ion source were set at 250  C and 300  C, respectively.
Run time for GC-MS analysis was 30 min.
CCD under RSM permits the analysis of experimental data and
optimization of impacts of parameters i.e. t, RT, i, and CFe on X1, X2
and X3. Polynomial Eq. (6) was used to determine the pertinent
model terms along the error function. Where, q0 is the constant
coefficient of model; qi represents the linear coefficient; qii and qij is
the interaction coefficient; k is the number of the factors or vari-
ables; xi & xj are variables; and kr is the considerable error. The in-
fluence of the process variables on the responses were analyzed
from an analysis of variance (ANOVA).
X
k X
k XX
X ¼ q0 þ qi xi þ qii x2i þ qij xi xj þ kr
i¼1 i¼1 i<j
textile industry wastewater. The best fitted RSM model was
quadratic model. The quality of quadratic model was evaluated by
exploiting sequential F-test, model summary and subsequent
ANOVA. The adequate precision for the responses X1, X2 and X3 was
23.936, 17.712, 16.273 respectively, which indicate an adequate
signal that the model can be used to navigate the design space. The
value of adequate precision above 4, it indicates that suggested
model is efficient to analyze the relation between variables and the
responses. The model's lack of fit F-values were insignificant for X1,
X2 and X3. The statistical analysis using ANOVA for the responses X1,
X2 and X3 of the continuous EF treatment of textile wastewater,
with a model Fe value as shown in Table 2. It explicit that, the
quadratic model was significant with 95% confidence level. The
total variations in the actual versus predicted were less than 1.5%.
High values of coefficients of determinants R2, Adjusted R2 and
predicted R2 (Table SM-3) showed that the experimental values are
in good agreement with the predicted values. Further, the valida-
tion of quadratic model was supported by the predicted versus
observed plots and residual plots (Fig. SM-2). The quadratic model
best fitted the experimental data, and the models is represented by
Eqs. (7)e(9) in terms significant process parameters. In case of X1*t,
CFe, i, i2, RT 2, C2Fe, t*RT, t*i; X2*t, RT, i, t2, RT 2, i2, CFe 2, RT*CFe, i*CFe;
(6) X3*t, i, t2, i2, t*RT, t*CFe, RT*CFe, i*CFe were significant model terms.

Multi-response optimization using desirability function
approach was used to simultaneously maximize the % COD
removal, % color removal, and to minimize the energy
consumption.
3. Results and discussion
3.1. Regression model fitting and ANOVA
Experiments suggested by CCD (Table 1) were performed to
determine the response X1, X2 and X3 of continues EF process for
X1 ¼ 71.82 þ (11.69  t) þ (5.65  i) e (5.2  CFe) e (2.72  R2T) e
(7.55  i2) e (4.97  C2Fe) e (2.45  t x RT) e (2.6  t x i) (7)
X2 ¼ 92.53 þ (9.14  t) e (2.07  RT) þ (2.33  i) e (7.39  t2) e (5 
R2T) e (3.96  i2) e (3.2  C2Fe) þ (6.32  RT x CFe) þ (3.77  i x CFe)(8)
X3 ¼ 0.017 þ (3  103 x t) þ (3.4  103 x i) e (2.1  103 x t2) e
(1.52  103 x i2) e (1.6  103 x t x RT) e (2.6  103 x t x
CFe) þ (1.3  103 x RT x CFe) þ (1.2  103 x I x CFe) (9)
 P. Kaur et al. / Chemosphere 207 (2018) 690e698 693

Table 2
Analysis of variance for the %COD removal, % color removal and energy Consumption.

% COD Removal %Color Removal Energy Consume

Source Sum of Squares DF Mean Square F-Value Prob > F Sum of Squares DF Mean Square F-Value Prob > F Sum of Squares DF Mean Square F-Value Prob > F

Model 7055.1 14 503.9 36 <0.0001 5354.6 14 382.5 24 <0.0001 9.3  104 14 6.6  105 20.5 <0.0001
t 3277.6 1 3277.6 234.2 <0.0001 2004.4 1 2004.4 125.9 <0.0001 2.2  104 1 2.2  104 68.6 <0.0001
RT 46.5 1 46.6 3.3 0.0881 103.0 1 103.0 6.5 0.0224 8.4  106 1 8.4  106 2.6 0.1270
i 766.9 1 766.9 54.8 <0.0001 130.1 1 130.1 8.2 0.0119 2.9  104 1 2.9  104 90.5 <0.0001
CFe 648.0 1 648.0 46.3 <0.0001 6.6 1 6.6 0.4 0.5298 5.4  106 1 5.4  106 1.7 0.2142
t2 31.3 1 31.3 2.2 0.1552 1497.4 1 1497.4 94.1 <0.0001 1.3  106 1 1.3  104 39.6 <0.0001
RT 2 203.2 1 203.2 14.5 0.0017 686.4 1 686.4 43.1 <0.0001 4.5  106 1 4.5  105 1.4 0.2541
i2 1561.6 1 1561.5 111.5 <0.0001 429.8 1 429.8 27 0.0001 6.3  105 1 6.3  105 19.7 0.0005
CFe 2 678.3 1 678.3 48.4 <0.0001 282.4 1 282.4 17.7 0.0008 1.2  106 1 1.2  106 0.4 0.5561
t* RT 95.8 1 95.9 6.9 0.0194 17.8 1 17.8 1.1 0.3071 3.9  105 1 3.9  107 12.3 0.0031
t*i 108.2 1 108.2 7.7 0.0140 3.0 1 3 0.2 0.6694 7.2  105 1 7.2  107 0.2 0.6424
t * CFe 22.2 1 22.2 1.6 0.2275 52.5 1 52.5 3.3 0.0893 1.1  104 1 1.1  104 33.6 <0.0001
RT * i 1.9 1 1.9 0.1 0.7120 15.9 1 15.9 1 0.3328 2.7  106 1 2.7  106 0.8 0.3722
RT * CFe 22.6 1 22.6 1.6 0.2228 639.7 1 639.7 40.2 <0.0001 2.5  105 1 2.5  105 7.8 0.0138
i* CFe 29.4 1 29.5 2.1 0.1674 227.0 1 227.0 14.3 0.0018 2.5  105 1 2.5  105 7.6 0.0146
Residual 209.9 15 13.9 238.7 15 15.9 4.8  105 15 3.2  106
Lack of Fit 162.4 10 16.2 1.7 0.2875 162.1 10 16.2 1.1 0.5073 3.2  105 10 3.2  106 1 0.5571
Cor Total 7265.0 29 5593.3 29 9.7  104 29

3.2. Process parameters effects
The relative contribution of EF parameters: t, RT, i and CFe on X1,
X2 and X3, were evaluated using ANOVA based p-values. (P < 0.05)
indicates that model term were significant i.e. parameters had a
significant influence on the variability of the responses. The syn-
ergistic and antagonistic effect of interactive parameters on the
responses was studied in 3-D response surface graph.
The interactive effect of parameters i, t, RT and CFe for the X1 is
represented in Fig. 1a, b and c. It has been seen that at the higher
and lower values of i, X1 was found always decreasing. A sharp
increase in X1 with increasing t can be observed with rise in i from
0.25 to z1.25 A. However, for i ¼ 1.25 A, at steady state
(t ¼ 140 min), showed maximum X1 (Fig. 1a). The effect of
increasing CFe with increased i on the X1 is shown in Fig. 1b.
Increasing CFe from 0.2 mM to 0.4 mM increases the X1 at all i
values, and decreased sharply for all CFe > 0.4 mM. Increasing i
increases the X1 up to 1.25 A, and for i > 1.25 A, X1 decreased
sharply. RT and t are the crucial parameters for continuous EF
treatment process. Fig. 1c illustrates that the X1 increases with
increasing RT value. However, X1 is marginally affected for all
RT > 150 min. This trend was observed true at any t value. Further, at

Fig. 1. 3D response surface and contour plots for the EF of textile industry wastewater; (a, b, c) %COD removal versus i, t, CFe and RT; (d, e, f) %color removal versus i, t, CFe and RT. (For
interpretation of the references to color in this figure legend, the reader is referred to the Web version of this article.)
694 P. Kaur et al. / Chemosphere 207 (2018) 690e698
lower RT value (RT < 150), increasing t value always increases the X1.
However, for all RT > 150 min, increasing t upto z140 min first in-
creases the X1 value and it is nearly unaffected for t > 140 min.
Therefore, observed steady state time is z 140 min.
The influences of parameters i, t, RT and CFe on the X2 are also
illustrated in Fig. 1d, e and f. Similar trend of effects of these pa-
rameters on X2 was observed as on X1. Fig. 1d shows the interaction
of CFe and i on the X2. It can be observed that X2 is increasing for
0.2 mM < CFe< 0.4 mM, however, for all CFe> 0.4 mM, it is
decreasing. This effect of increasing CFe on X2 was found true for all i
values. Further, increasing i up to i ¼ 1.25 A, X2 was found
increasing, and was observed decreasing beyond 1.25 A. Fig. 1e
shows the interaction of CFe and RT on the X2. Similar to X1, X2 was
also observed increasing with the RT values up to RT z 140 min.
Beyond RT z 140 min, X2 was observed decreasing sharply. This
was found true at all CFe values. In Fig. 1f, it can be seen that the
increasing t increases the X2 up to t z 135 min, and beyond this the
change in X2 is marginal. This was true for all RT values. However, at
any t value, increasing RT value, first increases the X2 up to
z140 min and then starts decreasing beyond 140 min of RT value.
Fig. 2a and b attributed that energy consumption is minimum at
the steady state. In the higher range of RT, X3 was increasing with
the increase in t. X3 was also increased with the increase in i at all
the t values as shown in Fig. 2b.


Investigation of interaction parameters asserted that OH
mediated direct oxidation and chloro species generated via Eqs.
(13) and (14) mediated indirect oxidation (Brillas and Casado, 2002;
Sire
s et al., 2014), since textile wastewater was rich of chloride ions,
was responsible for the expulsion of COD and color at the steady


state condition. The OH generated at anode is adsorbed on the
surface of anode via Eq. (10), and the COD/color is reduced through
oxidation via Eqs. (11) and (12) (Chen, 2004; Santos et al., 2011).
Ti/RuO2 þ H2O / Ti/RuO2(
OH) þ Hþ þ e
COD/color þ Ti/RuO(2þ1) / (COD/color)̶ O þ Ti/RuO2
COD/color þ Ti/RuO2(
OH) / CO2 þ Hþ þ e þ Ti/RuO2
2Cl⁻ / Cl2 þ 2e⁻
Cl2 þ H2O / HOCl þ H⁺ þ Cl⁻
COD/Dye þ HOCl/Cl2 / chlorinated organic compounds
(COC) þ H2O
Fig. 2. 3D response surface plots for the EF of textile industry wastewater Energy consumption versus i, t, RT.
COC þ Ti/RuO2(
OH) / CO2 þ Hþ þ e þ Ti/RuO2 þ Cl (16)
The steady state of a continuous EF reactor for textile waste-
water was attained at z2.3 h of elapsed time for COD removal and
it is 2.1 h for color removal. It implied that color removal was rapid
process, which indicates that coloring components of the dyes
degraded into colorless organic and inorganic products, and further
degradation was followed by
OH mediated oxidation. COD removal
was lacking behind because high bond dissociation energy of
colorless organic and inorganic products. It was evident that,
increasing RT after z142, disturbs the steady state profile so, X1 and
X2 decreases (Korbahti and Tanyolac, 2009). It can also be
concluded that due to disturbance of steady state steric hindrance
between the reaction molecules increases. It ultimately affected the
degradation process. CFe and i were significant parameter in EF
process. CFe >5.5 at i > 1.01, influences the negative impact on the
electro-chemical reaction, because of scavenged hydroxyl radicals
and generation of hydroperoxyl radicals (Eq. (17)) (Brillas et al.,
2009), which have low oxidation power. Increase in i and at
higher CFe, in the wastewater also enhanced the competitive reac-
tion between the hydroxyl ions and the ferrous ion which could
decline the X1 & X2 process has been shown in Eq. (18).
(17)
Fe2þþ OH/Fe3þþOH


(18)


It was proclaimed that, COD and color removal were due to OH
mediated oxidation on the surface of Ti/RuO2 anode and mediated
oxidation by Cl2 and HOCl. Chloro-mediated oxidation attributed


chlorinated organic compounds, which further undergo OH
mediated oxidation in the bulk. The X3 in continuous EF process
was relatively increased at low RT and the minimum X3 was ob-
(10) tained for 2.3 h of RT. The EF reactor could be operated at optimum
RT for cost driven purpose. Increase in i > 1.10 A disturbs steady
(11) state condition the X3 increases.
(12) 3.3. Optimization
(13) The optimization of operating parameters with the responses
(X1, X2 and X3) for the treatment of textile industry wastewater
(14) using EF process, multi response optimization technique with
desirability function was carried out (Kushwaha et al., 2011) Eq.
(19). Optimization of the EF process was composed by the set of
(15) constraints as shown in Table SM-4.
 P. Kaur et al. / Chemosphere 207 (2018) 690e698 695

One-sided desirability di is used in the study given by: compounds were observed in the range of l, ~280e345 shown in
8 Fig. SM-3. Low intensity peaks can be seen with l, ~280e310 nm
> 0 and l, ~330e345 nm. Sharp peaks of high absorption intensity with
>
<
>
Xi  Ximin
r if Xi  Ximin l, ~310e330 nm can be seen. Further, there was a radicle change in
di¼ if Ximin < Xi < Ximax (19) the absorption spectra of treated textile wastewater at t ¼ 137 min
>
> Ximax  Ximin
>
: if Xi  Ximax showed there was no high intensity peaks with l, 200e280 nm and
1
~350e400 nm. After EF treatment all aromatic compounds were
eliminated. Small intensity peaks were observed at l, ~280e315 nm
where, Xi is response values, Xi-min and Xi-max is minimum and
and were generated during the EF process indicating the degra-
maximum acceptable values of response i, and r is weight and a
dation of compounds. So, to explore the small intensity trans-
positive constant. Here, weight for all the responses were same and
formed components of treated textile wastewater GC-MS analysis
set to be r ¼ 1.
was performed.
Thus, the desirability for response X1 is calculated by Eq. (20)
Lists of identified compounds of untreated and treated textile
with acceptable X1-min and X1-max values as 27% and 100%, respec-
wastewater are shown in Tables 3a and 3b. Detailed information of
tively (Table SM-4).
identified compounds in untreated textile wastewater is presented
8 elsewhere (Kaur et al., 2018). The identified compounds by GC-MS
> 0
>
<
>
X1  27
 if X1  27 analysis of untreated wastewater were mostly aromatic in nature
d1¼ if 27 < X1 < 100 (20) (Table 3a) and their range was of 200e275 nm, which supports the
> 100  27
>
>
: if X1  100 spectrophotometric analysis of untreated textile wastewater as
1 shown in Fig. SM-3.The highest matching% shown for 3,4-dihydro-
4-(1,3-dioxolan-2-yl)-5,7-dimethoxy-1(2H)-benzopyran-2-one
Similar to equation (20), desirability for responses X2 and X3
and its peak area was also maximum l, ~308. The spectrophoto-
were calculated by equations (21) and (22), respectively.
metric range of polyaromatic compounds was 238e310 ranges
8 (Fig. SM-3) and also identified in GC-MS analysis as shown in
> 0
>
<
>
X2  49
 if X1  49 Table 3b.
d2¼ if 49 < X1 < 100 (21) Since, textile industry wastewater bears high chloride concen-
>
> 100  49
>
: if X1  100 tration, therefore, toxic and carcinogenic chlorinated organic
1 compounds may possibly be generated during the EF process via
Eq. (13)e(15). GC-MS analysis of treated wastewater identifies four
8
> 0 different type of non-chlorinated organic transformation com-
>
<
>
X3  0:0009
 if X1  0:0009 pounds (Dibutyl phthalate, 5,7-Dimethoxy-2,3-dihydro-4H-chro-
d3¼ if 0:0009 < X1 < 0:025 (22) men-4-one, 1-acetamidoadamantane,
>
> 0:025  0:0009
>
: if X1  0:025 Tetradecamethylcycloheptasiloxane), which were not originally
1 present in untreated textile wastewater (Table 3a). Therefore, the
The overall desirability (D) was calculated by the following Eq. treated textile wastewater is free from the toxic and carcinogenic
(23). chlorinated organic compounds. However, from the point of view of
disposability, it is necessary to evaluate the toxicity of the treated
D ¼ ðd1  d2  d3 Þ1=n (23) textile wastewater bioassay for acute toxicity towards possible toxic
transformation/degraded compounds (Table 3b). For this purpose,
where, d1, d2 and d3 are the individual desirability, and n is the standard procedure IS: 6582 with Aploclzeilus panchax organism
number of responses. was followed. Aploclzeilus panchax organisms are sensitive re-
The most appropriate optimization condition was found to be sponders to the water contamination. The organisms were selected
t ¼ 137 min i ¼ 1.10 A, RT ¼ 142 min and CFe ¼ 0.55 mM, which randomly from the stock. The selected organisms were distributed
showed highest overall desirability, D ¼ 0.8. At this optimum at random in the various vessels having test sample. The duration of
condition, the X1, X2 and X3 suggested by RSM under CCD were 85%, the test was 96 h. After 96 h, count of the dead organisms was
94% and 0.017 Wh/mg COD removed respectively. To verify the performed for each vessel after 2, 6, 24 and 48 h, and the death
acceptability of the optimization analysis, actual experiments were numbers or survival of the organisms represented in terms of
performed in duplicate and average values of responses X1, X2 and percentage.
X3 at the optimum condition was found to be 84.16%, 94% and Test result showed 100% mortality within 1 min for the un-
0.015 Wh/mg of COD removed, respectively, which were closer to treated textile wastewater, however, no death was observed in 96 h
the predicted values as shown in Table SM-5. It also demonstrates for treated textile wastewater. Acute toxicity bioassay test proved
that modeling and optimization using RSM under CCD was suc- that the untreated textile wastewater was highly toxic and lethal if
cessfully performed. disposed to water bodies. However, toxicity was sufficiently
reduced for EF treated textile wastewater indicating transformation
products in treated wastewater are not acute toxic and can be safely
3.4. Treated wastewater disposability and electrodes dispose in the environment.
characterization Due to mediated indirect oxidation with Cl2 and HOCl via Eq.
(15), the organics are first converted to toxic and carcinogenic
Disposability study was performed by identifying the trans- chlorinated organic compounds and further may oxidized to CO2
formation products in treated wastewater and compounds/or- via direct oxidation method Eq. (16). Therefore, characterization of
ganics originally present in untreated textile wastewater through anode material is necessary. The composition of electrodes before
spectrophotometric and GC-MS analysis. Also, bioassay test was and after EF treatment was investigated by SEM/EDX. The SEM
performed to test the toxicity of treated wastewater. images of fresh and used Ti/RuO2 electrodes showed almost same
Spectrophotometric analysis showed that all the compounds of morphology as shown in Fig. SM-4. It was observed at 1000
the textile wastewater were degraded but certain new transformed magnification that morphology of the electrodes after EF treatment
696 P. Kaur et al. / Chemosphere 207 (2018) 690e698

Table 3a
Identified compounds of untreated textile waste water by GC-MS Analysis.

S. No. Compound Molecular Mass

1 Tetradecamethylcycloheptasiloxane 519
2 Iron monocarbonyl 1,3 butadiene 1,4, dicarbonic acid diethyl ether 438
3 Adamantan-1-yl(phenyl)[(trimethylsilyl)oxy]acetonitrile 339
4 1,1,1,3,5,7,9,11,11,11-Decamethyl-5-(trimethylsiloxy)hexasiloxane 490
5 3,3,5-Triethoxy-1,1,1,7,7,7-hexamethyl-5-(trimethylsilyloxy)tetrasiloxane 474.917
6 Dodecamethylcyclohexasiloxane 444
7 Decamethylcyclopentasiloxane 370
8 3-Octanol 2-[(R)-(4-methylphenyl)sulfinyl]-1-(trimethylsilyl) 340
9 3-Isopropoxy-1,1,1,7,7,7-hexamethyl-3,5,5-tris(trimethylsiloxy)tetrasiloxane 577
10 (5R,7R,8E,10E)-2,2,3,3,5,15,15,16,16-Nonamethyl-4,14-dioxa-3,15-disilaheptadeca-8,10-dien-7-ol 414.77
11 Benzoic acid, 2,4bis [(trimethyl silyl)oxy]-, trimethylsilyl ester 370
12 Tetracosamethylcyclododecasiloxane 888
13 Octadecamethylcyclononasiloxane 667
14 Icosamethylcyclodecasiloxane 740
15 Silicone oil 9999
16 Trimethylsilyl 3,5-bis[(trimethylsilyl)oxy]benzoate 370
17 Hexadecamethylheptasiloxane 532

Table 3b
Compounds identified after EF treatment of textile waste water by GC-MS Analysis.

S. No. Compound Retention Time Molecular Mass Matching % Remark

1 Butyl phthalate 20.02/21.51/21.16/21 278 95.2%/81.3%/92.9% Transformation products

2 5,7-Dimethoxy-2,3-dihydro-4H-chromen-4-one 24.06/15.12 208 84% Transformation products
3 1-acetamidoadamantane 21.91 193 90.7% Transformation products
4 Tetradecamethylcycloheptasiloxane 15.65 519 84% Transformation products

is not much affected except small loss of RuO2 coating. Elemental
distribution on the surface of fresh and used Ti/RuO2 electrodes was
determined through EDX. EDX analysis showed the presence of
Titanium (68.65%), oxygen (24.36%), ruthenium (15.15%) elements
on the surface of fresh electrode. EDX analysis of used electrodes
showed the presence of carbon (3.48%), oxygen (45.66%), titanium
(35.71%), and ruthenium (6.99%) on the surface. The presence of
carbon on the surface of used electrodes showed that
OH mediated
oxidation was prominent in the degradation process.
3.5. Degradation mechanism
The spectrophotometric analysis and GC-MS analysis shows the
presence of poly-aromatic compounds in the treated textile
wastewater. The detected compounds contains low molecular
weight elements such that silicon, carbon, hydrogen, oxygen and
nitrogen. In the present study, two types of degradation processes
were involved in the degradation of textile wastewater pollutants:

untreated samples shows almost complete mineralization occurs
OH mediated oxidation and chlorine species mediated oxidation.
Transformation compounds generated during the EF treatment
process were very few. The possible degradation mechanism of
pollutants in textile wastewater is shown in Fig. 3..
The compounds detected in textile industry wastewater i.e.
Decamethylcyclopentasiloxane, Trimethylsilyl 3,5-bis[(trime-
thylsilyl)oxy]benzoate, Adamantan-1-yl(phenyl)[(trimethylsilyl)
oxy]acetonitrile, (5R,7R,8E, 10E)-2,2,3,3,5,15,15,16,16-Nonamethyl-
4,14-dioxa 3,15-disilaheptadeca-8,10-dien-7-ol, 3,3,5-Triethoxy-
1,1,1,7,7,7-hexamethyl-5-(trimethylsilyloxy)tetrasiloxane, 3-
Isopropoxy-1,1,1,7,7,7-hexamethyl-3,5,5-tris(trimethylsiloxy)tetra-
siloxane, 1,1,1,3,5,7,9,11,11,11-Decamethyl-5-(trimethylsiloxy)hex-
asiloxane, Octadecamethylcyclononasiloxane,
Icosamethylcyclodecasiloxane, Iron monocarbonyl 1,3 butadiene
1,4, dicarbonic acid diethyl ether, Silicone oil, Hex-
adecamethylheptasiloxane undergo
OH mediated oxidation.
Chlorine species mediated degradation also exists because
textile industry wastewater was rich in chloride content. It was
observed that compounds of the textile industry wastewater were
completely eliminated and some compounds undergo partial
degradation and transformed into Dibutyl phthalate, 5,7-
Dimethoxy-2,3-dihydro-4H-chromen-4-one, 1-
acetamidoadamantane, Tetradecamethylcycloheptasiloxane. Also,
due to chlorine species mediated oxidation of these compounds,
toxic chlorinated compounds may be generated. However, the final
transformed compounds detected (Table 3b) showed the absence
of chlorinated-compounds. Since, the degradation process is
mediated by the chlorine species, chlorinated organic compounds
are generated during the EF process, however, those compounds
are oxidized by
OH mediated oxidation in bulk (Fig. 3). It can also be
confirmed from the absorption band of spectrophotometric anal-
ysis with l, 200e280 nm (Fig. SM-3) that no chlorinated compound
was present in the treated textile wastewater. Small spectropho-
tometric bands of transformed compounds were observed for l,
280e340 nm due to partial degradation. The comparison of the
spectrophotometric analysis and GC-MS analysis of treated and
during the EF process. Therefore, it can be concluded that,
OH
mediated oxidation was prominent in case of EF treatment process.
3.6. Kinetic of EF degradation process
At optimum parameters of the EF process, kinetics of COD and
color removal was studied. In present study, Second order model is
fitted to the experimental data obtained from treatment of the
textile effluent by EF process at optimum conditions (i ¼ 1.10,
CFe ¼ 0.55 mM, RT ¼ 142 min, t ¼ 137 min) for COD removal and
Color removal according to the rate equation.
dCS
¼ k½CS 2 (24)
dt
On integrating between known limits and rearranging, the
above model becomes
 P. Kaur et al. / Chemosphere 207 (2018) 690e698
Fig. 3. Persuasive mechanism of degradation of textile industry wastewater by EF process.
1 1
¼ þ Kt (25)
½Cs ½Co
where, Co initial color intensity or initial COD concentration, Cs final
color intensity or final COD concentration, t elapsed time (min), k
second order rate constant (mg min L1). Fig. SM-5 showed the
values of rate constant of second order reaction kinetics are
2  105 and 9.5  103 min1 along with the value of R2 value
0.9931 and 0.9966 for X1 and X2, for COD and Color removal,
respectively. It was evident, that COD removal and Color removal
was successfully described from kinetic study, but color removal
was faster than COD removal.
3.7. Operational cost analysis
Operational cost analysis is important within the criteria for the
application of EF process at the industrial scale. For the application
of EF treatment method operational cost is calculated in terms of
per Kg of COD removal. In present study, the specific energy
consumed is ~15 kWh/kg of COD removed for continuous EF
treatment of textile wastewater at optimum operational conditions.
The total operational cost consists of number of costs but in case of
EF electrodes and energy cost is most important. The Ti/RuO2
electrodes purchased for EF from Titanium Tantalum Products
Limited, Chennai, India at the cost of $83 and its life span is 2.5 y at
697
the voltage <6. The cost of electricity in India is ~ $ 0.083/kWh. So,
the total operating cost is $9.75/kg of COD removed. It is calculated
by adding electrode cost and energy cost. In literature, it is reported
that electric energy consumed during the electrochemical process
is varies from 1.2 to 200 KWh/kg of COD removal (Vlyssides and
Israilides, 1997; Vlyssides et al., 1999, 2002; Kushwaha et al.,
2010). This variation in energy consumption or cost analysis de-
pends upon the nature of wastewater and electrode material.
Certain authors have investigated operating cost using different
types of electrodes and wastewater. Operating costs at the opti-
mum conditions for dye house wastewater was 7.282 $/kg COD for
Fe electrode and 14.257 $/kg COD for Al electrode using continuous
electro-coagulation process (Kobya et al., 2016). The reported
operating cost for Pistachio processing industry wastewater was
17.06$/kg COD by electro-Oxidation Using Graphite Anode (Fill
et al., 2014). Batch and continuous electrochemical oxidation of
textile wastewater using serpentine flow reactor operational cost
estimation was 10.2 and 5.83 USD m3 (Pillai and Gupta, 2017). It is
concluded that EF is a cost effective process among all the EAOP's
because it doesn't produce any secondary pollutants. The waste-
water treated by EF process is not toxic for the environment and
further treatments are not necessary so, single process is efficient to
treat non-biodegradable and toxic wastewaters.
698 P. Kaur et al. / Chemosphere 207 (2018) 690e698
4. Conclusions
The optimization of operational parameters in continuous mode
for the textile industry wastewater was done successfully. Spec-
trophotometric and GC-MS analysis clearly showed that
OH
mediated oxidation was prominent in the degradation process of
textile wastewater components. Due to high chloride content in
textile wastewater, chlorinated organic compounds were expected
in the treated wastewater, however, GC-MS analysis revealed
absence of chlorinated organic compounds. Some other non-
chlorinated transformation compounds were detected. This sug-
gested that, the organics (COD/color) are first converted to toxic
and carcinogenic chlorinated organic compounds via indirect
oxidation mechanism through Cl2 and HOCl and further were
oxidized to CO2 via direct oxidation mechanism through
OH.
Further, bioassay test revealed EF treated wastewater is safe to
dispose in the environment.
Acknowledgement
Authors acknowledge to the University Grant Commission, India
to provide MANF fellowship (MANF-2015-17-PUN-49188) to the
first author of this article.
Appendix A. Supplementary data
Supplementary data related to this article can be found at
https://doi.org/10.1016/j.chemosphere.2018.05.114.
References
Asghar, A., Abdul Raman, A.A., Ashri Wan Daud, W.M., 2015. Advanced oxidation
processes for in-situ production of hydrogen peroxide/hydroxyl radical for
textile wastewater treatment: a review. J. Clean. Prod. 87, 826e838.
Bansal, S., Kushwaha, J.P., Sangal, V.K., 2013. Electrochemical treatment of Reactive
Black 5 textile wastewater: optimization, kinetics, and disposal study. Water
Environ. Res. 85, 2294e2306.
Brillas, E., Casado, J., 2002. Aniline degradation by Electro-Fenton and peroxi-
coagulation processes using a flow reactor for wastewater treatment. Chemo-
sphere 47, 241e248.

s, I., Oturan, M.A., 2009. Electro-Fenton process and related electro-
Brillas, E., Sire
chemical technologies based on Fenton's reaction chemistry. Chem. Rev. 109,
6570e6631.
Chen, G., 2004. Electrochemical technologies in wastewater treatment. Separ. Purif.
Technol. 38, 11e41.
Chen, W., Liu, J., 2012. The possibility and applicability of coagulation-MBR hybrid
system in reclamation of dairy wastewater. Desalination 285, 226e231.
lu, R., Yilmaz, A.E., Bayar, S., 2014. Electro-oxidation of Pista-
Fill, B.A., Boncukcuog
chio processing industry. Wastewater Using Graphite Anode. Clean 42,
1232e1238.
Garcia-Segura, S., Brillas, E., 2016. Combustion of textile monoazo, diazo and triazo
dyes by solar photoelectro-Fenton: decolorization, kinetics and degradation
routes. Appl. Catal. B Environ. 181, 681e691.
Georgiou, D., Melidis, P., Aivasidis, A., 2002. Use of a microbial sensor: inhibition
effect of azo reactive dyes on activated sludge. Bioproc. Biosyst. Eng. 25, 79e83.
Ghanbari, F., Moradi, M., 2015. A comparative study of electrocoagulation, elec-
trochemical Fenton, electro-Fenton and peroxi-coagulation for decolorization of
real textile wastewater: electrical energy consumption and biodegradability
improvement. J. Environ. Chem. Eng 3, 499e506.
Izares, P., Martianez, Fabiola, Jimeanez, Carlos, Rodrigo, M., 2006. Coagulation and
electro coagulation of wastes polluted with dyes. Environ. Sci. Technol. 40,
6418e6424.
Kaur, P., Kushwaha, J.P., Sangal, V.K., 2018. Electrocatalytic oxidative treatment of
real textile wastewater in continuous reactor: degradation pathway and
disposability study. J. Hazard Mater. 346, 242e252.
Kaur, P., Kushwaha, J.P., Sangal, V.K., 2017. Evaluation and disposability study of
actual textile wastewater treatment by electro-oxidation method using Ti/RuO2
anode. Process Saf. Environ. Protect. 111, 13e22.
Kobya, M., Gengec, E., Demirbas, E., 2016. Operating parameters and costs assess-
ments of a real dyehouse wastewater effluent treated by a continuous elec-
trocoagulation process. Chem. Eng. Process 101, 87e100.
Korbahti, B.K., Tanyolac, A., 2009. Electrochemical treatment of simulated industrial
paint wastewater in a continuous tubular reactor. Chem. Eng. J. 148, 444e451.
Kushwaha, J.P., Srivastava, V.C., Mall, I.D., 2011. Studies on electrochemical treat-
ment of dairy wastewater using aluminum electrode. AIChE J. 57, 2589e2598.
Kushwaha, J.P., Srivastava, V.C., Mall, I.D., 2010. Organics removal from dairy
wastewater by electrochemical treatment and residue disposal. Separ. Purif.
Technol. 76, 198e205.
Lin, H., Zhang, H., Wang, X., Wang, L., Wu, J., 2014. Electro-Fenton removal of Orange
II in a divided cell: reaction mechanism, degradation pathway and toxicity
evolution. Separ. Purif. Technol. 122, 533e540.
Martinez-Huitle, C.A., Brillas, E., 2009. Decontamination of wastewaters containing
synthetic organic dyes by electrochemical methods: a general review. Appl.
Catal. B Environ. 87, 105e145.
Meric, S., Kaptan, D., Olmez, T., 2004. Color and COD removal from wastewater
containing Reactive Black 5 using Fenton's oxidation process. Chemosphere 54,
435e441.
Mukimin, A., Vistanty, H., Zen, N., 2015. Oxidation of textile wastewater using
cylinder Ti/PbO2 electrode in electrocatalytic tube reactor. Chem. Eng. J. 259,
430e437.
Mukimin, A., Zen, N., Purwanto, A., Wicaksono, K.A., Vistanty, H., Alfauzi, A.S., 2017.
Application of a full scale electrocatalytic reactor as real batik printing waste-
water treatment by indirect oxidation process. J. Environ. Chem. Eng 5,
5222e5232.
Nasr, B., Abdelatif, G., Can ~ izares, P., Saez, C., Lobato, J., Rodrigo, M.A., 2005. Elec-
trochemical oxidation of hydroquinone, resorcinol, and catechol on boron-
doped diamond anodes. Environ. Sci. Technol. 39, 7234e7239.
Nidheesh, P.V., Gandhimathi, R., 2014. Removal of Rhodamine B from aqueous so-
lution using graphiteegraphite electro-Fenton system. Desalination. Water.
Treat 52, 1872e1877.
Oturan, N., Brillas, E., Oturan, M.A., 2012. Unprecedented total mineralization of
atrazine and cyanuric acid by anodic oxidation and electro-Fenton with a
boron-doped diamond anode. Environ. Chem. Lett. 10, 165e170.
Pajootan, E., Arami, M., Rahimdokht, M., 2014. Discoloration of wastewater in a
continuous electro-Fenton process using modified graphite electrode with
multi-walled carbon nanotubes/surfactant. Separ. Purif. Technol. 130, 34e44.
Pillai, M.I.S., Gupta, A.K., 2017. Performance analysis of a continuous serpentine flow
reactor for electrochemical oxidation of synthetic and real textile wastewater:
energy consumption, mass transfer coefficient and economic analysis.
J. Environ. Manag. 193, 524e531.

s, I., 2012. Finding the best Fe2þ/Cu2þ combination for the
Salazar, R., Brillas, E., Sire
solar photoelectro-Fenton treatment of simulated wastewater containing the
industrial textile dye Disperse Blue 3. Appl. Catal., B 115, 107e116.
Santos, I.D., Afonso, J.C., Dutra, A.J.B., 2010. Behavior of a Ti/RuO2 anode in
concentrated chloride medium for phenol and their chlorinated intermediates
electrooxidation. Separ. Purif. Technol. 76, 151e157.
Santos, I.D., Afonso, J.C., Dutra, A.J.B., 2011. Electrooxidation of phenol on a Ti/RuO2
anode: effect of some electrolysis parameters. J. Braz. Chem. Soc. 22, 875e883.

s, I., Brillas, E., 2012. Remediation of water pollution caused by pharmaceutical
Sire
residues based on electrochemical separation and degradation technologies: a
review. Environ. Int. 40, 212e229.

s, I., Brillas, E., Oturan, M.A., Rodrigo, M.A., Panizza, M., 2014. Electrochemical
Sire
advanced oxidation processes: today and tomorrow. a review. Environ. Sci.
Pollut. Res. 21, 8336e8367.
Sun, Y., Pignatello, J.J., 1993. Photochemical reactions involved in the total miner-
alization of 2,4-D by iron (3þ)/hydrogen peroxide/UV. Environ. Sci. Technol. 27,
304e310.
Vlyssides, A.G., Israilides, C.J., 1997. Detoxification of tannery waste liquors with an.
electrolysis system. Environ. Pollut. 97, 147e152.
Vlyssides, A.G., Karlisa, P.K., Rori, N., Zorpas, A.A., 2002. Electrochemical treatment
in relation to pH of domestic wastewater using Ti/Pt electrodes. J. Hazard Mater.
B95, 215e226.
Vlyssides, A.G., Loizidou, M., Karlis, P.K., Zorpas, A.A., Papaioannou, D., 1999. Elec-
trochemical oxidation of a textile dye wastewater using a Pt/Ti electrode.
J. Hazard Mater. B70, 41e52.
Wang, A., Qu, J., Ru, J., Liu, H., Ge, J., 2005. Mineralization of an azo dye acid red 14
by electro-Fenton’s reagent using an activated carbon fiber cathode. Dyes Pig-
ments 65, 227e233.
Zhou, M., He, J., 2007. Degradation of azo dye by three clean advanced oxidation
processes: wet oxidation, electrochemical oxidation and wet electrochemical
oxidationda comparative study. Electrochim. Acta 53, 1902e1910.