Journal of Hazardous Materials 351 (2018) 90–97

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Journal of Hazardous Materials

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

Tertiary treatment of landfill leachate by an integrated Electro-Oxidation/ T

Electro-Coagulation/Electro-Reduction process: Performance and
mechanism
⁎
Jing Dinga, Liangliang Weia, Huibin Huanga, Qingliang Zhaoa, , Weizhu Houa,
Felix Tetteh Kabuteya, Yixing Yuana, Dionysios D. Dionysioub
a
State Key Laboratory of Urban Water Resources and Environment (SKLUWRE), School of Environment, Harbin Institute of Technology, Harbin 150090, China
b
Environmental Engineering and Science Program, Department of Chemical and Environmental Engineering, University of Cincinnati, Cincinnati, OH 45221, United States

G RA P H I C A L AB S T R A C T

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

Keywords: This study presents an integrated Electro-Oxidation/Electro-Coagulation/Electro-Reduction (EO/EC/ER) process

Landfill leachate for tertiary landfill leachate treatment. The influence of variables including leachate characteristics and op-
Electro-Oxidation eration conditions on the performance of EO/EC/ER process was evaluated. The removal mechanisms were
Electro-Coagulation explored by comparing results of anode, cathode, and bipolar electrode substitution experiments. The perfor-
Electro-Reduction
mance of the process in a scaled-up reactor was investigated to assure the feasibility of the process. Results
DSA electrodes
showed that simultaneous removal of carbonaceous and nitrogenous pollutants was achieved under optimal
conditions. Ammonia removal was due to the free chlorine generation of EO while organic matter degradation
was achieved by both EO and EC processes. Nitrate removal was attributed to both ER and EC processes, with the
higher removal achieved by ER process. In a scaled-up reactor, the EO/EC/ER process was able to remove
50–60% organic matter and 100% ammonia at charge of 1.5 Ah/L with energy consumption of 15 kW h/m3.
Considering energy cost, the process is more efficient to meet the requirement of organic removal efficiency less
than 70%. These results show the feasibility and potential of the EO/EC/ER process as an alternative tertiary
treatment to achieve the simultaneous removal of organic matter, ammonia, nitrate, and color of leachate.

⁎
Corresponding author.
E-mail addresses: zhql1962@163.com, qlzhao@hit.edu.cn (Q. Zhao).

https://doi.org/10.1016/j.jhazmat.2018.02.038
Received 31 October 2017; Received in revised form 6 February 2018; Accepted 21 February 2018
0304-3894/ © 2018 Elsevier B.V. All rights reserved.
J. Ding et al.
1. Introduction
During the process of sanitary landfilling or temporary storage for
waste incineration, leachates are produced as a result of rainwater
percolation, moisture presence and biological process of the solid
wastes [1]. The treatment for landfill leachate is a great challenge be-
cause of the leachate complex, refractory, and varied composition [2].
Biological treatments, including anaerobic and aerobic processes, are
commonly used as first step to remove most organic pollutants from
raw landfill leachate [3]. Then physical-chemical processes are fol-
lowed to effectively treat the complex biological effluent and deal with
the residual pollutants. Such processes include multistage membrane
technology [3,4], coagulation/precipitation methods [5,6], activated
carbon filtration process [7], and advanced oxidation processes [7,8].
Electrochemical treatment has been successfully applied in complex
wastewater treatment and has attracted much attention due to its en-
vironmental compatibility, high removal efficiency, easy operation, and
possibility for automation [9,10]. Among the electrochemical technol-
ogies, the most studied for the treatment of landfill leachates are EO
and EC. Previous studies investigated the behavior of EO for landfill
leachate on the removal of organic compounds, color, and ammonia
nitrogen [11–13]. Anodic oxidation in EO using different anode mate-
rials such as dimensional stable anode (DSA, Ti based metal coated with
Ru, Ir or Rh oxides) [11,14,15], boron-doped diamond (BDD) [16,17],
thin film oxides (PbO2, SnO2) [13,17], and carbon-based electrode
[2,18], can achieve direct and indirect oxidation of organics and am-
monia by active chlorine species (ClO−, HClO, and Cl2) or hydroxyl
radicals (%OH) [12]. Apart from anode materials, research has also fo-
cused on the effect of operating parameters, for example chloride
concentration, current density, electrolysis time, initial pH, and role of
additional electrolytes [11–13]. Owing to its high efficiency and ver-
satility, EO has been applied as pretreatment and post treatment tech-
nology for raw leachate and its biological effluent [2,19]. The EO as
pretreatment process was evaluated to improve the biodegradability of
sanitary landfill leachate and achieved an increase of the ratio between
biochemical oxygen demand (BOD) and chemical oxygen demand
(COD) (BOD/COD) from 0.3 to 0.88 [20]. Turro et al. used EO for the
treatment of stabilized landfill leachate and obtained 90% COD, com-
plete color, and total phenol removal under the optimal operating
conditions [11]. Del Moro et al. investigated the comparison of EO as a
standalone and as post treatment process, indicating the economic su-
periority of EO combined with biofilter [15].
EC is an effective and simple method for treating wastewater, such
as landfill leachate [1,5,21], tannery [22,23], and textile industrial
effluent [9,24], which are often tainted with color substances, sus-
pended solids, organic, inorganic, and heavy metal pollutants that
could be flocculated. In the EC process, the coagulation agents are
generated in situ by the EO of “sacrificial electrode”, undergo desta-
bilization, and aggregate to form flocs with contaminants [25]. The
most widely used anode materials for EC are iron and aluminum, which
always hydrolyze to polymeric iron and aluminum hydroxides. Iron
electrode material is considered to be more appropriate for EC in lea-
chate tertiary treatment because it is less toxic and more acceptable in
the environment [26]. Lacasa et al. also indicated that the cost of EC by
iron is lower than that by aluminum [27]. Electro-Flotation (EF) always
takes place in EC since hydrogen bubbles are produced at the cathode
and some flocculated pollutants are floated by natural buoyancy to the
surface. Important operating factors influencing the EC performance
include inter-electrode distance, mechanical stirring, current density,
pH, and conductivity [1,9,28]. The EC processes have been shown high
effectiveness not only in the removal of color [26], refractory organic
matter [5], and heavy metals [23], but also in the elimination of in-
organic contaminants, such as nitrate [27,29] and phosphates [27]. The
feasibility of EC on treating leachate was examined, achieving high
removal efficiency for COD, turbidity, color, UV254, and 40% nitrate
removal, but the process was found not appropriate for the removal of
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Journal of Hazardous Materials 351 (2018) 90–97
ammonia from leachate [21]. Besides EC, the ER process is also popular
for nitrate removal [30,31]. In the ER process, electrons from the
cathode surface react with nitrate to form intermediate nitrite [32] and
nitrogen gas as the final product [33]. In our previous study, nitrate
removal with graphite felt (GF) as cathode in dual-chamber cell showed
high performance and broad application prospects [34].
In recent years, the combination of electrochemical methods has the
potential to eliminate various contaminants and enhance the treatment
efficiency [35]. The significance of this work is to explore an integrated
electrochemical process that employs iron bipolar electrode and eval-
uate its performance as an alternative treatment process for the removal
of both carbonaceous and nitrogenous contaminants in landfill lea-
chate. There are only few articles in the literature that deal with topics
related to bipolar electrochemical system. Mameri et al. reported the
use of bipolar electrodes resulted in increase of the anode area and
reduction in electrolysis time [36]. Various bipolar electrodes with
different forms of anodes were applied to expand the capabilities of
electrochemical processes by various researchers. The continuous alu-
minum bipolar ECEO-EF reactor was designed and evaluated for si-
multaneous removal of ammonia and phosphate for wastewater effluent
[37]. Llanos and Cotillas carried out an integrated electro-disinfection/
EC process with iron or aluminum bipolar electrode to remove Escher-
ichia coli and turbidity for urban wastewater treatment and reuse
[38,39]. Peroxielectrocoagulation/EO/EF process was constructed with
aluminum bipolar electrodes for effective removal of organic pollutants
from the olive mill wastewater and achieved increase in biodegrad-
ability index (BOD/COD) from 0.29 to 0.46 [40].
In our previous studies, we investigated the performance of ER on
nitrate reduction [34] and an integrated EO/ER process on simulta-
neous removal of ammonia, nitrate, and coliforms [41]. Motivated by
our previous results, an EO/EC/ER process, consisting of DSA as anode,
GF as cathode, and perforate iron plate as bipolar electrode, was de-
veloped and applied for the treatment of actual (field) leachate biolo-
gical effluent in this study. The design of bipolar electrode between
anode and cathode could achieve simultaneous removal of residual
COD, ammonia, and nitrate in the leachate. To the authors’ best
knowledge, this integrated process of EO/EC/ER has not yet been re-
ported. The aim of this work was to evaluate the performance of this
EO/EC/ER process for the removal of organic and nitrogen con-
taminants. Performance evaluation included the effects of several
parameters, such as chloride concentration, pH, type of anode mate-
rials, inter-electrode gap, and flow velocity. The removal mechanism of
this process was explored by comparing results of four parallel ex-
periments. In addition, the feasibility of this integrated process was
evaluated in a scaled-up reactor on the basis of pollutants removal and
energy consumption.
2. Materials and methods
2.1. Experimental set-up and operation
Experiments were conducted in batch mode, with recirculation
(Fig.1). BDD or DSA (Ir-Ru oxide cover, DSA1 or Ir-Ta-Sn oxide cover,
DSA2) were used as anode, GF or titanium net (Ti) was served as
cathode, while iron net (Fe) was introduced between anode and
cathode as bipolar electrode. The BDD used was silicon based electrode
and was purchased from Neocoat SA, Switzerland. The perforated iron
electrodes were polished and cleansed in distilled water before use.
Details of DSA, GF and titanium electrodes are available in the litera-
ture [34,41]. A potentiostat (Zhaoxin Corp., JPS-3005, 0–30 V, China)
supplied electric power for this process. The design of the experiments
is shown in Table S1. The electrochemical process was carried out in a
0.12 L reactor with immersed electrode area of 10 cm2 for model and
actual leachate. A scaled-up reactor of 2.8 L volume and the electrode
area of 100 cm2 was applied for actual leachate to evaluate the feasi-
bility of this EO/EC/ER process.
J. Ding et al.
Fig. 1. Experimental setup of the EO/EC/ER process.
2.2. Model solution and actual landfill leachate
Model solution and actual landfill leachate with different con-
centrations were used in this study. The model solution was obtained by
dissolving NaCl, NH4Cl, and NaNO3 in distilled water. The actual lea-
chate was the effluent from the secondary sedimentation tank in a
municipal sanitary landfill facility, located in northeast of China. The
pollutants in leachate of this landfill site were removed by two stage
biological treatment, followed by microfiltration and nanofiltration
processes. The leachate was collected in barrels after the biological
process, and kept in 4 °C refrigerator until use. The characteristics of the
model solution and actual leachate are presented in Table 1. In the
studies aimed to investigate the influence of process parameters,
chloride ion in actual leachate was increased up to the desired con-
centration of 2500 mg/L, 5000 mg/L, 7000 mg/L, and 9000 mg/L by
dosing NaCl. The pH of actual leachate was adjusted by adding NaOH
or H2SO4 according to the requirements of the experiment design (see
Table S1). In a scaled-up reactor, actual leachate with two levels of
concentration of pollutants was applied as the influent. The details of
initial concentrations of pollutants in different assays are shown in
Table S1.
2.3. Analytical methods
Ammonia nitrogen (NH4+-N) and organic matter as chemical
oxygen demand (COD) were quantified according to standard methods
[42]. Color removal efficiency was calculated by spectrophotometry at
410 nm. Total nitrogen (TN) was determined with the Carbon and Ni-
trogen Analyzer (Shimadzu TOC-VCPN, Japan). Nitrate nitrogen
(NO3−-N), nitrite nitrogen (NO2−-N) and chloride inorganic anions
(Cl− and ClO3−) were determined by ion chromatography (IC, Dionex
ICS3000, America) with a Dionex Ion Pac AS11-HC 4 × 250 mm anion
exchange column. Total free chorine (chlorine, hypochlorite, and hy-
pochlorous acid) was measured with the N,N-diethyl-p-phenylenedia-
mine (DPD) standard method [42]. After four-hour natural sedi-
mentation, total soluble iron ions from the supernatant of these samples
were measured by inductively coupled plasma emission spectrometer
Table 1
The characteristics of the model solution and actual leachate used in this study.
Wastewater pH NO3−-N NH4+-N COD (mg/L)
(mg/L) (mg/L)
Model solution 7.5 100 100 – 5000
Actual leachates 7.4–8.5 35–128 49–130 130–600
Journal of Hazardous Materials 351 (2018) 90–97
Fig. 2. Removal of ammonia and nitrate for model solution and actual leachate with DSA
anode by EO/EC/ER process (pH: 7.5, chloride ion: 5000 mg/L, initial NH4+-N and
NO3−-N: 100 mg/L).
(ICP, PE Optima 5300 DV, America). The precipitates in the reactor
were collected, dried in oven after three times rinse by distilled water,
and milled for the analysis of inorganic components (C, N) by Elemental
Analyzer (Elementar, Vario Micro cube, Germany).
The removal of pollutants was represented against the electric
charge (Q), as calculated in Ding et al. [41], which was related to both
current density and time. The energy consumption was estimated ac-
cording to Eq. (1), where W is the energy consumption (kWh/m3), Q is
the electric charge (Ah/L), and v is the cell potential (V).
W=Q×v (1)
3. Results and discussion
3.1. Performance and influence factors of EO/EC/ER process
3.1.1. Influence of leachate characteristics
3.1.1.1. Model solution and actual leachate. Fig. 2 shows the variations
of ammonia and nitrate during the EO/EC/ER process of model solution
containing ammonia and nitrate and actual leachate. Ammonia
concentration decreased with electric charge and could be completely
removed in model and actual leachate before 1.5 Ah/L, indicating no
obvious difference of performance on ammonia removal in model and
actual leachate. This behavior indicated that ammonia removal was
mainly due to the electro-generation of free chlorine species (Eqs.
(2–4)) and the subsequent oxidation (Eq. (5)) [14].
2Cl− → Cl2 + 2 e− (2)
−
Cl2 + H2O → HOCl + Cl + H +
(3)
HOCl ↔ ClO + H− +
(4)
−
2NH4+ + 3 HOCl → N2 + 3 H2O + 5 H + 3Cl +
(5)
However, a quite different performance on nitrate removal was
observed in model solution and actual leachate (Fig. 2). Comparing
nitrate profiles during EO/EC/ER process, nitrate removal occurred at a
slower rate in actual than model solution, which is similar to the finding
using another electrochemical reactor in a previous study [41]. The
applied charge necessary to remove 67% nitrate was 4.3 and 16 Ah/L
for model solution and actual leachates, respectively. This decrease on
nitrate removal efficiency could be explained by the occurrence of other
Cl− (mg/L) oxygen-contained anions and organic matter in actual leachate [34].
The comparison between the actual leachate with model solution aimed
to indicate the necessity of applying actual leachate in the studies of
1826–2530 nitrate removal. To better evaluate the performance of EO/EC/ER
process, all the work in below was carried out with actual leachate.
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J. Ding et al.
3.1.1.2. Chloride concentrations. The effect of chloride concentration on
ammonia removal in EO has been proved to be positive due to the
indirect oxidation process [43] and was investigated in previous studies
[14,44]. A positive influence of a higher chloride concentration on
ammonia removal during EO/EC/ER process is presented (Fig. S1a).
The continuously produced free chlorine may be preferentially
consumed by ammonia oxidation before 2Ah/L, its concentration
increased in leachate after depletion of easily oxidized pollutants
(Fig. S1b). Free chlorine concentration increased with chloride
concentration and electric charge after electric charge of 4 Ah/L. A
chloride concentration of 5000 mg/L was applied in the follow up
experiments to achieve complete ammonia removal.
3.1.1.3. pH. The removal of ammonia, COD and TN during the EO/EC/
ER process was also affected by the variation of pH value (3, 5, 7, 9, and
11) (Fig. S2). The ammonia removal efficiency at 0.9 Ah/L charge
declined sharply at an acidic pH value of 3, which indicated that initial
pH should be kept over 5 to increase the production of chlorine. The
removal efficiency of TN (Fig. S2b) remained almost unchanged (from
71% to 77%) with the change of pH from 3 to 9. The process with an
initial pH ranging from 7 to 9 exhibited no significant change for
ammonia, TN, and COD removal, indicating no extra chemicals were
required to adjust pH when treating actual leachate.
3.1.2. Influence of operation conditions
3.1.2.1. Anode material. Fig. 3 shows the removal of ammonia (a), COD
(b), color (c), and the evolution of free chlorine, chlorate (d) during the
integrated process with DSA1, DSA2, and BDD anodes. The obtained
ammonia removal efficiency using DSA1, DSA2, and BDD was 100%,
87%, and 84% at 1.5 Ah/L electric charge while the COD removal
efficiency reached 26%, 24%, and 23%, respectively, as shown in
Fig. 3a and b. DSA materials are classified as “active electrodes” due to
more catalytic active sites on the surface for chlorine generation [1].
BDD is a popular but expensive anode material, which represents “non-
active electrodes”. In contrast to the DSA anodes, BDD has a high
overpotential for oxygen evolution and is likely to oxidize organics to
CO2 [10,45]. Indeed, in a one-compartment EO cell for the abatement
of membrane concentrates the performance of BDD was better than that
Fig. 3. Variation of ammonia (a), COD (b), color (c), free chlorine (d), and chlorate (d) with electric charge during the process with DSA1, DSA2, and BDD anodes (Actual leachate, pH:
7.5, chloride ion: 5000 mg/L, initial NH4+-N and NO3−-N: 100 mg/L, COD: 600 mg/L).
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Journal of Hazardous Materials 351 (2018) 90–97
of DSA on COD removal and current efficiency [46]. The different
results obtained here were due to the coupling of several removal
mechanisms on COD removal in this process.
The integrated process with DSA1, BDD, and DSA2 also resulted in
88%, 84%, and 81% decolorization at 1.5 Ah/L as shown in Fig. 3c.
According to the results of Figs. 2 and 3a–c, EO/EC/ER process is ef-
fective for ammonia and color removal, and capable of removing partial
nitrate and COD for actual leachate. In the process, free chlorine was
produced and consumed with all investigated anodes, as shown in
Fig. 3d. The higher formation rate of chlorate on the anodes after am-
monia complete removal in Fig. 3d indicated that free chlorine is easy
to react with ammonia instead of decomposition to form chlorate,
which is also supported by previous studies using BDD anode [16,43].
Chlorate generated on BDD anode was higher than that on DSA type
anode, with the concentrations of 230 mg/L, 10.9 mg/L, and 8.4 mg/L
with BDD, DSA1, and DSA2 at 1.5Ah/L electric charge. Similar trends
that more chlorate was generated on BDD than DSA anode were also
observed in Polcaro et al. [47]. The formation of chlorate on BDD
suggested higher health risk for chlorine by-product using this anode
material. In contrast to BDD, DSA type anode is made of inexpensive
material, which is available in various geometries which makes it a
suitable material for application on larger scale. DSA1 was chosen as the
anode material in this research because of its lower electrical resistivity
compared with DSA2.
3.1.2.2. Inter-electrode gap. When the gap increased from 2.5 to 5.7 cm,
the electric charge consumed for > 97% ammonia removal increased
from 1.3 to 1.7 Ah/L (Fig. S3). No significant difference was observed
for COD removal under 2.5 and 5.7 cm distance, with about 50% COD
removed at 4 Ah/L. The difference in COD removal in the EC process
was also not significant between 2.0 and 4.0 cm distance in the previous
study [21]. Shorter distance minimizes the IR drop, facilitates the
electron transfer, and further enhances the ammonia oxidation around
the anode. However, shorter distance can also induce faster electrode
passivation and create difficulties in engineering operations. An
adequate inter electrode gap of 2.5 cm was determined after
balancing the removal efficacy and operational feasibility of the EO/
EC/ER process.
J. Ding et al.
Fig. 4. Ammonia (a), COD (b) and nitrate (c) removal in systems with different electrode
usage (DSA1 as anode, Fe as bipolar electrode, GF as cathode, abbreviated as DSA-Fe-GF;
DSA1 as anode, Ti as bipolar electrode, GF as cathode, abbreviated as DSA-Ti-GF; DSA1 as
anode, Fe as bipolar electrode, GF as cathode, abbreviated as DSA-Fe-Ti; Ti as anode, Fe
as bipolar electrode, GF as cathode, abbreviated as Ti-Fe-GF; Actual leachate, pH: 7.5,
chloride ion: 5000 mg/L, initial NH4+-N and NO3−-N: 100 mg/L, COD: 372 mg/L).
3.1.2.3. Wastewater flow velocity. Flow velocity from 10 to 150 mL/min
has less influence on ammonia removal, with complete removal before
1.5 Ah/L (Fig. S4a). Slight decreases on color, COD, and nitrate removal
are observed with the increase of velocity (Fig. S4b). The use of stirring
in EC process could influence the precipitation of flocs in situ generated
by electric charge [48]. Similarly, suitable flow velocity will benefit the
94
Journal of Hazardous Materials 351 (2018) 90–97
EO/EC/ER process by supplying a more homogeneous solution to
promote the contact of pollutants with coagulants, oxidants and
reductants. The disturbance and breakup of flocs precipitation in EC
process also should be avoided when the velocity is increased.
Depending on the results, a velocity of 10 mL/min was adopted as
more suitable for this EO/EC/ER process.
3.2. Removal mechanisms of EO/EC/ER process
The performance of the four systems with different electrode type
for ammonia, COD, and nitrate removal was investigated and the re-
sults are compared in Fig. 4. Ti net with low activity was used as anode,
cathode and bipolar electrode for the substitution of DSA1, GF and Fe,
respectively. The ammonia concentration remained constant during
1.5 Ah/L run with Ti net as anode, while ammonia decreased sharply
and complete ammonia removal was achieved at 1.5 Ah/L with DSA1 as
anode (Fig.4a). This indicated the ammonia removal in EO/EC/ER
process was predominately attributed to free chlorine generated in EO
process, regardless of the electrode materials used for bipolar electrode
and cathode. The EC process has been found to be not effective on the
removal of ammonia [21]. In other words, this novel EO/EC/ER process
could provide the capability of removing ammonia compared with the
single EC process.
The highest COD removal efficiency of 84% was achieved when
using DSA1 as anode, Fe as bipolar electrode and GF as cathode after
around 16 Ah/L run, followed by 81% removal rate with Ti net cathode,
while the removal efficiency only reached 45% with when Ti net bi-
polar electrode (Fig. 4b). The perforated iron bipolar electrode is re-
markable to be a sacrificed material to induce EC process under applied
voltage, whereas Ti net as bipolar electrode is inactive for EC process
[27,39]. This indicated the removal process accounting for COD re-
moval included both EO and EC in this process, the proportion of which
seemed equal. Fernandes et al. applied the combined EC + EO process
to remove COD and enhance the biodegradability of landfill leachate
[20], where around 40% COD could be removed after 3h EC and ad-
ditional 45% COD was further eliminated by 8h EO process with BDD
anode at 1A in the two separate systems. Because both EC and EO are
able to remove COD from wastewater, this EO/EC/ER system could
improve COD removal efficiency by integrating EO and EC in one re-
actor, another important advantage of which is the use of single power
supply to achieve both EO and EC process.
In this EO/EC/ER process, 65% nitrate removal was also observed
after the end of run (Fig. 4c). As indicated in previous study [34],
higher nitrate reduction rate (70%) was obtained with GF cathode
material than with Ti cathode (8%), indicating Ti cathode surface ex-
hibits very low activity for nitrate reduction. The experiments on ni-
trate removal induced by EO/EC and EO/ER process was conducted by
replacing the cathode and bipolar electrode with Ti net, reaching 29%
and 47% nitrate conversion efficiency, respectively. The feasibility of
ER or EC processes on nitrate removal has been presented in the study
of Koparal and Öğütveren [30]. The total nitrogen content of the dried
flocs was 0.18% and 0.16% in the DSA-Fe-GF and DSA-Fe-Ti systems,
while 2.31% and 2.16% of total carbon was detected in the same
samples. These results directly confirmed the partial transfer of organic
and nitrogen species from aqueous solution to ferric hydroxide pre-
cipitates. The conversion and reduction of nitrate to N2 gas or NH4+ is
the main reaction and pathway in ER on the cathode [34,49], while
nitrate removal is also achieved by absorbing on the surface of growing
iron-hydroxide precipitates in EC process [29]. Thus, in the integrated
process, nitrate removal was attributed to both ER and EC processes,
with the higher removal proportion of nitrate obtained by the ER pro-
cess. This is also the first time to integrate ER and EC in one reactor to
enhance nitrate conversion.
The possible mechanisms for pollutant degradation by this novel
EO/EC/ER process are illustrated in Fig. 5. As reported, DSA1 anode
was able to oxidize ammonia to nitrogen gas [14] and mineralize
J. Ding et al.
Fig. 5. Possible reactions and removal mechanisms in the EO/EC/ER process.
organic matter [11] due to the formation of free chlorine species (Eqs.
(2–4))). The concentration of free chlorine produced by DSA1 was
higher than that of BDD (Fig. 3d), thus DSA1 showed a higher oxidation
activity of ammonia removal than BDD. Chloride ions were recycled in
the solution after oxidation by electron and reaction with ammonia,
thus promoting ammonia removal. As one of most commonly haloge-
nated by-compounds, Trihalomethanes (THMs) with 12 μg/L and
14 μg/L were found in EO process for WWTP effluent tertiary treatment
[41] and seawater recirculating aquaculture system [50], respectively.
The THMs in EO/EC/ER process will be produced resulted by the EO
process, thus the research of chlorinated organic compounds presented
in EO/EC/ER process deserves further investigation.
Iron electrode is an excellent sacrificial anode in the EC process
[20,27], and it can also be used as bipolar electrode to generate ferric
hydroxide floc by virtue of the induced voltage [39]. Organic matter
precipitated with flocs in the EC process during the degradation of
anodic oxidants. Previous references also pointed out that nitrate re-
moval took place with the enmeshment of coagulant precipitate
[27,30]. Additionally, GF cathode had good efficiency for nitrate re-
moval in the ER process based on the results of substitution experiments
(Fig. 4d) and those of a previous study [34]. The direct reduction of
nitrate by electrons was easily influenced by leachate characteristics,
such as oxygen contained anions and organic matter (Fig. 2). The re-
moval of aquatic TN (Fig. S2b) suggested the nitrogen species trans-
formation from liquid to other phases (gas and solid phases).
To sum up, the simultaneous removal of COD, ammonia, nitrate,
and color was markedly accomplished using a single potentiostat by
this EO/EC/ER process, and therefore the usage efficiency of electric
charge was significantly increased.
3.3. Performance and energy consumption of scaled-up EO/EC/ER process
In a scaled-up reactor of 2.8 L, the removals of pollutants including
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Journal of Hazardous Materials 351 (2018) 90–97
Fig. 6. Variation of COD, ammonia, nitrate, color, and iron species with Q increase under
different initial concentrations of pollutants in the scaled-up reactor (a: high initial pol-
lutants concentration; b: low initial pollutants concentration, more details of concentra-
tions shown in Table S1).
COD, ammonia, nitrate, and color and the variation of total soluble iron
were determined and results are shown in Fig. 6. Independent of initial
pollutant concentrations, the profile of concentration of iron ions in
both experiments showed an increase followed by a decrease during
EO/EC/ER process. The fluctuation of iron ions was attributed to the
iron hydroxide generation and the following precipitation of the sus-
pended or dissolved pollutants from the aqueous phase, which verified
the proposed mechanism in Fig. 5. Similar behavior of soluble iron ions
concentration peak was reported in a previous EC study [20]. Specially,
total iron concentration reached the highest of 5.5 mg/L in Fig. 6a
whereas the peak value of 5.3 mg/L was observed in Fig. 6b at 1 Ah/L.
Prolonging electric charge, the iron concentrations indicated a sharp
decrease followed by a slower decrease in Fig. 6a. At the end of both
experiments, iron concentrations decreased below 0.5 mg/L.
The application of scaled-up reactor led to a faster removal of COD
from the solution. The variation of COD indicated an initial sharp de-
cline, and then a smooth decrease, compared with continuous decrease
in the small-size reactor (Figs. 3b and Figure 4b). At charge of about
1.5 Ah/L, COD removal efficiency achieved 50% in Fig. 6a and 60% in
Fig. 6b, higher than that of 27% obtained in the small-size reactor in
Fig. 4b. At the end of experiments in Figs. 4b and Figure 6a (about
14 Ah/L), both COD concentrations decreased by 84–85%. The faster
decrease in COD in the scaled-up reactor is probably due to the en-
hanced precipitation with the iron flocs under larger reaction space.
However, the scaled-up reactor promoted a lower nitrate removal of
45% (Fig. 6a), compared with that of 64% in the small-size reactor
(Fig. 4c). Furthermore, a lower nitrate removal efficiency of 10% is
presented in Fig. 6b. The poor performance of nitrate removal was
possibly due to variation of hydraulic condition in the scaled-up
J. Ding et al.
Fig. 7. Variation of energy consumption with the change of COD removal efficiency in the
scaled-up reactor.
reactor, which accelerated the anodic interference and oxidation of
intermediate products of ER process. Thus, the decline of nitrate re-
moval in ER process on the cathode was observed in the scaled-up re-
actor. The rapid removal of other pollutants such as ammonia and color
is shown in Fig. 6. Complete removal of ammonia was achieved at the
charge of 1.5 Ah/L in Fig. 6a and 1 Ah/L in Fig. 6b. Compared with the
results in Fig. 4a, it indicated the decrease of ammonia in the EO/EC/
ER process was independent of reactor size. The concentrations of COD
and ammonia could meet the requirements of Standard for Pollution
Control on the Landfill Site of Municipal Solid Waste (GB 16889-2008,
COD below 100 mg/L, ammonium nitrogen below 25 mg/L) at the
charge of 2.8 Ah/L (Fig. 6a) and 1 Ah/L (Fig. 6b).
Independent of initial COD, the electric energy of 11 kW h/m3 could
achieve 40–43% COD removal (Fig. 7). The pursuit of higher COD re-
moval efficiency increased the energy consumed. For the initial COD of
130 mg/L, the EO/EC/ER process removed 60% COD and 100% am-
monia with energy of 15 kW h/m3. The energy consumed to remove
64% COD with the initial COD of 372 mg/L is 21 kW h/m3. The energy
used to remove residual COD increased more dramatically thus re-
sulting in the slope between W and % COD removal soared after 70%
COD removal (divided by red dot line in Fig. 7).
The energy values of COD removal to refine biological effluent was
reported to be more acceptable on the basis of economic consideration,
as the energy consumption calculated by Del Moro et al. [15] was
465.2 kW h/m3 for the electrochemical treatment of raw leachate with
initial COD of 3937 mg/L to reach a 500 mg/L COD. Compared to other
electrochemical processes on leachate treatment, the energy values in
Fig. 7 fall within the range of previously reported values. Wang et al.
[51] gave energy cost of conventional and enhanced electrode system
with 300 and 180 kW h/kg COD (approximate 15 and 9 kW h/m3 after
calculation) to remove around 42% COD from secondary leachate in
industrial wastewater. The energy cost for similar COD removal per-
formance here was 11 kW h/m3, meanwhile, 50 mg/L ammonia was
completely removed at this charge cost in our study. In other words, the
EO/EC/ER process demonstrated multifunctional performance and
electrical energy was more effectively consumed to remove COD, am-
monia, nitrate, color, and other pollutants simultaneously.
Taking into account its economic feasibility, this EO/EC/ER process
is more suitable to be applied when the requirement of COD removal
efficiency is less than 70%. This integrated process tested as a tertiary
technology for leachate biological effluent has advantages on energy
consumption compared with other electrochemical processes.
Moreover, the cost of this electrochemical process could be further
decrease through optimization of fluid distribution and upgrading of
electrode materials.
96
Journal of Hazardous Materials 351 (2018) 90–97
4. Conclusion
(1) The integrated EO/EC/ER process demonstrated promising perfor-
mance for tertiary treatment of actual landfill leachate on accom-
plishing simultaneous removal of organic matter, ammonia, nitrate
and color. The optimal operation conditions of this system were
5000 mg/L chloride ions, DSA1 as anode, 2.5 cm electrode gap,
10 mL/min flow velocity. pH adjustment is not required before this
process.
(2) In EO/EC/ER process, free chlorine generated on DSA anode in EO
process was identified as the main oxidant responsible for ammonia
removal. EC process was conducted on the bipolar electrode via
induced voltage. Direct ER process occurred on GF cathode. Based
on the results of the electrode substitution experiments, COD de-
gradation was achieved by EO and EC process, while nitrate re-
moval was attributed to ER and EC processes, with the higher re-
moval proportion due to the ER process.
(3) The EO/EC/ER process was able to remove 50–60% COD and 100%
ammonia at charge of 1.5 Ah/L with energy consumption of
15 kW h/m3 in a scaled-up reactor. Considering energy consump-
tion, this process is more economical and efficient to meet the re-
quirement of COD removal efficiency less than 70%.
Acknowledgments
The authors gratefully acknowledge funding for this project from
the State Key Laboratory of Urban Water Resource and Environment
(No. 2016DX05), China Postdoctoral Science Foundation funded pro-
jects (No. 2017M611373), and Heilongjiang Postdoctoral Science
Foundation funded projects (No. LBH-Z16073), China. D. D. Dionysiou
also acknowledges support from the University of Cincinnati through a
UNESCO co-Chair Professor position on “Water Access and
Sustainability” and the Herman Schneider Professorship in the College
of Engineering and Applied Sciences.
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.jhazmat.2018.02.038.
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