Journal of Environmental Management 181 (2016) 515e521

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Journal of Environmental Management

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Research article

Electrochemical treatment of concentrate from reverse osmosis of

sanitary landfill leachate
Lazhar Labiadh a, b, Annabel Fernandes a, *, Lurdes Ciríaco a, Maria Jose

Pacheco a,
Abdellatif Gadri b, Salah Ammar b, c, d, Ana Lopes a
a
FibEnTech/UBI and Department of Chemistry, Universidade da Beira Interior, 6201-001 Covilha ~, Portugal
b
D
ep. de Chimie, Facult

e des Sciences de Gabes, Universit

e de Gabes, Cit

e Erriadh, 6072 Gab
es, Tunisia
c

Dep. de Chimie, Facult
e des Sciences de Bizerte, Universit

e de Carthage, 7021 Jarzouna, Tunisia
d
Laboratoire Photovoltaïque, Centre de Recherches et des Technologies de l’Energie Technopole Borj Cedria, Bp 95, Hammamm Lif, 2050, Tunisia

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

Article history: Conventional sanitary landfill leachate treatment has recently been complemented and, in some cases,
Received 5 February 2016 completely replaced by reverse osmosis technology. Despite the good quality of treated water, the ef-
Received in revised form ficiency of the process is low and a large volume of reverse osmosis concentrate has to be either dis-
29 June 2016
charged or further treated. In this study, the use of anodic oxidation combined with electro-Fenton
Accepted 30 June 2016
Available online 5 August 2016
processes to treat the concentrate obtained in the reverse osmosis of sanitary landfill leachate was
evaluated. The anodic oxidation pretreatment was performed in a pilot plant using an electrochemical
cell with boron-doped diamond electrodes. In the electro-Fenton experiments, a boron-doped diamond
Keywords:
Reverse osmosis concentrate
anode and carbon-felt cathode were used, and the influence of the initial pH and iron concentration were
Sanitary landfill leachate studied. For the experimental conditions, the electro-Fenton assays performed at an initial pH of 3 had
Electro-Fenton higher organic load removal levels, whereas the best nitrogen removal was attained when the electro-
Anodic oxidation chemical process was performed at the natural pH of 8.8. The increase in the iron concentration had an
adverse impact on treatment under natural pH conditions, but it enhanced the nitrogen removal in the
electro-Fenton assays performed at an initial pH of 3. The combined anodic oxidation and electro-Fenton
process is useful for treating the reverse osmosis concentrate because it is effective at removing the
organic load and nitrogen-containing species. Additionally, this process potentiates the increase in the
biodegradability index of the treated effluent.
© 2016 Elsevier Ltd. All rights reserved.

1. Introduction
Sanitary landfilling is the most common method used for
municipal solid waste disposal in many countries. This landfilling
process has one disadvantage of generating a concentrated effluent,
the leachate, which may exhibit acute to chronic toxicity (Lü et al.,
Abbreviations and symbols: AO, anodic oxidation; AOP, advanced oxidation
process; BDD, boron-doped diamond; BOD5, biochemical oxygen demand; COD,
chemical oxygen demand; DIC, dissolved inorganic carbon; DOC, dissolved organic
carbon; EAOP, electrochemical advanced oxidation process; EF, electro-Fenton; Esp,
specific energy consumption; HPLC, high performance liquid chromatography; I,
applied current intensity; RO, reverse osmosis; ROC, reverse osmosis concentrate;
SD, standard deviation; TDC, total dissolved carbon; TN, total nitrogen; U, cell
voltage; V, volume of the solution; t, time.
* Corresponding author.
E-mail address: annabelf@ubi.pt (A. Fernandes).
2008; Renou et al., 2008; Salem et al., 2008). In general, biological
and physical-chemical treatments are not good end-of-pipe solu-
tions for treating sanitary landfill leachates; as a result, technolo-
gies such as membrane processes have to be utilized to achieve full
leachate sanitation. Reverse osmosis (RO) is one approach being
implemented as a complement for other treatments or, in some
cases, is the only treatment. However, RO generates a large volume
of concentrate that has to be discharged or further treated (Renou
et al., 2008). Generally, these concentrates are recirculated into
sanitary landfills, resulting in the accumulation of pollutants and
leading to an increase in the electrical conductivity, chemical oxy-
gen demand (COD) and nitrogen content of the leachates. This
process also results in decreased effectiveness of the RO process
due to the increased fouling of the RO membranes (Talalaj and
Biedka, 2015). Thus, alternative solutions for treating the RO
concentrate of the sanitary landfill leachate are required.
Electrochemical advanced oxidation processes (EAOPs) have

http://dx.doi.org/10.1016/j.jenvman.2016.06.069
0301-4797/© 2016 Elsevier Ltd. All rights reserved.
516 L. Labiadh et al. / Journal of Environmental Management 181 (2016) 515e521
been receiving increasing attention in the approach to treating
synthetic and real wastewaters (Anglada et al., 2009; Chen, 2004;
Fernandes et al., 2015; Martínez-Huitle and Brillas, 2009; Sire
s
and Brillas, 2012). The simplest and the most popular EAOP is
anodic oxidation (AO), where organics can be oxidized by the
following processes: (i) direct electron transfer at the anode sur-
face; (ii) highly reactive hydroxyl radicals ($OH) weakly adsorbed at
the anode’s surface that are generated from water oxidation; and
(iii) mediators electrogenerated in the bulk solution, such as active
chlorine species, ozone, persulfates and hydrogen peroxide
(Panizza and Cerisola, 2009a, 2003). According to the literature, AO
provides a simple, viable and promising method for remediating
sanitary landfill leachates (Fernandes et al., 2015). Under appro-
priate experimental conditions, AO can remove most of the organic
load and almost all ammonia content. Additionally, it significantly
reduces the color without resulting in the accumulation of re-
fractory organics, allowing for high treatment efficiency without
the disadvantage of sludge production (Fernandes et al., 2015).
Removal of 100% of the COD and ammonium nitrogen content has
been achieved for the AO in sanitary landfill leachates using boron-
doped diamond (BDD) anodes (Anglada et al., 2010; Cabeza et al.,
2007a, 2007b).
Another promising EAOP used in wastewater treatment is the
electro-Fenton (EF) process (Atmaca, 2009; Barhoumi et al., 2015;
Panizza and Cerisola, 2001). The EF process is a method that pro-
motes the oxidation of organic compounds via an indirect elec-
trochemical oxidation through hydroxyl radicals produced in the
Fenton reaction (Eq. (1)).
Fe2þ þ H2O2 / Fe3þ þ HO þ OH
In this process, both H2O2 and Fe2þ, can be electrogenerated in
situ (Deng and Englehardt, 2006), reducing the cost related to H2O2
consumption, which is the main cost factor for consumables in the
setting of traditional AOPs based on Fenton’s reaction (Malato et al.,
2009). Hydrogen peroxide can be generated in situ from the two-
electron reduction of O2 on cathodes, such as gas diffusion elec-
trodes, reticulated vitreous carbon or graphite-felt, according to Eq.
(2) (Brillas et al., 2009; Oturan et al., 2008; Panizza and Cerisola,
2001):
O2 þ 2Hþ þ 2e / H2O2
An advantage of the EF process over the classical chemical
Fenton’s reagent is that Eq. (1) is electrocatalyzed because Fe2þ ions
are rapidly regenerated from the reduction of Fe3þ ions at the
cathode through Eq. (3) (Brillas et al., 2009; Labiadh et al., 2015).
Fe3þ þ e / Fe2þ
The EF process has been used to treat many organic pollutants,
enabling their complete mineralization (Barhoumi et al., 2015; Flox
et al., 2009; Mhemdi et al., 2013; Panizza and Cerisola, 2009b), as
well as sanitary landfill leachates, and there have been promising
results (Atmaca, 2009; Lin and Chang, 2000; Zhang et al., 2006).
According to the literature, the optimum pH of the solution for
the EF process is 3.0, which is close to the optimum value of 2.8 for
the chemical Fenton’s process, and its ability to oxidize the organic
load in wastewaters is closely related to the rate of Eq. (1), which
depends on the iron concentration and cathode type (Brillas et al.,
2009). For the EF process performed with a carbon-felt cathode,
optimal Fe2þ or Fe3þ concentrations of 0.1e0.2 mM have been
found (Labiadh et al., 2015; Ozcan et al., 2008; Panizza and Cerisola,
2009b; Sire
s et al., 2007), whereas 0.5e1.0 mM Fe2þ and 4.0 mM
3þ
Fe are the most adequate for O2 or air-diffusion electrodes due to
their greater efficiency for H2O2 generation through Eq. (2) and
smaller rate of Eq. (3) (El-Ghenymy et al., 2014; Isarain-Cha
vez
et al., 2010; Ruiz et al., 2011).
In the EF process, the use of an undivided cell with a high O2-
overpotential anode, such as BDD, accelerates the degradation of
organic matter because it can also be oxidized by adsorbed hy-
droxyl radical (BDD($OH)) and formed as an intermediate of the
anodic water discharge (Panizza and Cerisola, 2009a). The BDD
anode is better than other typical electrodes, such as Pt and PbO2
(Ciríaco et al., 2009; Flox et al., 2009; Mhemdi et al., 2013),
improving the destruction of aromatic compounds and generation
of carboxylic acids (Brillas et al., 2009; Mhemdi et al., 2013; Panizza
and Cerisola, 2009a). Moreover, the electrogenerated H2O2 is
partially oxidized to O2 at the anode, producing the weaker oxidant
hydroperoxyl radical (HO2) as an intermediate (Brillas et al., 2009).
The aim of this work was to treat a concentrate obtained during
RO of a leachate from a municipal sanitary landfill with the com-
bination of anodic oxidation with a BDD anode and EF with a
carbon-felt cathode and a BDD anode, as well as to study the in-
fluence of the different experimental conditions on the energetic
costs of the organic load and ammonium nitrogen removal. The
sequence of AO followed by EF was chosen because i) AO is known
for its higher ability than EF to treat very complex effluents, even
those with high suspended solid contents, such as the raw samples
used in this study, and ii) EF is expected to perform organic matter
oxidation at lower energetic costs when the sample mainly consists
of dissolved matter. The influence of the pH and iron content on the
performance of the EF process efficiency was studied.
(1) 2. Experimental
2.1. Sample characterization
The reverse osmosis concentrate (ROC) of the sanitary landfill
leachate used in this study was collected in June 2015 from an
intermunicipal sanitary landfill facility. This site, which serves a
population of over 368,000 inhabitants in 19 municipalities, has an
onsite facility capable of treating up to 175 m3 of leachate per day.
The treatment applied at this landfill site consists of two reverse
osmosis systems followed by a stripping column. With the reverse
osmosis process, more than 96 m3 of the leachate concentrate is
(2) returned to the sanitary landfill per day. The characteristics of the
ROC of the sanitary landfill leachate used in this study are pre-
sented in Table 1.
2.2. Electrochemical experiments
The AO pretreatment was conducted in a semi-pilot plant
(3) operating in batch mode with recirculation at room temperature
and natural pH without the addition of background electrolyte. A
BDD DiaCell 100 electrochemical cell with an electrode area of
70 cm2 and a DiaCell-PS1500 power supply with automatic polarity
reversal were used. During the assays, automatic polarity reversal
occurred every minute. Assays were performed for 24 h at an
applied current intensity of 4.9 A and a flow rate of 500 L/h using
10 L of ROC of the sanitary landfill leachate. After the AO treatment,
the solution was submitted to the electro-Fenton process.
The EF experiments were conducted in batch mode with stirring
using an open, undivided and cylindrical glass cell and 250 mL of
solution over a period of 8 h. A graphite-felt piece (Carbone Loraine)
with a thickness of 0.5 cm and an immersed area of 60 cm2 was
used as the cathode, and a BDD electrode purchased from Adamant
Technologies with an immersed area of 20 cm2 was used as an
anode. The anode was centered in the electrochemical cell and
surrounded by the cathode, which covered the inner wall of the
 L. Labiadh et al. / Journal of Environmental Management 181 (2016) 515e521 517

cell. H2O2 was produced from reducing the O2 dissolved in the Table 1
solution (Eq. (2)). Continuous O2 saturation at atmospheric pres- Physicochemical characteristics of the reverse osmosis concentrate of the sanitary
landfill leachate and solution obtained after anodic oxidation pretreatment (AO
sure was ensured by bubbling compressed air through a fritted pretreated).
glass diffuser at 1 L/min, starting 10 min before electrolysis, to reach
a steady O2 concentration. To optimize the experimental condi- Parameter (g/L)a Mean value (±SDb)

tions, different iron concentrations between 10 (natural iron con- ROC AO pretreated
centration) and 27 mg/L and different initial pH conditions, namely, COD 9.9 ± 0.4 6.5 ± 0.4
a pH of 3 and 5, were tested for an applied current intensity of 0.3 A. BOD5 4.3 ± 0.2 3.3 ± 0.1
A GW, Lab DC, model GPS-3030D (0e30 V, 0e3 A) was used as the BOD5/COD 0.43 ± 0.04 0.51 ± 0.05
DOC 3.6 ± 0.3 2.61 ± 0.05
power supply. Electrochemical experiments using the EF experi-
DIC 1.31 ± 0.03 0.92 ± 0.02
mental set-up were also performed with the AO-pretreated solu- TN 2.4 ± 0.3 2.16 ± 0.02
tion at natural pH conditions (8.8). In the assays performed with [NHþ 4] 3.0 ± 0.2 2.5 ± 0.1
additional iron, Fe2(SO4)3$5H2O was added to the solution 10 min [NO 3] <0.01 0.45 ± 0.04

before starting electrolysis to ensure complete dissolution. When [Cl ] 5.3 ± 0.2 5.1 ± 0.3
[ClO3] <0.01 0.14 ± 0.01
required, pH adjustments were performed by the addition of
[Fe] 0.0108 ± 0.0006 0.0103 ± 0.0005
concentrated H2SO4. pH 8.1 ± 0.1 8.8 ± 0.1
All electrochemical assays were performed at least in duplicate. Conductivity 31 ± 4 32 ± 1
The parameter values for the assays are given as mean values. a
Except for the BOD5/COD and pH values, which are dimensionless, and for
conductivity values, which are presented in mS/cm.
b
2.3. Analytical methods SD e Standard deviation.

Degradation tests were followed by analysis of the COD,

biochemical oxygen demand (BOD5), total dissolved carbon (TDC),
dissolved organic carbon (DOC), dissolved inorganic carbon (DIC)
and total nitrogen (TN), which were performed according to stan-
dard procedures (Eaton et al., 2005). COD determinations were
made using the closed reflux titrimetric method. The BOD5 was
evaluated by determining the oxygen consumption after 5 days of
incubation. The TDC, DOC, DIC and TN were measured using a
Shimadzu TOC-VCPH analyzer combined with a TNM-1 unit. Before
TDC, DOC, DIC and TN determinations, samples were filtered
through 1.2-mm glass microfiber filters.
The ammonium, nitrate, nitrite, chloride and chlorate ions
concentrations were determined by ion chromatography using a
Shimadzu 20A Prominence HPLC system that was equipped with a
Shimadzu CDD 10Avp conductivity detector. To determine the NHþ
4,
an IC YK-A Shodex (4.6 mm ID  100 mm) column was utilized. The
mobile phase consisted of 5.0 mM tartaric acid, 1.0 mM dipicolinic
acid and 24 mM boric acid aqueous solution at a flow rate of 1.0 mL/
min. The column temperature was 40  C. To evaluate the NO  higher when the assays were run at a natural initial pH. For
3 , NO2 ,
Cl and ClO levels, an IC I-524A Shodex (4.6 mm ID  100 mm)
3
anion column was employed. The mobile phase consisted of an
aqueous solution of 2.5 mM of phthalic acid and 2.3 mM of
tris(hydroxymethyl) aminomethane at a flow rate of 1.5 mL/min.
The column temperature was 40  C. All solutions for chromato-
graphic analysis were prepared with ultrapure water obtained with
Milli-Q® equipment. All eluents were HPLC grade and supplied by
Sigma-Aldrich.
The iron concentration was determined by flame atomic ab-
sorption spectrometry using a Perkin Elmer Apparatus, AAnalyst
800. The sample preparation followed a standard procedure that
includes HCleHNO3 acid digestion (Eaton et al., 2005).
The pH was measured using a HANNA pH meter (HI 931400).
The conductivity was determined using a Mettler Toledo conduc-
tivity meter (SevenEasy S30K).
3. Results and discussion
The ROC of the sanitary landfill leachate was first submitted to
an AO pretreatment, and Table 1 presents the obtained results. A
clarified solution was generated, which had approximately 65% of
the initial organic load and 83% of the ammonium nitrogen,
potentiating the application of a later treatment. With respect to
the iron concentration, and because AO pretreatment was per-
formed with automatic polarity reversal, no significant difference
was found between the iron content in the ROC and pretreated
solution.
Because ferrous ion concentrations between 6 and 12 mg/L are
reported in the literature as optimal for the EF process when a
carbon-felt cathode is used (Labiadh et al., 2015; Ozcan et al., 2008;
Panizza and Cerisola, 2009b; Sire
s et al., 2007), the first set of EF
experiments were performed without the addition of external iron.
Fig. 1 shows the results obtained for the EF assays performed using
the AO pretreated solution with a different initial pH at an applied
current intensity of 0.3 A. The following three different initial pH
conditions were studied: pH of 3, the optimum pH for the EF pro-
cess according to the literature (Panizza and Cerisola, 2003); pH of
5, a less costly solution for reagent addition; and natural pH (8.8),
the cheapest solution, even though it is not favorable for Fenton’s
reaction.
As in Fig. 1, acidic pH conditions led to higher COD removals, but
the total and ammonium nitrogen removal levels were much
instance, approximately 35% of the ammonium was removed after
8 h for natural pH, whereas at pH of 3, only a small change in the
ammonium concentration was observed. Additionally, natural pH
conditions favor the mineralization of organic compounds. Indeed,
the assays performed at different initial pH values yield similar DOC
removals, but much lower COD removal was observed with a nat-
ural initial pH. This means that oxidation in the assays run at a
natural pH leads to higher levels of organic compound combustion
instead of converting the compounds into other more oxidized
compounds, but that would remain in solution. These results can be
explained by considering that at a pH of 8.8, Fenton’s reaction (Eq.
(1)) was not favored because, for the experimental conditions of a
saturated oxygen concentration, hydrogen peroxide electro-
chemical production (Eq. (2)) is enhanced at pH 3 (Pimentel et al.,
2008), while the regeneration of ferrous ions (Eq. (3)) is inhibited
at pH > 4 due to the precipitation of ferric oxyhydroxides (Bigda,
1995; Lin and Lo, 1997; Nesheiwat and Swanson, 2000). There-
fore, at a natural pH, the oxidation of organic compounds mainly
occurred through the hydroxyl radicals generated from water
electrolysis at the BDD anode surface (Eq. (4)).
H2O / Hþ þ HO þ e (4)
In parallel with water electrolysis, and because the chloride
content in the pretreated ROC was as high as 5.1 g/L, the direct
518 L. Labiadh et al. / Journal of Environmental Management 181 (2016) 515e521
oxidation of a chloride ion at the anode produced chlorine (Eq. (5)),
which can in turn be hydrolyzed, resulting in hypochlorous acid

rez et al., 2012). According to the literature, ammonium
(Eq. (6)) (Pe
degradation mainly occurs as a result of indirect oxidation with
active chlorine species (Pe
rez et al., 2012). Therefore, the produced
hypochlorous acid can react with ammonium (Eq. (7) and (8)),
leading to its oxidation and to the formation of gaseous nitrogen
forms and nitrate (Pe
rez et al., 2012).
2Cl / Cl2 þ 2e
Cl2 þ H2O / HOCl þ Hþ þ Cl

2=3NHþ þ
4 þ HOCl/1=3N2 þH2 O þ 5=3H þCl
 
NHþ þ
4 þ 4HOCl/NO3 þ H2 O þ 6H þ4Cl
At pH values of 3 and 5, the electrochemical hydrogen peroxide
formation rate (Eq. (2)) was enhanced, favoring Fenton’s reaction
(Eq. (1)) as well as the reaction between hydroxyl radicals and
hydrogen peroxide (Eq. (9)) (Atmaca, 2009).
H2O2 þ HO / HO2 þ H2O
The increase in the level of oxidizing species present in solution
explains the higher COD removal under acidic pH conditions. The
low mineralization of the organic compounds under acidic pH
conditions can be explained by the fact that HO2 radicals produced
as in Eq. (9) present with weaker oxidizing ability compared to the
HO radical. Furthermore, the direct oxidation of chloride ions was
less favored under acidic pH conditions, and consequently, nitrogen
removal decreased.
Although no significant differences were found in COD removal
for the assays performed at an initial pH of 3 or 5, the total and
ammonium nitrogen removal levels increased with increasing
initial pH levels. This observation indicates that chlorine generation
is depressed with increasing hydrogen peroxide electrochemical
production, which is maximal at pH 3 (Pimentel et al., 2008).
Conversely, the amount of nitrate formed increased with
decreasing initial pH. These results indicate that HO and/or HO2
radicals formed under acidic pH conditions react preferably with
the organic nitrogen present in solution rather than with ammo-
nium, oxidizing it to nitrate, or that the formation rate of ammo-
nium from organic nitrogen equals the oxidizing rate of ammonium
to nitrate.
Regarding pH changes in the assays (inset of Fig. 1b), experi-
ments performed at natural pH did not show significant variations,
which can be explained by the buffering effect of these effluents
(Chiang et al., 1995). For the assays performed under initial acidic
conditions, a decrease in the pH was found, and this decrease has
previously been explained by the carboxyl acids formed during the
degradation process and oxygen evolution reaction (Zhang et al.,
2012).
Considering the results obtained in the experiments performed
under different initial pH conditions, a second set of assays was
performed in which the influence of the iron concentration was
studied. Two different initial pH conditions were chosen for this
study, natural pH, which results in the best nitrogen removal, and
pH 3, which is reportedly optimal for the EF process. As in Fig. 2,
when the iron concentration was increased from 10 to 16 mg/L
(corresponding to an addition of 0.1 mM of Fe2þ), COD, DOC,
ammonium and total nitrogen removal levels decreased for the
assays performed at natural pH. Therefore, at the end of the
treatments performed at natural pH with a natural iron content
(10 mg/L of iron), 24% of the initial COD was destroyed, but only 16%
was removed for 16 mg/L iron. This decrease in the organic load and
nitrogen removals can be explained by the side reactions between
the HO and HOCl with the ferrous ion (Eq. (10) and (11)), which are
enhanced by the addition of Fe2þ that will consume hydroxyl
radicals and hypochlorous acid. As a result, they are not available
for the oxidation of organic compounds and ammonium nitrogen.
HO þ Fe2þ / Fe3þ þ HO (10)
(5) 2Fe2þ þ 3HOCl þ 3H2O / 2Fe(OH)3 þ 3Cl þ 3Hþ (11)
(6) For the assays performed at an initial pH of 3, the addition of
0.1 mM of Fe2þ did not affect the COD and DOC removal, but it
(7) enhanced the ammonium and total nitrogen removal. This result
could indicate that Fenton’s reaction was enhanced by the addition
of extra iron, resulting in a competition between COD and ammo-
(8)
nium removal. Based on this result, the amount of iron was further
increased in the solution at an initial pH of 3 to a total iron con-
centration of 27 mg/L (corresponding to the addition of 0.3 mM of
Fe2þ). However, this further increase in the iron concentration
resulted in a decrease in the ammonium and total nitrogen removal
levels (Fig. 2c and d), which can be explained by the scavenging
(9) reaction between the HO and Fe2þ (Eq. (10)) that is further
enhanced by the excess of ferrous iron in solution. When the nitrate
concentration results are analyzed (inset of Fig. 2d), although the
addition of iron did not significantly influence the nitrate formation
in the experiments performed at natural pH, the addition of iron
decreased the amount of nitrate formed during the assays per-
formed at an initial pH of 3. Conversely, for a pH of 3, an exponential
increase in the amount of chlorate formed was observed when the
iron concentration was increased to 27 mg/L (Appendix 1b), indi-
cating that chloride is oxidized to chlorate to a greater extent. With
respect to the pH evolution in the assays (inset of Fig. 2c), the
addition of iron did not have any effect.
To analyze the energy consumptions associated with the
different experimental conditions, specific energy consumptions, in
Wh/g, based on COD or NHþ 4 removal were calculated using Eq. (12),
where U is the cell voltage (in V) resulting from the applied current
intensity I (in A) and Dt is the duration of the electrolysis (in h).
Additionally, V is the volume of the solution (in L), and DX is the
removed COD or NHþ 4 (in g/L) during Dt. The results are presented
in Table 2.
U I Dt
Esp ¼ (12)
V DX
In general, for the experimental conditions studied, the lowest
specific energy consumptions regarding COD removal were
attained for the assays performed at pH 3, although the same
conditions had the highest specific energy consumptions for NHþ 4
removal. By contrast, assays performed at natural pH without
added iron presented with slightly higher specific energy con-
sumptions for COD removal, but they had lower specific energy
consumptions for NHþ 4 removal. Considering these results and the
costs associated with the acidifying process, a natural pH and
natural iron concentration were chosen as the most favorable
conditions for treating the AO pretreated sample. The biodegrad-
ability index, determined as the ratio BOD5/COD, for these more
favorable conditions was also assessed, and a value of 0.51 was
obtained after the 8 h assay, indicating that the biodegradability
index did not change during this treatment.
A 24 h assay was performed at a natural iron concentration and
natural initial pH at 0.3 A to evaluate the treatment potential. The
results presented in Appendix 2 show that after 24 h of reaction,
the COD, DOC, NHþ 4 and TN removal rates were approximately 65%,
 L. Labiadh et al. / Journal of Environmental Management 181 (2016) 515e521 519

Fig. 1. Influence of the initial pH on the decays of (a) COD, (b) DOC, (inset of b) pH, (c) ammonium concentration and (d) TN and (inset of d) nitrate concentration during the EF
process. Sample e ROC pretreated by AO; Iron concentration ¼ 10 mg/L; I ¼ 300 mA; cathode e carbon-felt; and anode e BDD.

Fig. 2. Influence of the initial iron concentration on the decays of (a) COD, (b) DOC, (c) ammonium concentration, (inset of c) pH, and (d) TN and (inset of d) nitrate concentration
during the EF process. Sample e ROC pretreated by AO; I ¼ 300 mA; cathode e carbon-felt; and anode e BDD.
520 L. Labiadh et al. / Journal of Environmental Management 181 (2016) 515e521
Table 2
Specific energy consumptions for the assays performed at different initial iron
concentrations and different initial pH: Sample e ROC pretreated by AO; I ¼ 300 mA;
assay duration e 8 h; cathode e carbon-felt; and anode e BDD.
pH [Fe] (mg/L) Esp (Wh/gCOD) Esp (Wh/gNHþ
4)
3 10 45 680
16 42 205
27 48 545
5 10 47 145
Natural (8.8) 10 53 108
16 73 114
55%, 71% and 74%, respectively. Additionally, the nitrite and nitrate
concentrations increase until the 20 h assay. Afterwards, the nitrate
concentration stabilized and the nitrite concentration decreased.
Additionally, the chloride concentration decreased throughout the
assay, and chlorate formation increased exponentially. The results
of the corresponding 8 h assay are also presented in Appendix 2,
and the small differences observed in the results at 8 h assay are
mainly from the more exhaustive sample collection during the
shorter assay, which reduces the volume of the treated sample.
4. Conclusions
Anodic oxidation and electro-Fenton are effective technolo-
gies for treating reverse osmosis concentrate from sanitary
landfill leachates. In the combined AO and EF treatment
approach, utilizing the most favorable EF experimental condi-
tions (initial pH of 3 with 16 mg/L of iron at an applied current
intensity of 0.3 A; 8 h), the removal rates of COD, DOC, NHþ 4 and
total nitrogen were 60%, 53%, 33% and 22%, respectively. When
AO pretreatment was followed by electrochemical assays per-
formed at a natural initial pH of 8.8, a natural iron concentration
(10 mg/L), and an applied current intensity of 0.3 A for 8 h, the
Fenton reaction was negligible and anodic oxidation dominated.
In this case, the COD, DOC, NHþ 4 and total nitrogen removal rates
were of 48%, 42%, 50% and 35%, respectively, indicating that the
anodic oxidation process is more effective at removing N-con-
taining compounds than the EF process. Therefore, the experi-
mental conditions must be set according to the required
objectives. If the priority is organic load removal instead of N-
containing compound removal or the sample presents with low
nitrogen content, combined anodic oxidation followed by an
electro-Fenton process should be used, being necessary opti-
mizing the electro-Fenton process, i.e., pH adjustment of the
effluent to 3, and, depending on the iron concentration of the
sample, correct the iron content. When the primary goal is ni-
trogen removal, the anodic oxidation process should be utilized
because it results in high nitrogen removal without requiring pH
adjustment or the addition of iron. An increase in the biode-
gradability index of the treated effluent from 0.43 to 0.51 was
also attained for the different experimental conditions tested.
This demonstrated that the combined electrochemical tech-
niques could be used to eliminate the recalcitrant organic load
from ROC and increase the biodegradability, enabling its
discharge into urban wastewater treatment plants with biological
steps.
Acknowledgments
We thank Fundaça ~o para a Cie^ncia e a Tecnologia, FCT, for
funding the FibEnTech Research Unit and for the grant awarded to
A. Fernandes, SFRH/BPD/103615/2014. We thank University of
Gabes, in Tunisia, for providing partial financial support.
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.jenvman.2016.06.069.
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