Journal of Water Process Engineering 31 (2019) 100863

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Journal of Water Process Engineering

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Performance of electrocoagulation and electro-Fenton processes for T

treatment of nanofiltration concentrate of biologically stabilized landfill
leachate
⁎
Senem Yazici Guvenc , Kaan Dincer, Gamze Varank
Department of Environmental Engineering, Faculty of Civil Engineering, Yildiz Technical University, 34220 Davutpasa, Esenler, Istanbul, Turkey

A R T I C LE I N FO A B S T R A C T

Keywords: In the present work, experimental study for leachate nanofiltration concentrate treatment by electrocoagulation
Leachate nanofiltration concentrate and electro-Fenton processes using iron electrodes was carried out in a batch electrolytic reactor. Removal
Electrocoagulation efficiencies of 60.2% for total organic carbon (TOC), 69.4% for chemical oxygen demand (COD), and 87.6% for
Electro-Fenton color from the electro-Fenton process at the optimum operating conditions and 45% for TOC, 57.4% for COD,
COD fractions
and 77.1% for color from the electrocoagulation process at the optimum operating conditions respectively, were
obtained. Additionally the fraction of biodegradable COD increased from 6.37% to 17.04% and 30.08% after
electrocoagulation and electro-Fenton processes respectively. About 39% soluble COD and 82% particulate COD
removal efficiencies were obtained by electrocoagulation whereas 57% soluble COD and 81% particulate COD
removal efficiencies were obtained by electro-Fenton process. Electro-Fenton process was found to be more
effective than the electrocoagulation process with respect to the removal efficiencies of COD and TOC. However
both processes could be efficient methods for converting nonsoluble COD to soluble COD and removal of non-
biodegradable COD. As a result both of the processes could be used as a post-treatment method for leachate and
an effective method inert COD removal from leachate nanofiltration concentrate.

1. Introduction high concentrations of ions and small organic compounds. Because of

Pressure-driven membrane processes (microfiltration, ultrafiltra-
tion, nanofiltration, reverse osmosis) separate a feed stream into a
purified permeate fraction and a concentrated retentate fraction [1,2].
Ultrafiltration (UF) membranes remove macromolecules with a mole-
cular weight above 5000–100,000 whereas nanofiltration (NF) mem-
branes remove organic compounds with a molecular weight above
200–500 depending on the pore size [3,4]. The volume and composi-
tion of the waste stream from pressure-driven membrane processes
depends on the operation mode of the process [5]. NF and RO are
usually operated in cross-flow mode: the concentrate and the rinsing
water used for intermediate forward-flushing are the main waste
streams. The characteristics of the concentrate depend on the feedwater
characteristics, the pretreatment, the membrane process used, the re-
covery, and the additional chemicals used [6]. The concentrate to feed
volume ratio is 1–10% for MF and UF, 15–30% for NF, and 15–60% for
RO. The concentrate composition is largely determined by the pore size
of the membrane. MF or UF membrane concentrates contain suspended
solids and colloidal particles, whereas NF or RO concentrates contain
the increased concentrations of salts and small organic compounds
treatment of NF or RO concentrates are more difficult than MF or UF
concentrates [6].
The percolation of rainfall in combination with the decomposition
of landfilled solid waste generates highly contaminated liquid, called
“leachate” [7]. Leachate contains complex pollutants including dis-
solved organic matter, inorganic ions; heavy metals. inorganic salts, etc.
and requires an efficient treatment to minimize the high level of pol-
lutants prior to final discharge [7–9]. Conventional biological treatment
methods is an economical way to remove the biodegradable organic
compounds in the leachate and nitrification-denitrification processes
are used for ammonia removal after anaerobic treatment. However,
refractory organic compounds such as humic acid (HA), fulvic acid (FA)
and hydrophilic fractions can not be effectively removed by conven-
tional biological treatment [10–12]. Membrane separation processes
such as nanofiltration (NF) and reverse osmosis (RO) are increasingly
being used as a polishing step following biological treatment to remove
these refractory pollutants [13,14]. Nevertheless, membrane separation
processes do not really destruct the pollutants, but merely concentrate

⁎
Corresponding author.
E-mail addresses: syazici@yildiz.edu.tr (S. Yazici Guvenc), kaandncr17@gmail.com (K. Dincer), gvarank@yildiz.edu.tr (G. Varank).

https://doi.org/10.1016/j.jwpe.2019.100863
Received 10 October 2018; Received in revised form 24 April 2019; Accepted 24 May 2019
Available online 03 June 2019
2214-7144/ © 2019 Elsevier Ltd. All rights reserved.
S. Yazici Guvenc, et al.
them into smaller volumes of wastewater called membrane con-
centrates. Chaplin et al. [15] have found that electrochemical oxidation
using BDD electrodes has an advantage over other advanced oxidation
processes, as organics were readily oxidized in the presence of high
HCO3− concentrations. As a result, the membrane concentrates contain
high levels of refractory organic pollutants and inorganic salts.
The main treatment methods of concentrated leachate can be clas-
sified into four categories: (1) recirculation to landfills [16]; (2) soli-
dification/stabilization [17]; (3) evaporation/distillation [18]; (4) ad-
vanced oxidation processes [19]. The recirculation of concentrated
leachate to landfills may inhibit the microbial activity [20] whereas
evaporation/distillation method require high land utilization, high
operating costs [14]. Moreover the corrosion and fouling are the two
main problems in evaporation/distillation method due to the high
concentration of salts and inorganic matters [21]. Solidification and
stabilization of the leachate NF concentrate seems to be an acceptable
solution, except for the disposal of derived solidified products [17].
Among the four categories, AOPs is an attractive method to remove
recalcitrant organic compounds and to increase the biodegradability of
concentrated leachate.
By AOPs bio-refractory organic matters could be destroyed via the
oxidation by generation of radicals, such as non-selective hydroxyl ra-
dicals [22]. Fenton, electrochemical oxidation, UV photocatalyst and
ozone-based processses have been investigated intensively [11,18,23].
High sludge generation rate in Fenton process, low energy efficiency of
UV photocatalyst, high cost of ozonation processes are the big barriers
for the application. Electrochemical oxidation has been considered as
an attractive technology to treat membrane concentrates containing
mainly non-biodegradable organics and having high salinity and elec-
tric conductivity [12,14].
Electro-Fenton process can be defined as the combination of Fenton
and electro coagulation processes to increase the degradability of or-
ganic compounds present in high strength wastewaters. A substantial
increase in the oxidizing power of H2O2 occurs in the presence of
electrically assisted Fenton process. Generation of hydroxyl radicals is
enhanced by electricity ensuring considerable improvement of removal
of refractory organic pollutants [24]. Electro-Fenton process has two
different configurations. In the first one, Fenton reagents are added to
the reactor from outside and inert electrodes with high catalytic activity
are used as anode material while in the second configuration, only
hydrogen peroxide is added from outside and Fe2+ is provided from
sacrificial cast iron anodes.
The EF process based on the employment of a sacrificial iron anode
delivers Fe2+ ions into the solution (Eq. (1)) whilst simultaneously
occurs the reduction of water at the cathode (Eq. (4)); then the hy-
drogen peroxide is added in order to provide conditions for the Fenton
reactions (Eqs. (2) and (3)). Moreover, Fe2+ according to Eq. (4) may
be continuously regenerated at the cathode depending on the electro-
lytic cell setup [25,26].
Fe 2 + + H2 O2 → Fe 3 + + ∙OH + OH− (in bulk solution) (1)
Fe 2 + + ∙OH → Fe 3 + + OH− (in bulk solution) (2)
Fe3 + + H2 O2 → Fe 2 + + H+ + HO2 ∙ (in bulk solution) (3)
Fe 2 + + e− → Fe 2 + (cathode ) (4)
Another possible electrochemical method for recalcitrant and non-
biodegradable organic substances removal is EC process. In EC pro-
cesses, the coagulating ions are produced in situ. The process involves
three stages: (i) formation of the coagulants by electrolytic oxidation of
the ‘sacrificial electrode’, (ii) destabilization of the contaminants, par-
ticulate suspension and breaking of emulsions and (iii) aggregation of
the destabilized pHases forming flocs. In the first stage of EC process
applied current intensity, pH and the conductivity of the wastewater
effect the generation of metallic ions and accordingly effect the per-
formance of the process.
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Journal of Water Process Engineering 31 (2019) 100863
The main processes occuring in the electrolytic system when iron
anodes are used can be described by the reactions given in Eqs. (5)–(8).
At the anode, the Fe2+ is formed due to the Fe oxidation (Eq. (5)). At
the cathode, H2 gas is formed from the reduction of the protons in the
acidic medium (Eq. (6)) or from water reduction in the alkaline medium
(Eq. (7)). In both cases, pH of the wastewater increases during elec-
trolysis, and monomeric and polymeric hydroxyl complexes form (Eq.
(8)). The complexes have a pronounced tendency to polymerize at pH
3.5–7.0. Fe(OH)n remains in the aqueous stream as a gelatinous sus-
pension and may be removed from the wastewater by coagulation,
adsorption, co-precipitation and sweep flocculation [27,28].
Fe (s ) → Fe 2 + (aq) + 2e− (5)
2H+ (aq) + 2e− → H2 (g ) (6)
2H2 O (l) + 2e− → 2OH− (aq) + H2 (g ) (7)
Fe 2 + (aq) + 2OH− (aq) → Fe (OH )2 (s ) (8)
Leachate membrane concentrate pollutant concentration (especially
refractory pollutants) is much higher than raw leachate. Although E-
Fenton and EC technologies have been widely used for leachate treat-
ment [29–34], there is deficiency in evaluating the performance of E-
Fenton and EC processes in high-strength leachate membrane con-
centrates treatment. Zhou et al. [35] noted that 87.5% COD and 74.06%
NH3eN were removed from leachate membrane concentrate by elec-
trochemical oxidation using the high quality boron-doped diamond
electrodes. Huang et al. [36] reported that 79.2% COD was removed
from nanofiltration (NF) concentrate from mature landfill leachate by a
coupled process of coagulation and aerated internal micro-electrolysis
(IME) with the in situ addition of hydrogen peroxide (H2O2). Due to the
limited number of studies in the literature, this study focused on the
applicability of the electrofenton and electrocoagulation processes for
the treatment of the leachate nanofiltration membrane concentrate. Our
work aims (i) to compare the performance of E-Fenton and EC processes
for COD, TOC and color removal from biologically treated NF con-
centrate (ii) to optimize the factors effecting the processes for obtaining
maximum removal efficiencies (iii) to evaluate the effect of EF and EC
processes on COD fractions of the effluent.
2. Material methods
2.1. Leachate sampling and characteristics
The leachate used in this study was first treated in a two-stage ni-
trification/denitrification process following anaerobic biological tren-
atment, and then by ultrafiltration (UF) and nanofiltration (NF) mem-
brane processes were applied to the biologically treated leachate.
Leachate samples were collected, transferred and preserved according
to the Standard Methods for the Examination of Water and Wastewater
[37]. Leachate NF concentrate characterization is given in Table 1.
2.2. Experimental procedure
The plexiglas EC and EF reactors (Fig. 1) (height of 130 mm and
Table 1
Characterization of leachate NF concentrate.
Parameter Value
pH 7.74 ± 0.07
Conductivity (mS/cm) 18.72 ± 0.65
Chloride (mg/L) 7200 ± 25
COD (mg/L) 10,000 ± 200
TOC (mg/L) 3719 ± 42
TSS (mg/L) 33 ± 3
Color (mg/L Pt-Co) 14,850 ± 155
S. Yazici Guvenc, et al.
Fig. 1. Experimental setup for both EC and EF processes.
diameter of 90 mm) and four plate electrodes comprising of two anodes
and two cathodes (120 mm x 60 mm x 3 mm) were used in the present
study. The total effective electrode area was 46 cm2 whereas the dis-
tance between electrodes was 10 mm. The electrodes were connected in
monopolar mode to a digital dc power supply.
The chemicals (H2O2, H2SO4, NaOH) were obtained from Merck
company. In each experiment, 500 mL of leachate NF concentrate was
placed in the electrolytic reactor. pH of the solution was adjusted prior
to the experiments and the solution was agitated with a magnetic stirrer
at 200 rpm. In EF process a desired amount of H2O2 (mL) was added to
the electrolytic reactor before the electrical current was turned on. A
batch study was conducted to optimize parameters; pH, current density
and reaction time for EC and pH, current density, reaction time and
peroxide dosage for EF processes. Before each run, organic impurities
and oxide layer on electrode surfaces were removed by dipping for
2 min in a solution prepared by mixing HCl solution (35%) and hex-
amethylenetetramine aqueous solution (2.8%). The electrodes were
then dried, weighed and placed into the reactor. Experiments were
conducted at room temperature. The samples were filtered using a
45 μm millipore membrane paper before analysis.
2.3. Analytical method
The COD was determined using closed reflux-titrimetric method and
color was measured according to the Standard Methods for the
Examination of Water and Wastewater [37]. TOC concentrations were
measured using a Shimadzu TOC-Vcpn analyzer.
Total COD is divided into two main fractions; biodegradable and
non-biodegradable COD which are further subdivided into particulate
and soluble fractions [38,39]. The fractions of biodegradable and non-
biodegradable COD were determined through the aeration of 1000 mL
leachate NF concentrate sample (before and after oxidation processes).
The method used is [40]: mechanical mixer using magnetic stirrer was
supplied to provide sufficient mixing. An air pump was used for aera-
tion and the sample size was maintained at 1 L by distilled water ad-
dition to prevent water loss during aeration. COD was gradually mea-
sured until obtaining a constant value. The biodegradable COD fraction
was calculated using the following Eq. (9):
COD(bi) = COD(i) − COD(f )
(9)
where COD(bi) is the biodegradable COD fraction, CODi is the initial
total COD and CODf represents the final COD value after aeration. CODf
will be considered as the non biodegradable COD fraction. Soluble
COD(s) fraction was determined using the ZnSO4 coagulant method
[39,41]. One ml of ZnSO4 (0.6 M) reagent was added to 100 ml of the
sample and pH of sample was adjusted at 10.5. The sample was stirred
rapidly (350 rpm) for one minute then slowly (30 rpm) for 5 min using a
magnetic stirrer. The sample was then left for settling for an hour and
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Journal of Water Process Engineering 31 (2019) 100863
30 ml of the supernatant was extracted from the surface. COD of the
filtered supernatant was measured as soluble COD(s). The difference
between COD(s) and COD(i) was determined to be particulate COD
(PCOD). Fractions of soluble and particulate COD were calculated by
using Eqs. (3) and (4):
COD(s) (%) = [COD(s) / COD]*100 (10)
PCOD (%) = [(COD − COD(s) )/ COD]*100 (11)
where COD is the total COD (mg/L), PCOD is particulate COD (mg/L),
and COD(s) is the total soluble COD (mg/L).
The total soluble COD(s) determined by using Eq. (10) contains
biodegradable soluble CODsbi and non-biodegradable soluble COD(subi)
sub fractions. The value of soluble biodegradable COD(sbi) is reported as
COD(bi) as given by Eq. (12) [41], whereas the soluble non-biodegrad-
able COD(subi) was determined by the difference between COD(sbi) and
COD(s). The fractions of COD(sbi) and COD(subi) were determined using
Eqs. (12) and (13):
COD(sbi) (%) = [COD(bi) / COD(s)]*100 (12)
COD(subi) (%) = [(COD)(s) − COD(bi) )/COD(s)]*100 (13)
where COD(sbi) is the biodegradable soluble COD (mg/L), COD(subi) is
the non-biodegradable soluble COD (mg/L), COD(bi) is the biodegrad-
able COD (mg/L) in batch aeration system, and COD(s) (mg/L) re-
presents the total soluble COD (mg/L).
3. Results and discusson
3.1. Effect of pH
The pH is one of the most important factors for E-Fenton process. It
is reported by many researchers that the optimum pH of Fenton process
is around 3 [42,43]. Generally, the EF reaction is performed in acidic
conditions (pH ranging between 2.0 and 4.0) [44]. The optimum pH
value was 2.8 for hydroxyl radical production [45]. Fenton process is
less effective at pH < 3 due to the regeneration of Fe2+, through re-
action between Fe3+ and H2O2. Additionally, hydrogen peroxide would
remain steady according to the formation of oxonium ion at pH below 3
[46]. The efficiency of E-Fenton process decreases rapidly, at higher pH
values, especially pH > 5. This can be explained by the fact that H2O2
is unstable in basic solution and rapidly decomposes to oxygen and
water at neutral to high pH values [46]. The increase in pH during E-
Fenton process leads to electrocoagulation whereby pollutants are re-
moved by electrostatic attraction and/or complexation of reactions due
to the conversion of Fe2+ and Fe3+ to Fe(OH)n type structures [46,47].
In EC process, Ferrous ions are only oxidized to ferric ions if the pH
is above 5 even though complete oxidation only occurs at pH of around
S. Yazici Guvenc, et al.
Fig. 2. Effect of pH on leachate NF concentrate treatment by EF process (AC: 2 A; H2O2/COD: 1.25; t: 15 min).
8–9 [47–51]. As known ferrous ions are highly soluble, poor coagulants
with no adsorption capacity of pollutants. It can be concluded that the
optimum operating pH range of iron EC is 5–9 and operation at an
initial pH of 8–9 is favorable to ensure complete oxidation of ferrous
ions.
pH is a key factor influencing the EC process performance governing
the hydrolyzed metal species. Effluent pH after EC process increases for
acidic influent but decreases for alkaline influent, due to the buffering
effect of EC [52]. The pH increase in acidic medium can be attributed to
hydrogen evolution at the cathode while the pH decrease in alkaline
medium can be explained by the formation of hydroxide precipitates
that release H+ cations at the anode and the secondary reactions as
water oxidation, chlorine production and its hydrolysis. The pH of the
effluent changes only slightly when the initial pH value is in the neutral
range (around 6–8). Moreover, hydrogen bubbles produced at the
cathode are smallest and finest at neutral pH, providing sufficient sur-
face area for gas-liquid-solid interfaces and mixing efficiency to favour
the aggregation of tiny destabilized particles and colloids [52,53].
Effect of pH on EC and EF treatment of leachate NF concemtrate is
given in Figs. 2 and 3, respectively. Experimental study was conducted
Fig. 3. Effect of pH on leachate NF concentrate treatment by EC process (AC: 3.5 A; t: 15 min).
4
Journal of Water Process Engineering 31 (2019) 100863
at pH values in the range of 2–4.5 for EF process and 6–11 for EC
process. In EF treatment COD removal efficiency increased as pH value
increased from 2 to 3.5. Maximum COD removal (61.3%) was obtained
at pH value of 3.5 ± 0.1. In EC process COD removal efficiiency in-
creased as pH value increased from 6 to 8. No significat change was
observed at pH values around 8–9 then removal efficiency decreased.
Optimum pH value for EC process was determined to be 8 ± 0.05 with
the maximum COD removal efficiency of 49.1%. Effluent pH values
increased in EF process whereas effluent pH value increased at acidic
conditions, decreased at alkaline conditions in EC process. No sig-
nificant change between influent and effluent pH values was observed
at neutral values in EC process. These results were found to be con-
sistent with literature [54–56].
3.2. Effect of applied current
In electrochemical processes, the applied current is the driving force
for the discharge of oxygen at anode and the evolution of hydrogen at
cathode leading to the generation of hydrogen peroxide. Thereby,
higher applied current increases the amount of hydrogen peroxide
S. Yazici Guvenc, et al.
Fig. 4. Effect of current on leachate NF concentrate treatment by EF process (pH; 3.5; H2O2/COD: 1.25; t: 15 min).
produced, thus increasing the number of hydroxyl radicals in the
electrolyte medium, which are highly reactive [46,57]. Higher applied
current also means higher electro-regeneration of ferrous ion from
ferric ion. However the efficiency of E-Fenton process will decrease
after a limit value of the current applied because of the competitive
electrode reactions which inhibit main reactions in the electrolytic cell
[46,58].
In the EC and EF processes, reaction rate is controlled by current
[59,60] by controlling hydroxide flocs formation. Mohajeri et al. [61]
reported that they used the electrical current as 0–3 A from the ex-
perimental conditions for leachate treatment by electro-Fenton oxida-
tion. Similar to the stduy of Mohajeri et al. [61], effect of the current in
the EC and EF processes were studied in the range of 0.75–4.25 at op-
erating time of 0–30 min (Figs. 4 and 5). The removal efficiencies in-
creased with the increasing current. As current values increased, the
amount of hydroxide flocs formation increased, the density and size of
the bubbles increased, resulting in a faster removal of pollutants
[60,62,63]. Maximum pollutant removal was obtained at 3.5 ± 0.25 A
in EC process and 2.75 ± 0.1 A in EF process. No significant change
was observed at higher current values. But, very high current values
Fig. 5. Effect of current on leachate NF concentrate treatment by EC process (pH: 8; t: 15 min).
5
Journal of Water Process Engineering 31 (2019) 100863
negatively affect the EC efficiency reversing the charge of the colloids
and redispersing them.
3.3. Effect of hydrogen peroxide concentration
Removal efficiencies of pollutants increase with increase in H2O2
concentration leading to the increase in hydroxyl radical concentration.
At H2O2 concentration over optimum values efficiency of organic ma-
terial removal decreases because of the hydroxyl radical scavenging
effect of H2O2 and the recombination of the hydroxyl radicals [46,58].
Guvenc et al. [64] noted that they applied H2O2/COD ratio range of
0.4–2 in electro-Fenton oxidation. Similarly, the effect of H2O2/COD
ratio on removal efficiencies of COD, TOC and color was studied in the
range of 0.5–2 under optimum conditions (2.75 A and pH 3.5) (Fig. 6).
The removal efficiencies of COD, TOC and color increased as H2O2/
COD ratio increased from 0.5 to 1.25 then began to decrease. COD
removal efficiency increased from 53.6% to 68.9% when H2O2/COD
ratio increased from 0.5 ± 0.08 to 1.25 ± 0.18. Thereafter COD re-
moval rate decreased to 61.6% at H2O2/COD ratio of 2 due to the un-
desired OH scavenging reactions effect.
S. Yazici Guvenc, et al.
Fig. 6. Effect of H2O2/COD ratio on NF concentrate treatment by EF process (AC: 2.75 A; pH: 3.5; t: 15 min).
3.4. Effect of reaction time
Tak et al. [65] carried out experimental studies at 10–30 min in
electrocoagulation process and optimum condition was determined to
30 min. Similarly, reaction time range of 5–30 min in this study was
applied at EC and EF processes. Figs. 7 and 8 present the effect of re-
action time (5–30 min) on the removal efficiencies of COD, TOC and
color in EC and EF processes. The obtained results showed that removal
efficiencies increased by time. The COD removal could be attributed to
the precipitation of dissolved organics. The COD removal efficiency is
dependent on the quantity of hydroxide flocs that increase with the
increase in current density and time of electrocoagulation. COD con-
centration decreased rapidly in the first 10 min of the electrocoagula-
tion process. Higher removal efficiencies of COD were observed at
longer time periods and higher cell current values [66]. At shorter time
periods since the amount of precipitate formed was not high and im-
portant part of COD is soluble, lower removal efficiencies are observed
[67]. COD removal efficiency was determined to be 43% and 69.4%
after 10 ± 0.2 min and 30 ± 1.1 min operation time respectively in
EF process. In EC process COD removal efficiency was found to be
Fig. 7. Effect of reaction time on leachate NF comcentrate treatment by EF process (AC: 2.75 A; pH: 3.5; H2O2/COD: 1.25).
6
Journal of Water Process Engineering 31 (2019) 100863
43.5% and 53.6% after 10 ± 0.28 min and 30 ± 1.32 min operation
time, respectively.
3.5. Effect of water conductivity
The amount of the current density applied depends strongly on
conductivity and ionic strength of the wastewater. The current density
efficiency increases and the treatment time required to reach a given
removal yield decreases with increasing electrolytic conductivity.
Consequently, the energy consumption is reduced [68]. Electrical
conductivity of leachate NF concentrate is high with the value around
20 mS/cm. Effluent conductivity of EC and EF processes were found to
be higher than influent conductivity values. This can be explained by
the current applied by electricity to the wastewater.
3.6. Effect of EF and EC processes on COD fractions of NF concentrate
The fractionation of COD is the most important parameter for
evaluating leachate quality and deciding the treatment method. The
total COD is divided into two main fractions; biodegradable and
S. Yazici Guvenc, et al.
Fig. 8. Effect of reaction time on leachate NF concentrate treatment by EC process (AC: 3.5 A; pH: 8).
unbiodegradable COD (inert COD). The unbiodegradable COD fraction
is divided into soluble and particulate fractions whereas the biode-
gradable COD fraction is subdivided into soluble readily biodegradable
and particulate slowly biodegradable fractions [69].
The effect of oxidation processes on biodegradable and non-biode-
gradable COD fractions was given in Fig. 9. It can be seen from Fig. 9
that biodegradable COD fraction increased from 6.37% to 17.04% and
30.08% after EC and EF processes, respectively whereas the non-bio-
degradable COD fractions decreased from 93.63% to 82.96% and
69.92% after EC and EF processes, respectively. In previous studies
improvement for biodegradable COD fraction in stabilized landfill
leachate by advanced oxidation process was reported [41,70].
Determination of soluble COD is important in identifying other COD
fractions. Fig. 9 presents the soluble and particulate COD fractions of
leachate NF concentrate before and after EC and EF processes. The
results of the previous studies related with effect of advanced oxidation
processes on biodegradable and soluble characteristics of stabilized
leachate revealed that insoluble organics can be converted to soluble
ones [39,70]. Soluble and particulate COD fractions of leachate NF
concentrate were determined as 71.14%, 28.86%, respectively. COD(s)
fraction increased to 89% and 90.3% after 60 min EC and EF processes,
respectively. Soluble COD removal rate was determined to be 39% and
57% by EC and EF processes whereas particulate COD removal rate was
found to be 82% and 81% by EC and EF processes, respectively. The
results are consistent with the ones concluded by Abu Amr et al., [39]
and Hilles [70].
The total soluble COD(s) fraction in leachate is divided into two sub-
fractions; biodegradable soluble COD(sbi) and non-biodegradable so-
luble COD(subi) [41]. COD(sbi) and COD(subi) fractions of NF concentrate
were determined to be 8.95% and 91.05%. COD(sbi) fraction increased
to 19.1% and 35.5% and COD(subi) fractions decreased to 80.9% and
64.5% after EC and EF treatment, respectively.
3.7. Operational cost
Operational cost greatly determines the feasibility of any waste-
water treatment process. The operating cost was calculated using the
following equation [71,72].
Operational cost= aCenergy+ bCelectrode+ cCchemicals
(14)
where Cenergy is the energy consumption (kWh/m3), Celectrode is the
electrode consumption (kg/m3) and Cchemicals is the chemical con-
sumption (kg/m3) of wastewater treated. The chemical cost is
7
Journal of Water Process Engineering 31 (2019) 100863
negligible because it is less than 0.001 € per m3.The operational cost
includes also labor, maintenance and other fixed costs. The latter costs
items are largely independent of the type of the electrode material [73].
In this study, energy and electrode material costs are taken into account
as major cost items, in the calculation of the operating cost as kWh per
kg of COD removed.
The major operating cost component in electrocoagulation process
is electrical energy consumption (Cenergy). The electrical energy con-
sumption was calculated using the following equation [74]:
U× i× tEC
Cenergy=
v (15)
where Celectrode is the energy consumption (kWh/m3), U is the applied
voltage (V), I is the current (A), t is the electrocoagulation time (h), and
V is the volume of the wastewater (m3).
The amount of electrode dissolved was calculated theoretically by
using Faraday's law:
i×tEC × MW
Celectrode=
z×F×v (16)
where C (g/L) is the iron or aluminum concentration in the electrolytic
cell, I is the current (A), t is the electrocoagulation time (s), Mw is the
molecular weight of the anode (g/mole), z is the chemical equivalence,
F is the Faraday constant (96,500 C/mole) and V is the volume of the
wastewater (m3).
Operational cost was calculated to be 1.94 € per m3 and 1.82 € per
m3 for EC and EF processes respectively. Values of energy and electrode
consumptions in the EF process were found to be quite lower than that
in the EC process. However the operational cost of EF process under
optimum conditions was determined to be higher than that of EC pro-
cess since the cost increased considerably with H2O2.
4. Conclusion
In this study, effect of the operational parameters on the EC and EF
treatment of leachate NF concentrate was evaluated based on COD,
TOC and color removal efficiencies, operating cost and sludge amount.
The optimum operating conditions for EF process were determined as
pH 3.5, current 2.75 A, H2O2/COD ratio 1.25 and reaction time 30 min
whereas they were found to be pH 7, current 3.5 A and reaction time
20 min for EC process. COD, TOC and color removal efficiencies at
optimum conditions were determined to be 69.4%, 60.2% and 87.6% in
EF process while COD, TOC and color removal efficiencies at optimum
S. Yazici Guvenc, et al.
Fig. 9. Variations in COD fractions of leachate NF concentrate before and after EF (AC: 2.75 A; H2O2/COD: 1.25; pH: 3.5; t: 30 min) and EC (AC: 3.5 A; pH: 8; t:
20 min).
conditions were determined to be 57.4%, 45% and 77.1% in EC process.
Under optimum conditions, amount of the sludge generated in EC
process is much higher than the amount of sludge produced in EF
process. Higher increase in biodegradable COD fraction and higher
decrease in unbiodegradable COD fraction was obtained by EF process.
Also, higher insoluble COD fraction was converted to soluble COD by
EF process. Although they don’t reach to discaharge standards ac-
cording to the environmental regulations, they are applicable for re-
ducing inert COD load. The obtained results indicated both EC and EF
processes were very effective for the leachate NF concentrate treatment
especially in inert COD removal. Moreover, the results show that both
processes can be used as post treatment unit for biologically treatead
laechate. Consequently, it can be concluded that EF process can be
prefered for leachate NF concentrate due to high removal rates and low
sludge amount.
8
Journal of Water Process Engineering 31 (2019) 100863
Acknowledgement
The authors would like to thank the ISTAC (Istanbul Environmental
Management Industry and Trade Inc.) Management Office of
Komurcuoda Landfill site for providing the leachate NF concentrate
samples.
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