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

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

⁎
Corresponding author.
E-mail addresses: [email protected] (S. Yazici Guvenc), [email protected] (K. Dincer), [email protected] (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. Journal of Water Process Engineering 31 (2019) 100863

them into smaller volumes of wastewater called membrane con- The main processes occuring in the electrolytic system when iron
centrates. Chaplin et al. [15] have found that electrochemical oxidation anodes are used can be described by the reactions given in Eqs. (5)–(8).
using BDD electrodes has an advantage over other advanced oxidation At the anode, the Fe2+ is formed due to the Fe oxidation (Eq. (5)). At
processes, as organics were readily oxidized in the presence of high the cathode, H2 gas is formed from the reduction of the protons in the
HCO3− concentrations. As a result, the membrane concentrates contain acidic medium (Eq. (6)) or from water reduction in the alkaline medium
high levels of refractory organic pollutants and inorganic salts. (Eq. (7)). In both cases, pH of the wastewater increases during elec-
The main treatment methods of concentrated leachate can be clas- trolysis, and monomeric and polymeric hydroxyl complexes form (Eq.
sified into four categories: (1) recirculation to landfills [16]; (2) soli- (8)). The complexes have a pronounced tendency to polymerize at pH
dification/stabilization [17]; (3) evaporation/distillation [18]; (4) ad- 3.5–7.0. Fe(OH)n remains in the aqueous stream as a gelatinous sus-
vanced oxidation processes [19]. The recirculation of concentrated pension and may be removed from the wastewater by coagulation,
leachate to landfills may inhibit the microbial activity [20] whereas adsorption, co-precipitation and sweep flocculation [27,28].
evaporation/distillation method require high land utilization, high
Fe (s ) → Fe 2 + (aq) + 2e− (5)
operating costs [14]. Moreover the corrosion and fouling are the two
main problems in evaporation/distillation method due to the high 2H+ (aq) + 2e− → H2 (g ) (6)
concentration of salts and inorganic matters [21]. Solidification and
stabilization of the leachate NF concentrate seems to be an acceptable 2H2 O (l) + 2e− → 2OH− (aq) + H2 (g ) (7)
solution, except for the disposal of derived solidified products [17].
Among the four categories, AOPs is an attractive method to remove Fe 2 + (aq) + 2OH− (aq) → Fe (OH )2 (s ) (8)
recalcitrant organic compounds and to increase the biodegradability of Leachate membrane concentrate pollutant concentration (especially
concentrated leachate. refractory pollutants) is much higher than raw leachate. Although E-
By AOPs bio-refractory organic matters could be destroyed via the Fenton and EC technologies have been widely used for leachate treat-
oxidation by generation of radicals, such as non-selective hydroxyl ra- ment [29–34], there is deficiency in evaluating the performance of E-
dicals [22]. Fenton, electrochemical oxidation, UV photocatalyst and Fenton and EC processes in high-strength leachate membrane con-
ozone-based processses have been investigated intensively [11,18,23]. centrates treatment. Zhou et al. [35] noted that 87.5% COD and 74.06%
High sludge generation rate in Fenton process, low energy efficiency of NH3eN were removed from leachate membrane concentrate by elec-
UV photocatalyst, high cost of ozonation processes are the big barriers trochemical oxidation using the high quality boron-doped diamond
for the application. Electrochemical oxidation has been considered as electrodes. Huang et al. [36] reported that 79.2% COD was removed
an attractive technology to treat membrane concentrates containing from nanofiltration (NF) concentrate from mature landfill leachate by a
mainly non-biodegradable organics and having high salinity and elec- coupled process of coagulation and aerated internal micro-electrolysis
tric conductivity [12,14]. (IME) with the in situ addition of hydrogen peroxide (H2O2). Due to the
Electro-Fenton process can be defined as the combination of Fenton limited number of studies in the literature, this study focused on the
and electro coagulation processes to increase the degradability of or- applicability of the electrofenton and electrocoagulation processes for
ganic compounds present in high strength wastewaters. A substantial the treatment of the leachate nanofiltration membrane concentrate. Our
increase in the oxidizing power of H2O2 occurs in the presence of work aims (i) to compare the performance of E-Fenton and EC processes
electrically assisted Fenton process. Generation of hydroxyl radicals is for COD, TOC and color removal from biologically treated NF con-
enhanced by electricity ensuring considerable improvement of removal centrate (ii) to optimize the factors effecting the processes for obtaining
of refractory organic pollutants [24]. Electro-Fenton process has two maximum removal efficiencies (iii) to evaluate the effect of EF and EC
different configurations. In the first one, Fenton reagents are added to processes on COD fractions of the effluent.
the reactor from outside and inert electrodes with high catalytic activity
are used as anode material while in the second configuration, only 2. Material methods
hydrogen peroxide is added from outside and Fe2+ is provided from
sacrificial cast iron anodes. 2.1. Leachate sampling and characteristics
The EF process based on the employment of a sacrificial iron anode
delivers Fe2+ ions into the solution (Eq. (1)) whilst simultaneously The leachate used in this study was first treated in a two-stage ni-
occurs the reduction of water at the cathode (Eq. (4)); then the hy- trification/denitrification process following anaerobic biological tren-
drogen peroxide is added in order to provide conditions for the Fenton atment, and then by ultrafiltration (UF) and nanofiltration (NF) mem-
reactions (Eqs. (2) and (3)). Moreover, Fe2+ according to Eq. (4) may brane processes were applied to the biologically treated leachate.
be continuously regenerated at the cathode depending on the electro- Leachate samples were collected, transferred and preserved according
lytic cell setup [25,26]. to the Standard Methods for the Examination of Water and Wastewater
Fe 2 + + H2 O2 → Fe 3 + + ∙OH + OH− (in bulk solution) (1) [37]. Leachate NF concentrate characterization is given in Table 1.

Fe 2 + + ∙OH → Fe 3 + + OH− (in bulk solution) (2) 2.2. Experimental procedure

Fe3 + + H2 O2 → Fe 2 + + H+ + HO2 ∙ (in bulk solution) (3)
The plexiglas EC and EF reactors (Fig. 1) (height of 130 mm and
Fe 2 + + e− → Fe 2 + (cathode ) (4)
Table 1
Another possible electrochemical method for recalcitrant and non- Characterization of leachate NF concentrate.
biodegradable organic substances removal is EC process. In EC pro-
cesses, the coagulating ions are produced in situ. The process involves Parameter Value

three stages: (i) formation of the coagulants by electrolytic oxidation of pH 7.74 ± 0.07
the ‘sacrificial electrode’, (ii) destabilization of the contaminants, par- Conductivity (mS/cm) 18.72 ± 0.65
ticulate suspension and breaking of emulsions and (iii) aggregation of Chloride (mg/L) 7200 ± 25
the destabilized pHases forming flocs. In the first stage of EC process COD (mg/L) 10,000 ± 200
TOC (mg/L) 3719 ± 42
applied current intensity, pH and the conductivity of the wastewater
TSS (mg/L) 33 ± 3
effect the generation of metallic ions and accordingly effect the per- Color (mg/L Pt-Co) 14,850 ± 155
formance of the process.

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S. Yazici Guvenc, et al. Journal of Water Process Engineering 31 (2019) 100863

Fig. 1. Experimental setup for both EC and EF processes.

diameter of 90 mm) and four plate electrodes comprising of two anodes 30 ml of the supernatant was extracted from the surface. COD of the
and two cathodes (120 mm x 60 mm x 3 mm) were used in the present filtered supernatant was measured as soluble COD(s). The difference
study. The total effective electrode area was 46 cm2 whereas the dis- between COD(s) and COD(i) was determined to be particulate COD
tance between electrodes was 10 mm. The electrodes were connected in (PCOD). Fractions of soluble and particulate COD were calculated by
monopolar mode to a digital dc power supply. using Eqs. (3) and (4):
The chemicals (H2O2, H2SO4, NaOH) were obtained from Merck
COD(s) (%) = [COD(s) / COD]*100 (10)
company. In each experiment, 500 mL of leachate NF concentrate was
placed in the electrolytic reactor. pH of the solution was adjusted prior PCOD (%) = [(COD − COD(s) )/ COD]*100 (11)
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 where COD is the total COD (mg/L), PCOD is particulate COD (mg/L),
the electrolytic reactor before the electrical current was turned on. A and COD(s) is the total soluble COD (mg/L).
batch study was conducted to optimize parameters; pH, current density The total soluble COD(s) determined by using Eq. (10) contains
and reaction time for EC and pH, current density, reaction time and biodegradable soluble CODsbi and non-biodegradable soluble COD(subi)
peroxide dosage for EF processes. Before each run, organic impurities sub fractions. The value of soluble biodegradable COD(sbi) is reported as
and oxide layer on electrode surfaces were removed by dipping for COD(bi) as given by Eq. (12) [41], whereas the soluble non-biodegrad-
2 min in a solution prepared by mixing HCl solution (35%) and hex- able COD(subi) was determined by the difference between COD(sbi) and
amethylenetetramine aqueous solution (2.8%). The electrodes were COD(s). The fractions of COD(sbi) and COD(subi) were determined using
then dried, weighed and placed into the reactor. Experiments were Eqs. (12) and (13):
conducted at room temperature. The samples were filtered using a
COD(sbi) (%) = [COD(bi) / COD(s)]*100 (12)
45 μm millipore membrane paper before analysis.
COD(subi) (%) = [(COD)(s) − COD(bi) )/COD(s)]*100 (13)
2.3. Analytical method
where COD(sbi) is the biodegradable soluble COD (mg/L), COD(subi) is
The COD was determined using closed reflux-titrimetric method and the non-biodegradable soluble COD (mg/L), COD(bi) is the biodegrad-
color was measured according to the Standard Methods for the able COD (mg/L) in batch aeration system, and COD(s) (mg/L) re-
Examination of Water and Wastewater [37]. TOC concentrations were presents the total soluble COD (mg/L).
measured using a Shimadzu TOC-Vcpn analyzer.
Total COD is divided into two main fractions; biodegradable and 3. Results and discusson
non-biodegradable COD which are further subdivided into particulate
and soluble fractions [38,39]. The fractions of biodegradable and non- 3.1. Effect of pH
biodegradable COD were determined through the aeration of 1000 mL
leachate NF concentrate sample (before and after oxidation processes). The pH is one of the most important factors for E-Fenton process. It
The method used is [40]: mechanical mixer using magnetic stirrer was is reported by many researchers that the optimum pH of Fenton process
supplied to provide sufficient mixing. An air pump was used for aera- is around 3 [42,43]. Generally, the EF reaction is performed in acidic
tion and the sample size was maintained at 1 L by distilled water ad- conditions (pH ranging between 2.0 and 4.0) [44]. The optimum pH
dition to prevent water loss during aeration. COD was gradually mea- value was 2.8 for hydroxyl radical production [45]. Fenton process is
sured until obtaining a constant value. The biodegradable COD fraction less effective at pH < 3 due to the regeneration of Fe2+, through re-
was calculated using the following Eq. (9): action between Fe3+ and H2O2. Additionally, hydrogen peroxide would
COD(bi) = COD(i) − COD(f ) remain steady according to the formation of oxonium ion at pH below 3
(9)
[46]. The efficiency of E-Fenton process decreases rapidly, at higher pH
where COD(bi) is the biodegradable COD fraction, CODi is the initial values, especially pH > 5. This can be explained by the fact that H2O2
total COD and CODf represents the final COD value after aeration. CODf is unstable in basic solution and rapidly decomposes to oxygen and
will be considered as the non biodegradable COD fraction. Soluble water at neutral to high pH values [46]. The increase in pH during E-
COD(s) fraction was determined using the ZnSO4 coagulant method Fenton process leads to electrocoagulation whereby pollutants are re-
[39,41]. One ml of ZnSO4 (0.6 M) reagent was added to 100 ml of the moved by electrostatic attraction and/or complexation of reactions due
sample and pH of sample was adjusted at 10.5. The sample was stirred to the conversion of Fe2+ and Fe3+ to Fe(OH)n type structures [46,47].
rapidly (350 rpm) for one minute then slowly (30 rpm) for 5 min using a In EC process, Ferrous ions are only oxidized to ferric ions if the pH
magnetic stirrer. The sample was then left for settling for an hour and is above 5 even though complete oxidation only occurs at pH of around

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S. Yazici Guvenc, et al. Journal of Water Process Engineering 31 (2019) 100863

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 at pH values in the range of 2–4.5 for EF process and 6–11 for EC
with no adsorption capacity of pollutants. It can be concluded that the process. In EF treatment COD removal efficiency increased as pH value
optimum operating pH range of iron EC is 5–9 and operation at an increased from 2 to 3.5. Maximum COD removal (61.3%) was obtained
initial pH of 8–9 is favorable to ensure complete oxidation of ferrous at pH value of 3.5 ± 0.1. In EC process COD removal efficiiency in-
ions. creased as pH value increased from 6 to 8. No significat change was
pH is a key factor influencing the EC process performance governing observed at pH values around 8–9 then removal efficiency decreased.
the hydrolyzed metal species. Effluent pH after EC process increases for Optimum pH value for EC process was determined to be 8 ± 0.05 with
acidic influent but decreases for alkaline influent, due to the buffering the maximum COD removal efficiency of 49.1%. Effluent pH values
effect of EC [52]. The pH increase in acidic medium can be attributed to increased in EF process whereas effluent pH value increased at acidic
hydrogen evolution at the cathode while the pH decrease in alkaline conditions, decreased at alkaline conditions in EC process. No sig-
medium can be explained by the formation of hydroxide precipitates nificant change between influent and effluent pH values was observed
that release H+ cations at the anode and the secondary reactions as at neutral values in EC process. These results were found to be con-
water oxidation, chlorine production and its hydrolysis. The pH of the sistent with literature [54–56].
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- 3.2. Effect of applied current
face area for gas-liquid-solid interfaces and mixing efficiency to favour
the aggregation of tiny destabilized particles and colloids [52,53]. In electrochemical processes, the applied current is the driving force
Effect of pH on EC and EF treatment of leachate NF concemtrate is for the discharge of oxygen at anode and the evolution of hydrogen at
given in Figs. 2 and 3, respectively. Experimental study was conducted cathode leading to the generation of hydrogen peroxide. Thereby,
higher applied current increases the amount of hydrogen peroxide

Fig. 3. Effect of pH on leachate NF concentrate treatment by EC process (AC: 3.5 A; t: 15 min).

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S. Yazici Guvenc, et al. Journal of Water Process Engineering 31 (2019) 100863

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 negatively affect the EC efficiency reversing the charge of the colloids
electrolyte medium, which are highly reactive [46,57]. Higher applied and redispersing them.
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 3.3. Effect of hydrogen peroxide concentration
electrode reactions which inhibit main reactions in the electrolytic cell
[46,58]. Removal efficiencies of pollutants increase with increase in H2O2
In the EC and EF processes, reaction rate is controlled by current concentration leading to the increase in hydroxyl radical concentration.
[59,60] by controlling hydroxide flocs formation. Mohajeri et al. [61] At H2O2 concentration over optimum values efficiency of organic ma-
reported that they used the electrical current as 0–3 A from the ex- terial removal decreases because of the hydroxyl radical scavenging
perimental conditions for leachate treatment by electro-Fenton oxida- effect of H2O2 and the recombination of the hydroxyl radicals [46,58].
tion. Similar to the stduy of Mohajeri et al. [61], effect of the current in Guvenc et al. [64] noted that they applied H2O2/COD ratio range of
the EC and EF processes were studied in the range of 0.75–4.25 at op- 0.4–2 in electro-Fenton oxidation. Similarly, the effect of H2O2/COD
erating time of 0–30 min (Figs. 4 and 5). The removal efficiencies in- ratio on removal efficiencies of COD, TOC and color was studied in the
creased with the increasing current. As current values increased, the range of 0.5–2 under optimum conditions (2.75 A and pH 3.5) (Fig. 6).
amount of hydroxide flocs formation increased, the density and size of The removal efficiencies of COD, TOC and color increased as H2O2/
the bubbles increased, resulting in a faster removal of pollutants COD ratio increased from 0.5 to 1.25 then began to decrease. COD
[60,62,63]. Maximum pollutant removal was obtained at 3.5 ± 0.25 A removal efficiency increased from 53.6% to 68.9% when H2O2/COD
in EC process and 2.75 ± 0.1 A in EF process. No significant change ratio increased from 0.5 ± 0.08 to 1.25 ± 0.18. Thereafter COD re-
was observed at higher current values. But, very high current values moval rate decreased to 61.6% at H2O2/COD ratio of 2 due to the un-
desired OH scavenging reactions effect.

Fig. 5. Effect of current on leachate NF concentrate treatment by EC process (pH: 8; t: 15 min).

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S. Yazici Guvenc, et al. Journal of Water Process Engineering 31 (2019) 100863

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 43.5% and 53.6% after 10 ± 0.28 min and 30 ± 1.32 min operation
time, respectively.
Tak et al. [65] carried out experimental studies at 10–30 min in
electrocoagulation process and optimum condition was determined to 3.5. Effect of water conductivity
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- The amount of the current density applied depends strongly on
action time (5–30 min) on the removal efficiencies of COD, TOC and conductivity and ionic strength of the wastewater. The current density
color in EC and EF processes. The obtained results showed that removal efficiency increases and the treatment time required to reach a given
efficiencies increased by time. The COD removal could be attributed to removal yield decreases with increasing electrolytic conductivity.
the precipitation of dissolved organics. The COD removal efficiency is Consequently, the energy consumption is reduced [68]. Electrical
dependent on the quantity of hydroxide flocs that increase with the conductivity of leachate NF concentrate is high with the value around
increase in current density and time of electrocoagulation. COD con- 20 mS/cm. Effluent conductivity of EC and EF processes were found to
centration decreased rapidly in the first 10 min of the electrocoagula- be higher than influent conductivity values. This can be explained by
tion process. Higher removal efficiencies of COD were observed at the current applied by electricity to the wastewater.
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 3.6. Effect of EF and EC processes on COD fractions of NF concentrate
[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 The fractionation of COD is the most important parameter for
EF process. In EC process COD removal efficiency was found to be evaluating leachate quality and deciding the treatment method. The
total COD is divided into two main fractions; biodegradable and

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).

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S. Yazici Guvenc, et al. Journal of Water Process Engineering 31 (2019) 100863

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 negligible because it is less than 0.001 € per m3.The operational cost
is divided into soluble and particulate fractions whereas the biode- includes also labor, maintenance and other fixed costs. The latter costs
gradable COD fraction is subdivided into soluble readily biodegradable items are largely independent of the type of the electrode material [73].
and particulate slowly biodegradable fractions [69]. In this study, energy and electrode material costs are taken into account
The effect of oxidation processes on biodegradable and non-biode- as major cost items, in the calculation of the operating cost as kWh per
gradable COD fractions was given in Fig. 9. It can be seen from Fig. 9 kg of COD removed.
that biodegradable COD fraction increased from 6.37% to 17.04% and The major operating cost component in electrocoagulation process
30.08% after EC and EF processes, respectively whereas the non-bio- is electrical energy consumption (Cenergy). The electrical energy con-
degradable COD fractions decreased from 93.63% to 82.96% and sumption was calculated using the following equation [74]:
69.92% after EC and EF processes, respectively. In previous studies
U× i× tEC
improvement for biodegradable COD fraction in stabilized landfill Cenergy=
v (15)
leachate by advanced oxidation process was reported [41,70].
Determination of soluble COD is important in identifying other COD where Celectrode is the energy consumption (kWh/m3), U is the applied
fractions. Fig. 9 presents the soluble and particulate COD fractions of voltage (V), I is the current (A), t is the electrocoagulation time (h), and
leachate NF concentrate before and after EC and EF processes. The V is the volume of the wastewater (m3).
results of the previous studies related with effect of advanced oxidation The amount of electrode dissolved was calculated theoretically by
processes on biodegradable and soluble characteristics of stabilized using Faraday's law:
leachate revealed that insoluble organics can be converted to soluble
i×tEC × MW
ones [39,70]. Soluble and particulate COD fractions of leachate NF Celectrode=
z×F×v (16)
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, where C (g/L) is the iron or aluminum concentration in the electrolytic
respectively. Soluble COD removal rate was determined to be 39% and cell, I is the current (A), t is the electrocoagulation time (s), Mw is the
57% by EC and EF processes whereas particulate COD removal rate was molecular weight of the anode (g/mole), z is the chemical equivalence,
found to be 82% and 81% by EC and EF processes, respectively. The F is the Faraday constant (96,500 C/mole) and V is the volume of the
results are consistent with the ones concluded by Abu Amr et al., [39] wastewater (m3).
and Hilles [70]. Operational cost was calculated to be 1.94 € per m3 and 1.82 € per
The total soluble COD(s) fraction in leachate is divided into two sub- m3 for EC and EF processes respectively. Values of energy and electrode
fractions; biodegradable soluble COD(sbi) and non-biodegradable so- consumptions in the EF process were found to be quite lower than that
luble COD(subi) [41]. COD(sbi) and COD(subi) fractions of NF concentrate in the EC process. However the operational cost of EF process under
were determined to be 8.95% and 91.05%. COD(sbi) fraction increased optimum conditions was determined to be higher than that of EC pro-
to 19.1% and 35.5% and COD(subi) fractions decreased to 80.9% and cess since the cost increased considerably with H2O2.
64.5% after EC and EF treatment, respectively.
4. Conclusion
3.7. Operational cost
In this study, effect of the operational parameters on the EC and EF
Operational cost greatly determines the feasibility of any waste- treatment of leachate NF concentrate was evaluated based on COD,
water treatment process. The operating cost was calculated using the TOC and color removal efficiencies, operating cost and sludge amount.
following equation [71,72]. The optimum operating conditions for EF process were determined as
Operational cost= aCenergy+ bCelectrode+ cCchemicals pH 3.5, current 2.75 A, H2O2/COD ratio 1.25 and reaction time 30 min
(14)
whereas they were found to be pH 7, current 3.5 A and reaction time
where Cenergy is the energy consumption (kWh/m3), Celectrode is the 20 min for EC process. COD, TOC and color removal efficiencies at
electrode consumption (kg/m3) and Cchemicals is the chemical con- optimum conditions were determined to be 69.4%, 60.2% and 87.6% in
sumption (kg/m3) of wastewater treated. The chemical cost is EF process while COD, TOC and color removal efficiencies at optimum

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S. Yazici Guvenc, et al. Journal of Water Process Engineering 31 (2019) 100863

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. Acknowledgement

Under optimum conditions, amount of the sludge generated in EC
process is much higher than the amount of sludge produced in EF The authors would like to thank the ISTAC (Istanbul Environmental
process. Higher increase in biodegradable COD fraction and higher Management Industry and Trade Inc.) Management Office of
decrease in unbiodegradable COD fraction was obtained by EF process. Komurcuoda Landfill site for providing the leachate NF concentrate
Also, higher insoluble COD fraction was converted to soluble COD by samples.
EF process. Although they don’t reach to discaharge standards ac-
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