Ecotoxicology and Environmental Safety 145 (2017) 184–192

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Ecotoxicology and Environmental Safety

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

Treatment of highly toxic cardboard plant wastewater by a combination of MARK

electrocoagulation and electrooxidation processes
Erhan Gengec
University of Kocaeli, Department of Environmental Protection, Kocaeli, Turkey

A R T I C L E I N F O A B S T R A C T

Keywords: The objective of this study was to investigate the removal efficiencies of the electrochemical treatment systems
Cardboard Wastewater as an alternative for the treatment of cardboard plant wastewater (CPW). In accordance with this purpose, CPW
Toxicity was treated by electrocoagulation (EC) with Al electrodes and the effects of current density (CD), operating time
Electrocoagulation (t), and initial pH (pHi) were investigated. The results showed that EC at optimum treatment conditions (CD:
Electrooxidation
7.5 mA/cm2, pHi: 7.0 and t: 60 min) have limited removal efficiencies for total organic carbon (TOC; 17.1%) and
Boron-doped Diamond Electrode
chemical oxygen demand (COD, 14.2%), on the contrary of turbidity (98.7%). Due to the low TOC and COD
removal efficiencies, a secondary treatment was needed and the electrocoagulated effluent was subjected to
electrooxidation (EO) by using a boron doped diamond (BDD) electrode for investigating the effect of CD, t, pHi
and electrolyte concentration (Ce). Higher TOC (83.7%) and COD (82.9%) removal efficiencies were obtained by
EO under the optimum treatment conditions (CD: 100 mA/cm2, pHi: 7.2, Ce: 5.0 g/L Na2SO4 and t: 180 min). In
addition, a toxicity test was carried out to the raw and treated wastewater under the optimum operating con-
ditions. This study demonstrated that the combination of EC and EO have a satisfactory potential for real in-
dustrial wastewater with a high organic content, suspended solids and toxicity.

1. Introduction
The pulp and paper industry use lignocellulogic materials (wood
and/or recycled paper etc.) as a raw material, and produce paper,
cardboard and other cellulose-based products. During production of the
paper and cardboard, wastewater that has high suspended solids, color,
and organic substance in the range from 75 to 275 m3 per ton of pro-
duct (Jaafarzadeh et al., 2016) is generated. Moreover, this industrial
sector wastewater contains the chlorinated lignosulphonic acids, resin
acids, phenols and hydrocarbons besides dibenzo-p-dioxin and di-
benzofuran, highly toxic and recalcitrant compounds (Kumar et al.,
2015). Due to these components, these effluents are extremely ha-
zardous for the ecosystem because they exhibit a strong mutagenic ef-
fect, have acute toxicity, cause a decreasing of oxygen, and prevent
light penetration. Therefore, various wastewater treatment systems and
their combinations have been employed to minimize the negative in-
fluence of pulp and paper industry effluents on the environment until
now (Birjandi et al., 2014). Inside these treatment systems, coagulation
and flocculation processes in which polyaluminium chloride (PAC) and
aluminum sulphate are used are very effective for the removal of sus-
pended solids (SS), colloids and toxicity in wastewater. However, there
are two problems involving the potential ecotoxicity of metallic coa-
gulants and other toxic components in wastewater: (I) The production
of large volumes of toxic sludge, and (II) an increase in metal con-
centration in treated water are the main disadvantages of these systems.
Another alternative treatment system in the paper industry is the bio-
logical method (mainly aerated lagoon), which is commonly used due
to the low cost and minimal operation requirements. The biological
methods are also very effective for the removal of soluble and biode-
gradable organic pollutants (Pokhrel and Viraraghavan, 2004). How-
ever, the existence of bio-refractory components in wastewater, the
sensitivity of microorganisms to toxic material, production of high
amounts of sludge and lengthy time requirements are the disadvantages
of the biological methods (Renault et al., 2009). Due to the mentioned
disadvantages, a physico-chemical method is usually needed before a
biological method. Furthermore, adsorption, ozonation and membrane
filtration of chlorinated phenolic compounds and adsorable organic
halides and chemical oxidation of colorful components were carried out
effectively in paper industry wastewater (Pokhrel and Viraraghavan,
2004). However, these processes involve a great deal of disadvantages
such as high cost, selective removal and difficulties in practice. On the
other hand, due to the increasing fresh water cost and the limited dis-
charge standards of wastewater, the focus of researchers has shifted to
relatively new alternatives (Mansour and Kesentini, 2008) such as
electrochemical treatment systems. Electrocoagulation (EC), electro-
oxidation (EO), and electro-fenton (EF) are the most promising

E-mail address: erhan.gengec@kocaeli.edu.tr.

http://dx.doi.org/10.1016/j.ecoenv.2017.07.032
Received 5 June 2017; Received in revised form 10 July 2017; Accepted 15 July 2017
0147-6513/ © 2017 Elsevier Inc. All rights reserved.
E. Gengec
electrochemical treatment systems.
Due to a great deal of competitive advantages such as no selectivity
towards pollutants, low operating cost, easy operable equipment, short
operation time, low requirement of chemicals, and low production
amount of sludge, the EC process is frequently suggested in literature
for the removal of chemical oxygen demand (COD), biological oxygen
demand (BOD), total organic carbon (TOC), suspended solids (SS),
turbidity, and toxicity (David et al., 2015; Makwana and Ahammed,
2016). Generally, a power supply (alternating current; AC or direct
current; DC) and electrodes (aluminum or iron) are used during the EC
process and anode electrodes are consumed under a potential. Thus,
three successful stages during this process are realized: (i) formation of
coagulants by electrolytic oxidation of the sacrificial anode electrode,
(ii) destabilization of the pollutants, particulate suspension, and
breaking of emulsions, (iii) aggregation of the destabilized phases to
form flocs. The main reaction at the Al anode is shown as follows
(Dastyar et al., 2015; Elabbas et al., 2015; Ezechi et al., 2014; Hamdan
and El-Naas, 2014; Makwana and Ahammed, 2016; Mella et al., 2015;
Vasudevan, 2012; Zaidi et al., 2016):
Al → Al3 + + 3e−
In addition to aluminum dissolution, oxygen evolution is realized
via a reaction (Eqn. 2) at the anode:
2H2 O → O2(g) + 4H+ + 4e−
At cathode, hydrogen evolution is realized by the following reaction
(Eq. (3)) and the formed hydrogen causes the floatation of pollutants.
Moreover, the produced hydroxyls ions at cathode generally cause an
increase of pH.
3H2 O + 3e− → 3/2H2 + 3OH−
The hydrolysis constants for aluminum cover a very narrow range,
and all of the aluminum deprotonations are ‘squeezed’ into an interval
of three pH units. Therefore, except for a narrow pH region (approxi-
mately 5–8), the dominant soluble species are Al3+ at low pH and
Al(OH)−4 at high pH (Gengec et al., 2012; Kobya et al., 2014; Kobya and
Gengec, 2012). The produced positively charged metal ions (Al3+) in
the acidic conditions neutralize the negatively charged pollutants. At
about neutral pH (5–8) metal ions hydrolyze to monomeric-polymeric
aluminum hydroxides and amorphous species, Al(OH)3 (sweep coagu-
lation). Monomeric-polymeric species such as Al(OH)2 +, Al(OH)+2 ,
Al(OH)−4 , Al2 (OH)24 +, Al 6 (OH)15
3+ 4+
, Al7 (OH)17 4+
, Al8 (OH)20 , Al13O4 (OH)724+,
and Al13 (OH)34 transform initially into Al(OH)3(s) and finally poly-
5+
merize to Aln(OH)3n (Eqs. (4) and (5)) according to the pH of the
wastewater and concentration of Al:
Al3 + + 3H2 O → Al(OH)3(s) + 3H+
nAl(OH)3 → Aln (OH)3n
These hydroxides are excellent coagulants and cause adsorption of
pollutants. On the other hand, the formed negatively charged hydro-
xides such as Al (OH )−4 (Eq. (6)) usually reduce the removal efficiencies
at high pH values (> 9);
2Al + 6H2 O + 2OH → Al(OH)4 + 3H2(g)
Until now, EC technology has been reported as an effective treat-
ment system for industrial wastewater such as electroplating (Kobya
et al., 2016), distillery (David et al., 2015), tannery (Elabbas et al.,
2015), baker's yeast production (Gengec et al., 2012) and textile dyeing
(Kobya et al., 2014). Therefore, removal of turbidity and toxicity in
cardboard plant wastewater (CPW) can be carried out successfully by
EC. However, the mineralization of organic components in CPW up to
the legal discharge standards of wastewater does not seem possible via
EC.
EO is an effective method for the mineralization of organic sub-
stances in wastewater, though not for turbidity. Thus, the combination
Ecotoxicology and Environmental Safety 145 (2017) 184–192
of EC with EO can be a good alternative for treatment of the CPW
(Jaafarzadeh et al., 2016; Zaidi et al., 2016). In addition, EO presents a
large number of advantages: (I) the oxidation of pollutants up to the
final product or to less toxic by-products in contrast with coagulation,
membrane, filtration, and adsorption processes, (II) short oxidation
time requirements, no sludge problem, non-selective to toxic and non-
biodegradable material in contrast with biological oxidation processes,
and (III) addition of chemical reagents not required (except for elec-
trolytes or catalyst addition at low amounts) in contrast with chemical
oxidation. EO can be categorized as direct and indirect oxidation. In the
indirect oxidation process, oxidizing reagents such as chlorine, hypo-
chlorous acid, hypochlorite, hydrogen peroxide and ozone are formed
at the electrodes surfaces and then, destroy pollutants in wastewater.
The direct oxidation process involves (I) electron transfer to the pol-
lutants and (II) the forming of hydroxyl radicals on anode's surface
(Särkkä et al., 2015; Wu et al., 2014). When direct and indirect oxi-
dations are compared, direct oxidation has some advantages such as
requiring a lower amount of chemical substance and producing no
secondary contaminants (Särkkä et al., 2015). The electrocatalytic ac-
tivity and electrochemical stability of the electrode is a key point for
(1)
direct oxidation. Although several anode materials have been used in
the direct oxidation, the complete mineralization of the pollutants has
been possible by use of high oxygen overvoltage anodes such as SnO2,
PbO2 and boron doped diamond (BDD) (Panizza and Cerisola, 2001).
(2)
The BDD electrode has been identified as an excellent non-active anode
for the removal of pollutants in wastewater (Özcan et al., 2008) and the
formation of hydroxyl radical (•OH) on the BDD anode surface has been
reported as the main removal mechanism. Due to having an inert sur-
face and low adsorption capacity, the BDD surface interacts weakly
with the •OH. During EO with BDD, the complete mineralization of
(3)
pollutants in wastewater is possible due to the physisorbed •OH by the
following reactions (Eqs. (7) and (8), R: organic pollutants in waste-
water) (Gao et al., 2004; Marco Antonio Quiroz et al., 2006; Martínez-
Huitle and Ferro, 2006; Scialdone, 2009; Sires et al., 2014)
M+ H2 O → M(HO•) + H+ + e (7)
M(HO•) + R→ M + mCO2 + nH2 O + H+ + e (8)
Although scientists recent attention has focused on EO, there is a
lack of information in literature regarding EO: (I) removal efficiencies
of EO in different real wastewater (only 20% EO paper in the last 3
years have dealt with treatment of the real wastewater), (II) comparison
of the electrodes performance, (III) contribution level on removal effi-
ciencies of EO at a combination of different treatment systems, (IV)
removal mechanism, (V) electrical consumption (Sires et al., 2014) and
(VI) possible formation of toxic by-products. To the best of the author's
(4) knowledge, the combination of the electrocoagulation (Al electrode)
and electrooxidation processes (BDD electrode) has yet to be studied for
(5)
the treatment of CPW. Moreover, the influence of the EC and EO
combination on toxicity of real wastewater has not been investigated
sufficiently.
Therefore, the purposes of this study were: (I) present the combi-
nation of EC and EO as a competitive alternative for the treatment of
industrial wastewater with high suspended solids, organic content and
(6) toxicity, (II) investigate the effect of process conditions on removal
efficiencies, and (III) calculate the electrical and electrode consumption
during these processes.
2. Material and methods
2.1. Wastewater
The wastewater was taken from the starting point of a cardboard
plant treatment system. The coated cardboard is made out of recycled
paper and the annual cardboard production capacity of the plant has
reached 240,000 t (Table 1).
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E. Gengec
Table 1
Some physical and chemical specification of raw cardboard wastewater.
Parameters Parameters
Flow rate (m3/day)a 6000–8000 COD (mg/L)
pH 6.9–7.1 TOC (mg/L)
Conductivity (mS/cm) 2.271–2450 NH3-N (mg/L)
Turbidity (NTU) 783 SO4 (mg/L)
Total Solids (mg/L) 5000–5850 PO4-P (mg/L)
Settleable Solids (mL/L) 750–850 EC50b
Total Suspended Solids (mg/L) 3000–5000 EC20b
a
The information was supplied from the manufacturer. Other specifications were
measured during this work.
b
EC50 and EC20: The concentration of wastewater that causes 50 % and 20 % of
bacteria reduction relative to control sample, respectively.
2.2. The experimental set-up and analytical methods
The EC experiments were realized by a batch process using a 1 L
capacity of a reactor made from Plexiglas with dimensions of
12×11×11 cm. Aluminum (Al) plates (purity > 99.5%) with dimen-
sions of 5.0 × 8.0 × 0.3 cm were used as the sacrificial electrodes. In
each run, four Al plate electrodes (two anodes and two cathodes)
spaced by 0.5 cm were placed vertically in the reactor and connected at
the monopolar parallel mode. All the EC runs were performed with
0.85 L of wastewater at a constant 25 °C and 300 rpm (Heidolp MR
3000D). Before each run, the impurities on the electrode surfaces were
removed by a hydrochloric acid-hexamethylenetetramine aqueous so-
lution. The electrodes were dipped into the wastewater to a depth of
80 mm yielding a total effective electrode surface area of 120 cm2
(Gengec et al., 2012). Then, the current was arranged at the desired
value and the experiment was started. The samples taken from the EC
reactor at different operating times were analyzed. At the end of the EC
runs, electrical energy consumption (ENC, kWh/m3, Eqn. 9) and elec-
trode consumption (ELC, kg/m3, Eq. (10)) were calculated via Faraday's
Law:
U×i×t
ENC =
v (9)
i × t × Mw
ELC =
z×F×v
where U is cell voltage (V), I is current (A), t is operating time (s) and v
is volume (m3) of wastewater, Mw is molecular mass of aluminum
(26.98 g/mol), zAl is number of electron transferred (zAl = 3) and F is
Faraday's constant (96,487 C/mol).
EO experiments were conducted in batch mode by using an open,
undivided, glass cell (12 × 9 × 7 cm). The 0.75 L capacity glass cell
was surrounded by a double jacket for the circulation of external
thermostated water, controlled at 25 ± 1 °C. A thin-film of BDD elec-
trode was used in EO experiments and the effective area of the anodes
was 39 cm2. The BDD anode was supplied by DiaCCon GmbH, the
cathode was a stainless steel sheet and the inter-electrode distance was
about 1.5 cm. All EO experiments were performed with 0.5 L of was-
tewater at 300 rpm (Heidolp MR 3000D). Na2SO4 was preferred as an
electrolyte and added to the wastewater in various amounts. The
electrodes were connected to a digital DC power supply (Agilent 6675A
model; 30 V, 6 A) operated at galvanostatic mode and the current was
held constant at the desired values for each run.
The TOC levels were determined by the combustion of the samples
at 680 °C (Shimadzu, TOC-L model). COD measurements were realized
by Standard Methods (APHA, 1998). The pH of the sample was adjusted
with 0.1 M H2SO4 or NaOH and measured by a pH meter (WTW Inolab
pH 720). The analysis was triplicated and the average data was re-
ported. The accuracy of these measured values for COD, TOC and tur-
bidity were calculated below 3.0%.
Ecotoxicology and Environmental Safety 145 (2017) 184–192
2.3. The toxicity test
The toxicity test was performed according to the International
Standard Method (ISO) 21338: Water Quality-Kinetic determination of
2358 the inhibitory effects of sediment, other solids and colored samples on
1006 the light emission of Vibrio fischeri (kinetic luminescent bacteria test)
< 0.5
(International Standard Method 21338, 2010). Luminescence was
241
2.8 measured using a high performance Sirius luminometer and light
20.11 output was recorded automatically by FB12 software (Berthold detec-
6.52 tion systems, Germany). Then, the inhibition percentage, EC50 (the
concentration that causes 50% reduction of bacteria relative to control)
and EC20 values were calculated (Al-Mutairi, 2006; International
Standard Method 21338, 2010).
In brief, the toxicity test was realized over six steps: (I) the waste-
water was diluted with 2% NaCl solution to obtain dilution series (1:2,
1:4, 1:8, 1:16, 1:32 and 1:64), (II) the Vibrio fischeri was injected to the
diluted wastewater, (III) luminescence of Vibrio fischeri in diluted
wastewater was measured every 0.1 s during the initial five seconds,
(IV) the maximum value recorded, (V) II, III and IV steps were carried
out for all of the diluted wastewater and control samples, (V) lumi-
nescence of Vibrio fischeri was re-measured after a contact time of
30 min, (VI) the ratios of the inhibitory effect (Inh %) and effective
concentrations (EC20 or EC50) were calculated by the luminescence
results of bacteria in this dilution series.
3. Results and discussion
As seen in Table 1, CPW has a high organic content, suspended
solids and toxicity. In this study, the effect of initial pH (pHi), current
density (CD, mA/cm2), and operating time (t, min) were investigated
during EC with Al electrode. Following this, the electrocoagulated
wastewater was treated by EO processes under different experimental
conditions: pHi, CD, t, and electrolyte concentration (Ce) with BDD
electrode.
3.1. Effect of processes parameters on EC
It is well known that pHi, CD (A/m2) and t (min) are the major
parameters which affect the removal efficiencies in the EC process
(Hamdan and El-Naas, 2014; Jaafarzadeh et al., 2016; Kobya et al.,
(10) 2016; Makwana and Ahammed, 2016). The optimum values of these
parameters are changeable according to the characterization of the
wastewater (pHi, pollutants species, affinity of pollutants etc.) and
species of electrodes (Al, Fe etc.). Therefore, Al electrode was used as a
sacrificial electrode in this study and optimum process conditions were
evaluated by a series of experiments in order to remove the COD, TOC
and turbidity.
The effect of pHi on treatment efficiencies was examined at 3.0, 4.0,
6.0, 7.0, 9.0, and 10.0 pH's over a period of 60 min. It is clear that when
the pH value was altered towards two extremes, the TOC and COD
removal efficiencies decreased (Fig. 1a and b). The maximum removal
efficiencies were obtained for TOC (16.8%) and COD (10.1%) at pH 7,
and for turbidity (97%) at pHi 10. The original pHi value (pH 7) of CPW
seemed as the optimum one due to the unnecessary pH arrangement
and the obtained high removal efficiencies for TOC (16.8%), COD
(10.1%) and turbidity (95%, residual turbidity: 38 NTU).
During the EC process, three major interaction mechanisms, charge
neutralization, adsorption and sweep flocculation are dominant at dif-
ferent pH ranges and metal concentrations since pH and metal con-
centration affect the solubility of metal species in wastewater (Fig. 2c,
only mononuclear Al species were considered). In low pH values,
charge neutralization is dominant and realized by mono metal species
such as Al+3 which are produced at the anodes. These positively
charged metal ions neutralize the anionic charges of pollutants in
wastewater and reduce their solubility. Between the pH range 5.0–8.0,
amorphous metal hydroxides which have a large specific surface are
186
E. Gengec
Fig. 1. Effect of pH (CD: 6.0 mA/cm2, initial TOC: 1006 mg/L, initial COD: 2358 mg/L, and initial turbidity: 783 NTU) on (a) TOC, (b) COD, (c) turbidity, and (d) Activity–pH diagram for
Al(III) species in equilibrium with Al(OH)3 (amorphous) (Ghernaout et al., 2009; Metcalf and Eddy, 2004; Yilmaz et al., 2007).
formed and sweep flocculation of pollutants is possible. Moreover,
polynuclear and polymeric species at higher and lower pH values cause
adsorption (Elabbas et al., 2015; Gengec et al., 2012; Metcalf and Eddy,
2004). In this study, at 6.0 mA/cm2 and 7 of pH, the produced Al
concentration was calculated by Faraday's laws (Eqn. 10) as 1.76 × 10−3 ,
3.51 × 10−3 , 7.02 × 10−3 , 1.05 × 10−2 , 1.4 × 10−2 , 1.76 × 10−2 , and
2.11 × 10−2 molar for 5, 10, 20, 30, 40, 50, and 60 min, respectively.
According to these results and Fig. 1c, sweep flocculation seemed as the
dominant removal mechanism in this study.
As mentioned before, the pH and the Al concentration affect the
species of Al which not only influences the treatment efficiency but also
the operating cost of the EC process. According to Faraday Law's (Eq.
(10)), the dissolved amount of coagulant at the anode depends on
current density (calculated by dividing of the applied current by the
active electrode area), and operating time. Moreover, current density
and operation time determine the bubble production rate at the elec-
trode, which causes electroflotation. For the reasons mentioned above,
the effects of current density and operating time were investigated
(Fig. 2) in the range of 3.0–12.0 mA/cm2 and 0–60 min, respectively.
The maximum removal efficiencies at 3.0, 6.0, 7.5, 12.0 mA/cm2
during 60 min were obtained as 14.2%, 16.8%, 17.1%, and 18.2% for
TOC, 10.2, 11.0, 12.8, 13.8, and 14.1 for COD, and 92.3%, 95.9%,
98.7%, and 98.7% for turbidity, respectively. As seen in results, the
increased current density and operating time improved removal effi-
ciencies slightly and caused an increasing of electrical (Fig. 2c) and
electrode consumptions. The electrical (Eq. (9)) and electrode con-
sumptions (Eq. (10)) were calculated respectively as 1.85, 5.50, 9.18,
13.90, and 21.30 kWh/m3 and 0.142, 0.284, 0.355, 0.466 and 0.569 kg
Al/m3 for 3.0, 6.0, 7.5 and 12.0 mA/cm2 during 60 min. Thus, 7.5 mA/
187
Ecotoxicology and Environmental Safety 145 (2017) 184–192
cm2, 7 of pHi, and 60 min were selected as the optimum operating
conditions. The EC process was an effective method for the removal of
turbidity during the treatment of CPW. In addition, the quality of the EC
effluent under the optimum conditions (residual TOC: 834 mg/L re-
sidual COD:2025 mg/L and residual turbidity: 10 NTU) meets the reuse
standards for turbidity in the paper industry, which is 14–56 NTU
(Terrazas et al., 2010) during the paper bleaching stage. However, the
obtained TOC and COD removal efficiencies with the EC were very low
when compared with other studies which dealt with the treatment of
the paper industries wastewater by EC (Jaafarzadeh et al., 2016). The
various used raw materials (recycled paper, wood etc.) and the pro-
duction conditions of cardboard may cause this phenomenon. As a re-
sult, it was determined that the EC could be used efficiently for the
removal of high molecular weight dissolved organic matters (Kamali
and Khodaparast, 2015), turbidity and suspended solids and it is a
competitive alternative to be conducted prior to an oxidation treatment
system.
3.2. Effect of processes parameters on EO
During the EO process, the current density is one of the most im-
portant driving forces because it not only affects the degradation rate of
the EO but also the reactions rate (bubble production rate, O2 reduc-
tion/evaluation rates etc.) (Gengec et al., 2012; Kourdali et al., 2014).
Thus, the electrocoagulated CPW at the presence of 2 g/L Na2SO4 as the
electrolyte was treated at different current densities (from 25 mA/cm2
to 100 mA/cm2). When 25, 50, 75 and 100 mA/cm2 of the current
densities were applied, the removal efficiencies were increased to
47.5%, 66.8%, 77.9%, and 88.2% for TOC and 49.2%, 68.0%, 80.0%,
E. Gengec
Fig. 2. Effect of current density (pHi: 7.0, initial TOC: 1006 mg/L, initial COD: 2358 mg/L, and initial turbidity: 783 NTU) on (a) TOC (b) COD and (c) Turbidity.
and 89.2% for COD during 180. min (Fig. 3a and b), respectively. It is
well known that the rise of the current density causes the increase of
•
OH generation on the BDD anode. Therefore, higher removal effi-
ciencies were possible using an increased current density and these
results are well in agreement with literature. For instance, Jalife-Jacobo
et al. (2015) studied the diazo dye Congo Red (3 L of 100 mg/L) de-
gradation using a BDD anode. They reported that when the current
density rose from 7.5 to 50 mA/cm2 at the presence of Na2SO4, removal
efficiencies were increased from 15% to 50%, respectively. Moreover,
Jong Young Choi et al. (2010) investigated the effect of the various CD
(5, 15, and 25 mA/cm2) on the degradation of 1,4-dioxane, a refractory
water pollutant with COD = 32 mol O2/m3, by BDD electrode at 5.5 of
pHi, and the presence of 5 g/L of Na2SO4. They showed that a higher
current density had a much faster degradation rate. The complete de-
gradation of 1,4-dioxane occurred at about 18 min at 5 mA/cm2 and
7 min at 25 mA/cm2 (the results were seen at graph). As can be seen by
these studies, current density in EO systems affect the removal effi-
ciencies depending on other conditions such as pollutant type, the
presence of electrolyte, electrolyte species, operating time and pH.
It must be noted that the rise current density from 25 mA/cm2 to
100 mA/cm2 (Fig. 3c) not only increased the removal efficiencies but
also the electrical consumption (Eqn. 9) from 76.03 kWh/m3 to
678.28 kWh/m3 (average volt from 12.93 to 28.99). These higher
electrical consumptions should be decreased for economic reasons.
The best way of lowering electrical consumption was to decrease
wastewater resistance via the addition of electrolyte into the waste-
water. It is well known that adding electrolyte such as NaCl, KCl,
Na2SO4, HClO4, and H2SO4 decreased electrical consumption in all
electrochemical treatment processes. In addition to the decreasing
electrical consumptions, the inclusion of electrolyte usually causes an
188
Ecotoxicology and Environmental Safety 145 (2017) 184–192
increase of removal efficiencies (Jalife-Jacobo et al., 2015). Most stu-
dies have shown that the highest removal efficiencies were obtained by
usage of NaCl in comparison with other electrolytes. However, it was
reported that the usage of NaCl caused the production of many orga-
nochlorinated species as intermediates and final products that can be
even more harmful than the raw pollutants (Comninellis and Pulgarin,
1991; Gotsi et al., 2005; Sires et al., 2014). Therefore, Na2SO4 was used
between 2.0 g/L and 6.0 g/L of concentrations at 7.2 of pH and
100 mA/cm2 of CD in order to observe the effects of supporting elec-
trolyte on electrical consumption and removal efficiencies. The addition
of 2.0, 3.0, 4.0, 5.0, and 6.0 g/L Na2SO4 (Fig. 4a) decreased the po-
tentials of the process (28.99, 25.75, 22.46, 20.07, and 19.06 V) and
electrical consumption (678.29, 602.51, 525.64, 469.52 and
446.07 kWh/m3), respectively. According to these results, the addition
of 5.0 g/L Na2SO4 seemed as an optimum electrolyte concentration due
to providing balance between electrical and chemical consumption.
These results indicated that electrical consumption could be decreased
up to 34% by adding electrolyte. On the other hand, the effect of adding
electrolyte into wastewater was commonly reported as not only causing
the decrease of electrical consumption but also the increase of removal
efficiencies. Generally, significant progresses in removal efficiencies by
the forming of radicals and stable oxidants were reported by the usage
of Na2SO4 (Eqs. (11) and (12)) (Jalife-Jacobo et al., 2015; Sires et al.,
2014):
SO24− → (SO−4 )• + e− (11)
(SO−4 )• + (SO−4 )• → S2 O82 − (12)
However, in this study the increasing of electrolyte (2.0, 3.0, 4.0,
5.0, and 6.0 g/L Na2SO4) caused a slightly decreasing in removal
E. Gengec
Fig. 3. Effect of current density and time on (a) TOC removal, (b) COD removal and (c) electric voltage (pHi: 7.2, Ce: 2 g Na2SO4/L, initial TOC: 1006 mg/L, initial COD: 2358 mg/L, and
initial turbidity: 783 NTU).
efficiencies (88.24%, 87.28%, 84.92%, 83.66%, and 83.65% for TOC
and 89.2%, 85.8%, 82.6%, 82.86%, and 81.1% for COD) (Fig. 4a and
b). The stated decline in removal efficiencies (only 5% for TOC and 8%
for COD) showed that the radicals were not formed or the formed ra-
dicals (SO−4 )• had an antagonistic effect on the other components in
wastewater under tested conditions. Similar to our results, a slight de-
cline or no effect on removal efficiencies during an increased amount of
electrolyte was reported in some other studies (Bottesi, 2016; Choi
et al., 2010).
The pH of wastewater affects chemical properties of pollutants and
the interaction of pollutants with the electrode in EO. Therefore, the
effect of the initial pH was investigated in Na2SO4 medium (TOCi:
836 mg/L, CODi: 2025 mg/L, Ce: 5.0 g/L Na2SO4 and CD: 100 mA/
cm2). As seen in Fig. 5, after 180 min of electrolysis, the removal effi-
ciencies at pH 2.0, 4.0, 6.0, 7.2, 8.0, and 10.0 were recorded as 78.7%,
79.0%, 82.2%, 83.7%, 84.3% and 85.7% for TOC and 75.0%, 77.1%,
79.4%, 82.9%, 83.0% and 84.0% for COD, respectively. The degrada-
tion efficiencies during the EO were slightly higher at > 6 pH than
acidic medium. Therefore, EO results showed that the electro-
coagulated wastewater could be used in EO without any pH arrange-
ment due to the final pH of electrocoagulated wastewater measured as
7.2 under the optimum process condition of EC, as stated in Section 3.1.
Similar to our results, Lissens et al. (2003), Canizares et al.
(2004a,2004b) and Koparal et al. (2007) reported that the oxidation
process by BDD electrode is more favourable in neutral and/or alkaline
medium. On the other hand, Choi et al. (2010) indicated that pH had no
influence on removal efficiencies and Scialdone et al. (2008) reported
higher removal efficiencies at an acidic medium. According to this lit-
erature, it can be concluded that the effect of pH strongly depends on
189
Ecotoxicology and Environmental Safety 145 (2017) 184–192
the nature of the wastewater.
3.3. Evaluation of acute toxicity of wastewater during EC and EO
Generally, the toxicity levels of wastewater are identified by the
EC50 and EC20 values. The EC50 and EC20 values are the concentration
of wastewater that causes 50% and 20% of bacteria reduction relative
to a control sample, respectively. In this study, these values were de-
termined according to the ISO Standard Method (21338, 2010) by Vi-
brio fischeri, a species of bioluminescent bacterium.
The EC50 and EC20 values of raw wastewater were calculated as
20.11 and 6.52, respectively. It meant that the wastewater had high
acute toxicity and when wastewater was evenly diluted at the ratio of
20.11 and 6.52, it caused a 50% and 20% of bacteria reduction in
30 min, respectively. As seen in Table 2, the inhibition ratio for treated
wastewater by EC and EO were below 50% for the whole dilution series.
These results indicated that the treated wastewater was not toxic
(Kováts et al., 2012). Moreover, the measured negative inhibition va-
lues demonstrated that better life conditions for bacteria were formed
after treatment by EC and EO. The possible way for negative inhibition
values is explained by the presence of organic substances (non-toxic or
low concentration of toxic compound) which were used as nutrients by
bacteria and thus, the amount of bacteria increased. The obtained
toxicity test results were quite promising when compared with the lit-
erature. In contrast with our findings, some studies which dealt with
toxic wastewater reported that toxicity during the EO process rose due
to the increase of toxic materials such as organochlorinated species
(Chatzisymeon et al., 2006; Gotsi et al., 2005).
E. Gengec Ecotoxicology and Environmental Safety 145 (2017) 184–192

Fig. 4. Effect of electrolyte concentration and time on (a) electric potential, (b) TOC and (c) COD removal (CD:100 mA/cm2, pHi: 7.2, initial TOC: 1006 mg/L, initial COD: 2358 mg/L,
and initial turbidity: 783 NTU).

4. Conclusions fraction of organic component was removed during EO systems. Current

The EC and EO processes were used to treat cardboard plant was-
tewater. The optimum process conditions were determined as 7.5 mA/
cm2, 7.0 of pHi and 60 min for EC and 100 mA/cm2, pH of 7.2, 5.0 g/L
Na2SO4 and 180 min for EO. Satisfactory removal efficiencies for tur-
bidity (98.7%), TOC (86.4%) and COD (85.3%) were provided via a
combination of EC and EO under the optimum process conditions.
Treated wastewater by EC and EO had 347 mg/L of COD, 86.4 mg/L of
TOC, 10 NTU of turbidity and 9.2 of pH. It must be noted that EC only
provided an effective removal in turbidity. On the other hand, a large
density and operating time had an important effect on the removal
efficiency for both electrochemical treatment systems. Moreover, both
processes showed optimum removal efficiencies at a neutral pH value.
Thus, under the optimum processes conditions, a chemical addition for
pH arrangement was not necessary in either system. However, the ad-
dition of electrolyte during EO was necessary due to causing a decrease
of electrical consumption.
According to toxicity test results, EC with Al electrode has an im-
portant potential for decreasing acute toxicity in wastewater. In addi-
tion, the forming of toxic species, one of the disadvantages of the EO

Fig. 5. Effect of pH and time on (a) TOC and (b) COD removal (CD: 100 mA/cm2, Ce: 5.0 g Na2SO4/L, initial TOC: 1006 mg/L, initial COD: 2358 mg/L, and initial turbidity: 783 NTU).

190
E. Gengec
Table 2
The inhibition ratios for raw and treated wastewater at different dilution levels.
Wastewater Dilution Ratios (%) Inhibition Ratios (Inh %)
Raw EC effluent EO effluent
50.00 66.06 7.33 11.35
33.33 63.51 −3.47 −10.03
25.00 62.46 −10.47 −16.90
16.67 55.01 −13.51 −15.80
12.50 47.46 −17.84 −16.06
8.33 23.22 −9.98 −11.34
6.25 12.35 −8.69 −10.93
process, was not observed or the concentration of the toxic compound
was low and the bacteria were using it as nutrient. It meant that the
usage of Na2SO4 was a good choice in terms of toxicity test results. This
study demonstrated that the combination of EC and EO processes,
which have a great deal of advantages such as easy operable equipment,
short operation time, low requirement of chemicals, is a vigorous al-
ternative for the treatment of wastewater with a high turbidity, organic
content and toxicity.
Conflict of interest
The author declares that there are no conflicts of interest and affirm
that this paper consists of original and unpublished work.
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