Journal of Environmental Management 210 (2018) 328e337

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Journal of Environmental Management

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

Research article

Combined heterogeneous Electro-Fenton and biological process for

the treatment of stabilized landfill leachate
Archa Baiju a, R. Gandhimathi a, *, S.T. Ramesh a, P.V. Nidheesh b, **
a
Department of Civil Engineering, National Institute of Technology, Tiruchirappalli, Thuvakudi, Tamil Nadu, 620 015, India
b
CSIR- National Environmental Engineering Research Institute, Nagpur, Maharashtra, 440020, India

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

Article history: Treatment of stabilized landfill leachate is a great challenge due to its poor biodegradability. Present
Received 5 October 2017 study made an attempt to treat this wastewater by combining electro-Fenton (E-Fenton) and biological
Received in revised form process. E-Fenton treatment was applied prior to biological process to enhance the biodegradability of
29 November 2017
leachate, which will be beneficial for the subsequent biological process. This study also investigates the
Accepted 4 January 2018
efficiency of iron molybdophosphate (FeMoPO) nanoparticles as a heterogeneous catalyst in E-Fenton
process. The effects of initial pH, catalyst dosage, applied voltage and electrode spacing on Chemical
Oxygen Demand (COD) removal efficiency were analyzed to determine the optimum conditions. Het-
Keywords:
Leachate
erogeneous E-Fenton process gave 82% COD removal at pH 2, catalyst dosage of 50 mg/L, voltage 5 V,
Advanced oxidation process electrode spacing 3 cm and electrode area 25 cm2. Combined E-Fenton and biological treatment resulted
Electro-Fenton process an overall COD removal of 97%, bringing down the final COD to 192 mg/L.
Biological process © 2018 Elsevier Ltd. All rights reserved.

1. Introduction physicochemical techniques a better option for their treatment.

Sanitary landfilling is the most economic method accepted
worldwide for the elimination of Municipal as well as Industrial
solid waste (Zhang et al., 2012). Landfilling helps to minimize
environmental impacts by allowing the waste to degrade under
controlled conditions, where it's eventually transformed into rela-
tively inert and stabilized material (Renou et al., 2008). Still gen-
eration of heavily polluted leachates constitutes a major drawback
of sanitary landfill. Solid waste composition, landfill age, rainfall
patterns and properties of soil comes under the major parameters
influencing the characteristics of landfill leachate (Di Iaconi et al.,
2006; Hermosilla et al., 2009; Park et al., 2001). Based on the
“age” of landfill, leachate can be categorized as young (BOD5/
COD > 0.6), intermediate and stabilized/mature (BOD5/COD < 0.3).
High BOD5/COD ratio and high concentration of low molecular
weight organics, makes the young leachate susceptible to treat-
ment by biological techniques. Low BOD5/COD ratio and high
concentration of high molecular weight refractory organics being
the typical characteristics of mature landfill leachate, makes
* Corresponding author.
** Corresponding author.
E-mail addresses: rgmathii@nitt.edu (R. Gandhimathi), nidheeshpv129@gmail.
com, pv_nidheesh@neeri.res.in (P.V. Nidheesh).
Hence over the years, numerous physicochemical processes have
been tried either as a pre-treatment or for full treatment of stabi-
lized landfill leachate (Castrillo
n et al., 2010; Gao et al., 2015;
Kurniawan et al., 2006; Renou et al., 2008).
Out of the numerous physicochemical techniques that have
been studied over years in the treatment of mature landfill
leachate, Advanced Oxidation Processes (AOP's) have become a
popular one for the removal of refractory organics and ammonia-
nitrogen from wastewaters (De Morais and Zamora, 2005; Gogate
and Pandit, 2004; Primo et al., 2008). Their ability to mineralize
the refractory organics and thereby enhance the biodegradability of
wastewater, places the AOP's one notch above the conventional
physicochemical techniques (Chidambara Raj and Quen, 2005;
Pera-Titus et al., 2004; Primo et al., 2008). Being technically sim-
ple, economic and non-toxic iron and hydrogen peroxide as pri-
mary reactants; Fenton's process stand out as the most feasible AOP
(De Morais and Zamora, 2005).
Conventional Fenton process which makes use of homogeneous
catalyst, are faced with problems like slower ferrous ion regeneration
rate and excessive iron sludge production. But in order to commer-
cialize this technique, these drawbacks have to be overcome. This has
been targeted by the heterogeneous Electrochemical Advanced
Oxidation Processes (EAOP's), out of which electro-Fenton process
has come out as the popular EAOP (Brillas et al., 2009; Nidheesh et al.,

https://doi.org/10.1016/j.jenvman.2018.01.019
0301-4797/© 2018 Elsevier Ltd. All rights reserved.
 A. Baiju et al. / Journal of Environmental Management 210 (2018) 328e337
2013; Nidheesh and Gandhimathi, 2012). Applicability of heteroge-
neous E-Fenton process in stabilized landfill leachate treatment has
not yet been studied in detail. Iron-loaded Mangosteen Shell Powder
(Laiju et al., 2014) and Nanosized Zero Valent Iron particles
(Shafieiyoun et al., 2012) are two of the heterogeneous catalysts that
have been used in Fenton process for leachate treatment. Despite
their high effectiveness, AOPs become quite expensive if applied
alone (Silva et al., 2017). Greater resistance offered by the oxidation
intermediates to further chemical oxidation and failure in bringing
down the initial COD to meet the discharge standards, makes Fenton
a non-feasible technique in some cases. On the other hand, eco-
friendly biotreatment options require carefully maintained reaction
conditions and could be applied only to wastewaters with pollution
level that is non-toxic to microorganisms (Ganigue
et al., 2012; Guo
et al., 2013; Xiao et al., 2015). Considering the advantages and dis-
advantages of chemical oxidation and biological treatment,
combining these two would be a more feasible option (Oller et al.,
2011; Scott and Ollis, 1995). In the combined process, chemical
oxidation as an initial step would convert the persistent organic
pollutants into more biodegradable intermediates, which could be
easily removed in a subsequent biological step.
In the present study, Iron molybdophosphate is being used as
the heterogeneous E-Fenton catalyst. This catalyst was initially
used in the Photocatalysis for the degradation of malachite green
and was found to give promising results (Sharma et al., 2016).
Present study also aims to combine E-Fenton process with biolog-
ical processes for the successful mineralization of stabilized landfill
leachate.
2. Materials and methods
2.1. Leachate
Leachate used in the present study was collected from Ariya-
mangalam dumping site, Trichy, Tamil Nadu, India. Spread out over
43 acres of land, this is one of the oldest dump yard in Trichy. Nearly
20 L samples were collected in 10 L plastic cans. Samples were
stored at 4
C to arrest further biodegradation. Leachate charac-
terization was done as per standard methods (APHA, 2012).
2.2. Chemicals
Sodium molybdate (Na2MoO4), Orthophosphoric acid (H3PO4)
and Ferric nitrate nonahydrate (Fe(NO3)3.9H2O) were used in the
catalyst preparation. Other chemicals used in the E-Fenton study
includes H2SO4 and NaOH. Apart from these, Nutrient agar and
Nutrient broth were used in the preparation of inoculation me-
dium. Sterile saline water (0.9% NaCl) was used for serial dilution
while performing the biological study. All the chemicals used in the
study were obtained from Merck and were of analytical grade.
2.3. Electrodes
The electrodes used in the study were TiO2/Ti and Graphite as
anode and cathode respectively. Graphite electrodes were pur-
chased from Anabond Sainergy Fuel Cell India Private Limited,
Chennai, Tamil Nadu. Dimensions of the graphite electrode were
8 cm  7 cm x 0.5 cm. Dimensions of the TiO2/Ti electrode were
8 cm  7 cm x 0.4 cm. For E-Fenton process, the effective area of the
electrodes was kept as 25cm2.
2.4. Preparation and characterization of FeMoPO
Iron molybdophosphate (FeMoPO) catalyst was synthesized by
329
co-precipitation method (Sharma et al., 2016). For the catalyst
preparation 200mL of 0.1M Sodium molybdate (Na2MoO4) and
100 mL of 0.05M Orthophosphoric acid (H3PO4) were added drop
wise to 100mL of 0.1M Ferric nitrate nonahydrate (Fe(NO3)3.9H2O),
with constant stirring over a magnetic stirrer. Upon addition of
Na2MoO4 and H3PO4, the clear reddish brown solution of
Fe(NO3)3.9H2O changed to highly turbid creamish brown solution,
indicating the formation of FeMoPO nanoparticles. The reaction
between Fe(NO3)3.9H2O and Na2MoO4 results in the formation of
FeMoPO nanoparticles, where the Fe3þ ions are reduced to Fe2þ
ions by the acidic medium ensured by the addition of H3PO4. This
mixture was then stirred and refluxed for 18 h at 80
C over a
magnetic stirrer with hot plate. The precipitates so obtained were
filtered, washed and dried at 50
C in a hot air oven. A single run
yielded around 2.5 g of creamish brown FeMoPO nanoparticles.
Fourier Transform Infrared Spectroscopy (FTIR-2000, Perkin
Elmer) was used to determine the surface functional groups of
FeMoPO. FTIR spectra was recorded from 4000 cm1 to 400 cm1
using the KBr pellet method. Rigaku X-ray Diffractometer (D-Max/
Ultima III) was used to obtain the X-ray diffractogram of FeMoPO
samples. The prepared FeMoPO samples were exposed to X-ray
with 2q angle varying between 5⁰ and 80⁰. XRD was performed with
Cu Ka radiations at an applied voltage, current and scan rate of
40kV, 32mA, 40 min1 respectively. To understand the surface
morphology of FeMoPO samples, SEM analysis were performed in
JEOL JMT-300 operated at 15 kV, which uses high energy electron
beam to give microphotographs of the samples.
To investigate the stability and uniformity of the prepared
FeMoPO nanoparticles, Zeta potential and particle size measure-
ments were conducted in Malvern Zetasizer Nano ZSP. For the
measurement of Zeta potential, the powder sample was dispersed
in aqueous medium and loaded in the Zeta dip cell. Zetasizer makes
use of the Electrophoretic Light Scattering (ELS) technique for the
estimation of Zeta potential. For particle size measurement, the
powder sample was dispersed in aqueous medium and loaded in
Disposable sizing cuvettes of the Zetasizer, which applies Dynamic
Light Scattering (DLS) technique for particle size estimation.
2.5. E-Fenton Process
In electro-Fenton process, the experiment was carried out in a
batch reactor consisting of 1000mL borosil glass beaker. 750mL of
leachate was taken and initial pH was adjusted to 3 using 1N H2SO4.
Predetermined amounts of catalyst (iron molybdophosphate) were
added to the sample. Inner electrode spacing was maintained as
3cm. The electrodes were connected to a DC power supply. DC
voltage was maintained as 5 V. Aeration were given near cathode
using fish aerator for the in-situ generation of hydrogen peroxide.
Samples were withdrawn at regular time intervals (every 10min),
centrifuged at 7000 rpm (inorder to separate the sludge) for 10min
and the supernatant was collected for COD estimation. COD
reduction was expressed as the ratio of residual COD at time t (Ct) to
initial COD (C0). Further studies were carried out by varying the
initial pH, catalyst dosage, voltage and electrode spacing. Prior to
use in E-Fenton process, all electrodes were thoroughly cleaned
with water to remove any excess debris. The electrodes were then
soaked in 1N HCl for 1 h followed by 1M NaOH for another hour.
The electrodes were stored in distilled water when not in use. After
each use, the electrodes were washed in 1N HCl and 1M NaOH to
remove any possible contamination.
2.6. Biological study
As the E-Fenton treatment did not succeed in bringing down the
COD of leachate samples to meet the discharge standards, the
330 A. Baiju et al. / Journal of Environmental Management 210 (2018) 328e337

treated leachate (after E-Fenton process) was subjected to a sub- 3.2. Characterization of FeMoPO
sequent biological process. For the biological process, native bac-
terial species were isolated from soil samples acquired from the The characteristic XRD peaks (Fig. 1a) at 2q angles of 17.3⁰, 29.6⁰
leachate collection pit. The soil samples were prepared by diluting and 48.1⁰ corresponding to (102), (113) and (423) diffraction planes,
10 g soil in 90mL of distilled water and were incubated overnight at confirms the formation of Fe2MoP12 (Florke and Jeitschko, 1983).
37
C and 150 rpm. Serial dilutions (101, 102, 103, 104 and 105) The lattice parameters for Fe2MoP12 were a ¼ 13.725 Å, b ¼ 5.672 Å
were performed using sterile saline water (0.9% NaCl). Sterile agar and c ¼ 11.092 Å. Debye-Scherrer formula (Eqn. (1)) was used in the
plates were then inoculated with 1mL of diluted sample and estimation of average particle size of FeMoPO particles. In this
incubated overnight at 37
C. The plate which gave colonies in the formula, D corresponds to the average particle size, b is the full
range of 10e300 was chosen for further screening process. width at half maximum value of XRD diffraction lines, l is the
Distinct bacterial colonies were marked and these colonies were wavelength of X-ray radiation source (0.15405 nm), q is the half
individually incubated overnight in 250mL Erlenmeyer flasks hav- diffraction angle-Bragg angle (29.6⁰) and K stands for the Scherrer
ing 100mL of sterile Nutrient broth at 37
C and 110 rpm. Inorder to constant with a value ranging from 0.9 to 1 (K value of 0.9 was
screen out the efficient colonies, 100mL of pre-treated leachate was considered) (Nidheesh et al., 2014). The average crystalline size
inoculated with 1mL of the isolated colonies and were incubated thus determined from Scherrer's formula is 35nm.
overnight at 37
C and 110 rpm for duration of 3 days. Prior to this
step, the pre-treated leachate was heated at 70
C for 10min, so as
to remove any residual hydrogen peroxide (Roshini et al., 2017), Kl
D¼ (1)
which might otherwise be harmful to the microbes. The pH of bCosq
samples was adjusted to 8, as the soil from which the bacterial
species were isolated was found to be alkaline with a pH of 8.27.
The screened colonies (which gave COD removal efficiency greater
nl ¼ 2dsinq (2)
than 30%) were then subcultured and used for generation of mixed
bacterial culture. The lattice spacing between the diffraction planes were calcu-
For sub-culturing, 1mL of inoculum was added to 10mL of lated using the Bragg's Diffraction equation (Eqn. (2)) where, l is
nutrient broth and incubated overnight at 37
C and 110 rpm. The the wavelength of X-ray radiation source 0.15405 nm, q is the angle
mixed culture was established by adding 1mL from each of these between the incident rays and the surface of the crystal, d is the
subcultures to 100mL of sterile Nutrient broth and incubating lattice spacing and n is the order (n was taken as 1) (Kumar et al.,
overnight at 37
C and 110 rpm. Further batch studies were per- 2015). The lattice spacing's for planes (102), (113) and (423) were
formed on raw and pre-treated leachate using the mixed bacterial 5.19 Å, 3.02 Å and 1.88 Å respectively.
culture. 1mL of mixed culture was then added to 100mL of raw and FTIR analysis was carried out to study the functional groups of
pre-treated leachate, and incubated overnight at 37
C at 110 rpm the synthesized nanoparticle (Fig. 1b). The broad band at 3437cm1
for duration of 5days. Samples were withdrawn daily and were shows the stretching vibrations of hydroxyl groups of water with
centrifuged at 7000 rpm for 10min. The supernatant was collected intermolecular hydrogen bonds (El-Said et al., 2012). The sharp
for COD estimation. band at 1598cm1 may be due to HeOeH bending vibrations (El-
Said et al., 2012). The strong narrow band at 1383cm1 corre-
sponds to FeeH bending vibrations (Li et al., 2016). The character-
3. Results and discussions istic band in the range of 1000 to 1100cm1 corresponds to PeOeP
stretching vibrations (El-Said et al., 2012). The weak band at
3.1. Characteristics of leachate 787cm1 corresponds to FeeO stretching vibrations in Fe(OH)2
(Wang and Andrews, 2006) and the one in the range of 850 to
Leachate characterization was done as per standard methods 990cm1 represents the MoeOeMo stretching vibrations (Cooke,
(APHA, 2012) and the obtained results are given in Table 1. The 2005; Kumar et al., 2015; Sharma et al., 2016).
collected leachate had a pH of 8.28 and BOD/COD value of 0.03, and Scanning Electron Microscopy (SEM) was used to analyze the
can thus be categorized as stabilized landfill leachate. COD of sta- surface morphology of FeMoPO particles (Fig. 1c) and the results
bilized landfill leachate will normally be less than 4000 mg/L, but show that the prepared material was bead shaped structure in
the collected leachate had COD higher than 4000 mg/L. Similar appearance (Sharma et al., 2016). The size distribution of synthe-
results have been reported by Laiju et al. (2014). sized FeMoPO nanoparticles was carefully analyzed by using Mal-
vern Zetasizer Nano ZSP. The DLS measurements indicated that
FeMoPO nanoparticles in nanopure water had trimodal size dis-
Table 1 tributions. The size of particles ranged from 232nm to 4 mm, with
Leachate Characteristics before and after electro-Fenton Treatment.
the average size being 192.5nm. The particle size obtained by DLS
Sl. No. Parameters Values measurement was much larger than the size reported by Sharma
Raw Leachate Treated Leachate et al. (2016) using Transmission Electron Microscopy (TEM) im-
ages. Sharma et al. (2016) had reported the size of primary FeMoPO
1. pH 8.28 1.98
2. Electrical conductivity (mS/cm) 41281 55808
nanoparticles to be in the range of 10nme30nm; however in water
3. Total Dissolved Solids (mg/L) 26420 35550 they are aggregates having an average size of 192.5nm. Aggregates
4. Chlorides (mg/L) 6000 5988 larger than 2 mm accounted for only 6% of the total nanoparticle
5. Total alkalinity as CaCO3 (mg/L) 6375 0 mass.
6. Calcium (mg/L) 465 458
Zeta potential of nanoparticles is a measure of the magnitude of
7. Magnesium (mg/L) 1190 1182
8. BOD5,20 (mg/L) 220 517 their surface charges and an indicator of their stability behaviour in
9. COD (mg/L) 7184 1293 colloids or suspensions. The prepared FeMoPO nanoparticles had a
10. BOD5/COD 0.03 0.40 zeta potential of 18.1mV, indicating it to be unstable in colloids or
11. Iron (mg/L) 72.56 87.89 suspensions. The aggregate formation observed during the DLS
12. Copper (mg/L) 0.62 0.42
measurement is explained by this unstable nature.
 A. Baiju et al. / Journal of Environmental Management 210 (2018) 328e337 331

Fig. 1. (a) X-ray Diffractogram (b) FTIR Spectrum and (c) SEM image of FeMoPO Nanoparticles.

3.3. Stabilized landfill leachate treatment by E-Fenton process
In heterogeneous E-Fenton process, effect of catalyst dosage was
studied by varying dosages from 25 mg/L to 100 mg/L (Fig. 2a). The
other operating parameters were initial pH 3, voltage 5 V, electrode
spacing 3cm and electrode area 25cm2. An increase in catalyst
dosage initially increased the COD removal efficiency, but beyond
an optimum dosage, the removal efficiency had decreased. More-
over, the COD removal was rapid during the first 20 min; further
increase was at a slower pace. By 90min, almost steady state has
been achieved. The optimum catalyst dosage for electro-Fenton
process was 50 mg/L. Maximum COD removal observed for
electro-Fenton processes was 77%. At higher catalyst dosages, the
excess Fe2þ will act as hydroxyl radical scavenger and get oxidized
to Fe3þ as shown in Eqn. (3) (Atmaca, 2009). Thus the hydroxyl
radical available for oxidation of organic matter will be reduced,
thus lowering the COD removal efficiency. At lower dosages,
amount of Fe2þ leaching will be insufficient for sufficient hydroxyl
radical production, thereby lowering the COD removal efficiency
(Oturan et al., 2001).
332 A. Baiju et al. / Journal of Environmental Management 210 (2018) 328e337
Fig. 2. Effect of (a) Catalyst Dosage (Experimental conditions: initial pH 3, voltage 5 V,
electrode spacing 3cm and electrode area 25cm2) (b) solution pH (Experimental
_ /Fe3þ þ OH
Fe2þ þ OH (3)
To investigate the effect of pH on E-Fenton process, studies were
performed by varying pH from 1.5 to 5 (Fig. 2b). The other operating
parameters were catalyst dosage 50 mg/L, voltage 5 V, electrode
spacing 3cm and electrode area 25cm2. Efficiency of E-Fenton
process was found to be decreases with increasing solution pH. The
optimum pH for heterogeneous E-Fenton process was found to be 2
with a removal efficiency of 82%. As the pH was increased from 2 to
5, removal efficiency decreased from 82% to 50%. Instability of
hydrogen peroxide (Eqn. (4)) and formation of insoluble iron
hydroxocomplexes ([Fe(H2O)8(OH)2]4þ, [Fe2(H2O)7(OH)3]3þ and
[Fe2(H2O)7(OH)4]5þ) could be the reason for decrease in COD
removal efficiency at higher pH (Laiju et al., 2014; Nidheesh and
Gandhimathi, 2014). Also at higher pH, H2O2 decomposition can
be inhibited by the absence of protons, thereby reducing the pro-
duction of hydroxyl radicals, which reduces the efficiency of Fenton
process with increasing pH (Shafieiyoun et al., 2012).
2H2 O2 /2H2 O þ O2 (4)
H2 O2 þ Hþ /H3 Oþ
2 (5)
2Hþ þ 2e /H2 (6)
The solubility equilibrium of iron at pH less than 3.5 is mainly
controlled by Fe3þ ions (Nidheesh, 2015; Venu et al., 2016, 2014). At
lower pH (pH < 3), major amount of total iron exists in the form of
Fe2þ and Fe3þ, thus there is a greater chance of occurrence of
Fenton process at pH around 3 (Pignatello et al., 2006). In this study,
the optimum pH for the heterogeneous E-Fenton reaction was
observed as 2. Similar result was observed by Shafieiyoun et al.
(2012) for Fenton oxidation of landfill leachate using Zero Valent
Iron as heterogeneous catalyst. Formation of complexes iron spe-
cies and oxonium ion [H3O2]þ (Eqn. (5)) would slow down the re-
action at pH below the optimum value (Shafieiyoun et al., 2012;
Zhou et al., 2007). Also evolution of hydrogen gas (Eqn. (6)) at
lower pH would bring down the efficiency, as it would reduce the
generation of hydrogen peroxide (Wang et al., 2010).
The effect of applied voltage on heterogeneous electro-Fenton
process was studied by varying the voltage from 5 V to 12 V
(Fig. 2c). The other operating parameters were catalyst dosage
50 mg/L, pH 2, electrode spacing 3cm and electrode area 25cm2. A
slight increase in COD removal (from 82% to 83%) was observed as
the voltage was increased from 5 V to 8 V, which could be due to the
€
higher ferrous ion electro-regeneration from ferric ion (Ozcan et al.,
2009) as shown in Eqn. (7).
Fe3þ þ e /Fe2þ (7)
2H2 O/4Hþ þ O2 þ 2e (8)
:
H2 O /O H þ Hþ þ e (9)
Upon further increasing to 12 V, a sudden decrease in COD
removal to 79.6% was observed; which could be due to the
competitive electrode reactions like: oxygen discharge at anode as
in Eqn. (8) and hydrogen gas evolution at cathode as in Eqn. (6).
conditions: catalyst dosage 50 mg/L, voltage 5 V, electrode spacing 3cm and electrode
area 25cm2) (c) applied voltage (Experimental conditions: catalyst dosage 50 mg/L, pH
2, electrode spacing 3cm and electrode area 25cm2) and (d) electrode spacing
(Experimental conditions: catalyst dosage 50 mg/L, pH 2, voltage 5 V and electrode
area 25cm2) on electro-Fenton Process.
 A. Baiju et al. / Journal of Environmental Management 210 (2018) 328e337 333

These reactions inhibit main reactions shown in Eqn. (9) and Eqn.
(7) which lead to decrease in E-Fenton process efficiency with in-
crease in voltage (George et al., 2014, 2013). Though COD removal
slightly increased with increase in voltage from 5 V to 8 V, in the
further studies applied voltage was kept as 5 V itself, in order to
minimize treatment cost.
The effect of electrode spacing in heterogeneous E-Fenton pro-
cess was investigated by varying the electrode spacing from 2cm to
4cm (Fig. 2d). The other operating parameters were catalyst dosage
50 mg/L, pH 2, voltage 5 V and electrode area 25cm2. The ohmic
drop increase and mass transfer decrease of Fe3þ explains the slight
decrease in COD removal observed as the electrode spacing was
increased from 3cm to 4cm. When the electrode spacing was
reduced to 2cm, the efficiency further dropped due to the faster
electro-generation of Fe2þ to Fe3þ at anode as in Eqn. (10).
Fe2þ /Fe3þ þ e
efficiency (Laiju et al., 2014).
Catalyst recovered at the end of third recycle was further char-
acterized using SEM, XRD and FTIR (Fig. 5). These results confirmed
the presence of iron hydroxocomplexes and iron phosphates in the
recovered catalyst. These adsorbed iron phosphates and other
organic matter would deactivate the active catalytic sites. This
deactivation would reduce the iron leaching from the catalyst,
thereby reducing the efficiency of the process (Laiju et al., 2014).
3.6. Characterization of the recovered catalyst
In the X-ray Diffractogram of catalyst recovered from of E-Fen-
ton process (Fig. 5a), characteristic peak at 31.83⁰ confirms the
presence of Iron (II) Diphosphate Dihydrate (Fe2H4O9P2). The peak
at 56.60⁰ corresponds to the presence of Iron phosphate
(Fe6.23H1.55O24P6) (Dal Bo and Hatert, 2012). The presence of
(10)

3.4. Comparison study of electro-Fenton with different cases

The COD removal obtained by heterogeneous electro-Fenton

process under optimized conditions was then compared with the
COD removal obtained by two different cases (Fig. 3):

 Case 1: Aeration alone (by providing aeration alone in the

absence of catalyst and external current)
 Case 2: Electrolysis alone (by applying current in the absence of
catalyst and without aeration).

Electrolysis and Aeration as individual treatment option resul-

ted in only 58% and 55% COD removal respectively, when compared
to the 82% COD removal obtained by electro-Fenton process. In each
of these cases, a major fraction of COD removal is mainly due to the
precipitation of humic acids that take place during the initial pH
adjustment (Silva et al., 2017). The lower COD removal observed in
the aeration case implies that the oxidation potential of oxygen is Fig. 3. Performance of electro-Fenton Process under different Experimental Conditions
not sufficient to oxidize the organic matter present in leachate. (Experimental conditions: catalyst dosage 50 mg/L, pH 2, voltage 5 V and electrode
Moreover, the lower COD removal observed in case of electrolysis area 25cm2).
implies that electro-sorption accounts for only a minor fraction of
COD removal achieved through electro-Fenton. Thus major
pollutant degradation in E-Fenton is through the production of
hydroxyl radicals.

3.5. Catalyst Reusability Study

The ability to be recovered and reused makes the heterogeneous

catalysts superior to the homogeneous catalysts. Due to the pre-
cipitation of humic acids during the initial pH adjustment, the re-
covery of catalyst as such was not possible. Volume of sludge
produced during heterogeneous electro-Fenton process was
320 mL/L. The sludge thus collected at the end of electro-Fenton
process was first dried in a hot air oven at 103
C for 24hrs and
subsequently kept in muffle furnace at 550
C for 15min in order to
remove the adsorbed organics and recover the catalyst particles.
The recovered catalyst was then reused in electro-Fenton process
for over 3 cycles.
In electro-Fenton process, the efficiency decreased from 82% to
78% at the end of first recycle and subsequently dropped to 75% at
the end of third recycle (Fig. 4). The decrease in efficiency over
subsequent cycles could be due to the adsorption of inorganic
compounds that precipitate out during the treatment process upon Fig. 4. Catalyst Reusability Study for electro-Fenton Process (Experimental conditions:
the active catalytic sites. This would decrease the iron leaching rate pH 2, Catalyst dosage 50 mg/L, Electrode spacing 3cm, Voltage 5 V, Electrode area
of recovered catalyst, thereby resulting in lower COD removal 25cm2).
334 A. Baiju et al. / Journal of Environmental Management 210 (2018) 328e337

(c)

Fig. 5. (a) X-ray Diffractogram (b) FTIR Spectrum and (c) SEM image of Recovered Catalyst.

Fe2MoP12 is indicated by the peak at 45.61⁰, which appears to be
slightly shifted when compared to the peak at 48.1⁰ in the X-ray
diffractogram of FeMoPO.
The FTIR spectrum (Fig. 5b) observed for the recovered catalyst
was identical to that of FeMoPO, thereby indicating the presence of
FeMoPO nanoparticles in it. The FTIR spectrum of catalyst recovered
from electro-Fenton process has shifted upwards with respect to
that of FeMoPO, thereby indicating a decrease in concentration of
the functional groups. In electro-Fenton process, due to the electro-
regeneration of Fe2þ ions from Fe3þ ions, precipitation of iron in the
form of iron hydroxide complexes will be comparatively less. Thus
the iron content of the catalyst recovered from electro-Fenton
process is primarily due to the presence of FeMoPO nanoparticles
in it.
As this catalyst is further reused, its iron content decreases due
to the leaching of Fe2þ ions. This explains the upward shift of the
FTIR spectrum of catalyst recovered from electro-Fenton process
with respect to that of FeMoPO. The strong band in the range of
1000 to 1100cm1 corresponds to the PeOeP stretching vibrations
(El-Said et al., 2012). Phosphates from FeMoPO nanoparticles may
 A. Baiju et al. / Journal of Environmental Management 210 (2018) 328e337
leach into the system during the recycle. This explains the decrease
in intensity of PeOeP vibrations in the FTIR spectrum of catalyst
recovered from electro-Fenton process when compared to that of
FeMoPO nanoparticles. The band observed for catalyst in the range
of 850 to 990cm1 corresponding to OeMoeO vibrations (Cooke,
2005; Kumar et al., 2015; Sharma et al., 2016) is almost absent in
the FTIR spectrum of the recovered catalyst. The additional weak
bands observed at ~2110cm1 and ~2828cm1 might correspond to
Metal(M)-H and NHþ
3 stretching vibrations respectively (Cooke,
2005). This is explained by the NH3eN content of the leachate.
Stabilized landfill leachate usually has an NH3eN content greater
than 400 mg/L. Under acidic conditions, NH3eN converts to
ammonium ions which could adsorb onto the catalyst, thereby
resulting in the additional band at ~2828cm1. The surface of
recovered catalyst had flaky appearance when compared to the
bead shaped appearance of FeMoPO nanoparticles as shown in SEM
image (Fig. 5c).
3.7. Comparison of leachate characteristics before and after E-
Fenton treatment
The characteristics of the leachate before and after electro-
Fenton treatment (Table 1) were analyzed as per standard
methods (APHA, 2012). It could be seen that the leachate that was
initially alkaline has become acidic after E-Fenton process, with
zero alkalinity. The TDS content seems to have increased after
treatment, thereby resulting in an increase in electrical conduc-
tivity. The COD of raw leachate have reduced from 7184 mg/L to
1293 mg/L at the end of 90min of E-Fenton treatment. While
BOD5,20 has increased from 220 mg/L to 517 mg/L at the end of E-
Fenton process. Thus the overall BOD5/COD ratio increased from
0.03 to 0.40, which indicates an enhancement in biodegradability of
the leachate. This enhancement in biodegradability has been
brought about by the oxidation of organic pollutants in raw
leachate to easily biodegradable intermediates by the hydroxyl
radicals.
The iron content in leachate seems to have slightly increased
after treatment. This could be due to the additional iron that could
have leached from the catalyst or it could be due to electro-
regeneration of ferrous iron from ferric iron, causing more iron to
Fig. 6. COD removal observed for the isolated colonies.
335
exist in its soluble from as Fe2þ. The value of chlorides, calcium and
magnesium appears to be more or less the same before and after
treatment. The copper content seems to have slightly decreased by
0.2 mg/L, which could be due to its adsorption onto the sludge. Also,
the colour of leachate after treatment had changed from dark
brown to light yellow.
3.8. Biological treatment
At the end of 90min of electro-Fenton treatment, the COD of
stabilized landfill leachate had reduced from 7184 mg/L to
1293 mg/L, and the BOD5/COD ratio had increased from 0.03 to
0.40. As per The Environment Protection Act (Ministry of
Evironment and Forest, 1986) for any trade effluent to be dis-
charged into inland surface water or onto marine coastal area, its
COD should be less than 250 mg/L. Thus in the present study,
electro-Fenton process did not succeed in bringing down the COD
of leachate to meet the discharge standards. But it did succeed in
improving the biodegradability of leachate. Thus a subsequent
biological treatment was carried out to check if the COD could be
further reduced to meet the discharge standards. The biological
treatment involved the following steps:
 Isolation of native bacterial species.
 Screening of native bacterial species based on their COD removal
efficiency.
 Generation of mixed bacterial culture.
 Application of mixed bacterial culture to raw and pre-treated
leachate.
Native bacterial species were isolated from soil samples ac-
quired from the leachate collection pit. Out of the five different
dilutions (101, 102, 103, 104 and 105) prepared, 103 dilution
agar plate gave countable number of colonies (in the range of
10e300). From this plate, 10 distinct colonies were picked for the
screening study, and were numbered from 1 to 10. Among the 10
colonies, three of them (Colony No. 1, 2 and 10) gave COD removal
greater than 30% from the pre-treated leachate (Fig. 6).
The three colonies that were screened out were further used in
the generation of the mixed bacterial culture. 1mL of the mixed
bacterial culture was then added to raw and pre-treated leachate.
Fig. 7. COD Removal obtained using Mixed Bacterial Culture for raw and pre-treated
Leachate (Experimental conditions: pH 8, Temperature 37
C, 1mL Inoculum dosage).
336 A. Baiju et al. / Journal of Environmental Management 210 (2018) 328e337
COD removal efficiency was then monitored for a period of 5 days
(Fig. 7). It could be seen that COD removal observed for raw
leachate was only 17%, which could be due to its low BOD5/COD
ratio of 0.03. While for pre-treated leachate, 82% COD removal was
observed. The final COD of raw and pre-treated leachate were
5956 mg/L and 192 mg/L respectively. The overall COD removal
efficiency at the end of combined heterogeneous electro-Fenton
and biological process was 97%. Similar to the present work,
Roshini et al. (2017) analyzed the efficiency of combined E-Fenton
and biological process for the treatment of industrial textile
effluent. COD removal by E-Fenton process was 48%, while the
combined process resulted in 86% COD removal. Thus coupling E-
Fenton with a subsequent biological treatment proves to be more
effective than individual treatment options.
4. Conclusions
In the present study, Iron molybdophosphate (FeMoPO) was
synthesized by co-precipitation method and used as a heteroge-
neous E-Fenton catalyst for stabilized landfill leachate treatment.
The results indicated that 82% COD removal was achieved at
optimal conditions: pH 2, catalyst dosage 50 mg/L, voltage 5 V,
electrode spacing of 3cm and electrode area 25cm2. The COD was
reduced from 7184 mg/L to 1293 mg/L. An enhancement in
biodegradability was observed, the BOD5/COD ratio increased from
0.03 to 0.4. Catalyst reusability studies indicated that the recovered
catalyst could be effectively reused upto three cycles. Subsequent
biological treatment using native bacterial species further brought
down the COD to 192 mg/L. Thus electro-Fenton combined with
biological process proved to be an effective alternative for treat-
ment of stabilized landfill leachate.
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