Đlhan F., Apaydın Ö., Kurt U., Arslankaya E., Gönüllü M.T.

, “Treatment of Leachate by Electrocoagulation and

Electrooxidation Processes”, Third International Conference on Environmental Science and Technology
(ICEST), August. 6-9, 2007, Houston—Texas, USA

TREATMENT OF LEACHATE BY ELECTROCOAGULATION AND

ELECTROOXIDATION PROCESSES

Fatih Đlhan, Ömer Apaydin, Uğur Kurt, Ertan Arslankaya, M.Talha Gönüllü
(Yildiz Technical University, Beşiktaş, Istanbul, Turkey)

ABSTRACT: Leachate has a complex structure and high pollute characteristics, and therefore its
treatment is much harder to meet the national discharge standards. Many treatment methods have been
proven to supply a satisfying treatment requirement. In this study, the advanced treatment methods
electrocoagulation (EC) and electrooxidation (EO) processes were compared with each other based on
main organic pollutants existing in leachate. The samples of leachate were supplied from Odayeri
Landfill Site in Istanbul. At the beginning of the study, electrocoagulation (with Aluminum and Iron
electrodes) electrooxidation (with Ti/Pt and Ti/RuO2 electrodes) and chemicalcoagulation were
compared with each other via COD and NH3-N removal rate. In EC process with Al electrodes, the
results showed that NH3-N removal efficiency was obtained 9.8%, and COD removal efficiency was
also obtained as 49.8% for 30 min of reaction time. After 30 min of operation, pH increased from 8.1
to 9.2 and the temperature increased from 24.2 ◦C to 26.4 ◦C. In EO process with Ti/Pt electrodes, the
results showed that NH3-N removal efficiency was determined as 83.9% and COD removal efficiency
was also obtained as 52.9% for 360 minutes of reaction time. After 360 min of operation, pH increased
from 7.7 to 8.3 and the temperature increased from 23.1 ◦C to 51.7 ◦C. The results of the study revealed
that electrocoagulation and electrooxidation methods can be used as pre-treatment method for leachate
treatment.
Key Words: Electrocoagulation, Electrooxidation, Leachate, Treatment, COD, NH3-N, Treatment cost.

INTRODUCTION
Leachate becomes ahead of wastewaters as being the most difficult to treat as it is a wastewater with a
complex and widely variable content generated within a landfill. By today, many treatment methods
for its treatment have been proven. Chemicalcoagulation (CC) process has been used widely in order
to treat water and wastewater for many decades. So it is known that CC involves in chemical
destabilization of particles and in the formation of larger particles through perikinetic flocculation. In
the CC process, it is used typical coagulants and flocculants include natural and synthetic organic
polymers, metal salts such as alum or ferric sulfate, and prehydolized metal salts such as
polyaluminum chloride and polyiron chloride (Metcalf&Eddy inc., 2003). In recent decades,
electrochemical treatment having features like relatively more economic and higher treatment
efficiency has been a promising method. Electrocoagulation (EC) is one of the simple and efficient
electrochemical methods for the purification of many types of water and wastewaters [Un et al., 2006].
In this technique, which is characterized by its simple equipment, easy operation, and decreased
amount of sludge, the coagulant is generated by electrolytic oxidation of an appropriate anode material
that leads, at an appropriate pH, to the insoluble metal hydroxide which is able to remove a large
variety of pollutants [Adhoum, and Monse, 2004]. These metal hydroxide species neutralize the
electrostatic charges on suspended solids and oil droplets to facilitate agglomeration or coagulation
and resultant separation from the aqueous phase [Mollah et al., 2001]. The mechanism of EC is
extremely dependent on the chemistry of the aqueous medium, especially its conductivity. The
mechanism of generating ions by EC can be explained with the examples of iron and aluminum, which
was used as both the anode and cathode in this study. In an electrolytic system, iron produces iron
hydroxide. In the case of iron or steel and aluminum anodes, two mechanisms for the production of the
metal hydroxide have been proposed [Rajeshwar and Ibanez, 1997; Chen, 2004]. The reactions for
electrocoagulation (EC) process are given in Equation 1-11.

Mechanism 1:
→ 4 Fe 2+ (aq ) + 8e −
Anode: 4 Fe( s )  (1)
 → Al(3aq+ ) + 3e −
Al  (2)
Chemical: 4 Fe 2+ (aq ) + 10 H 2 O (l ) + O2 ( g ) 
→ 4 Fe(OH ) 3 ( s ) + 8H + (aq) (3)
Al(3aq+ ) + 3H 2O 
→ Al (OH )3 + 3H (+aq ) (4)
Cathode: 8 H + (aq ) + 8e − 
→ 4 H 2 ( g ) (5)
Mechanism 2:
Anode: → Fe 2+ (aq ) + 2e −
Fe( s )  (6)
Chemical: Fe 2+ (aq) + 2OH − (aq ) 
→ Fe(OH ) 2 ( s ) (7)
Al 3+ + 3OH − → Al (OH )3 (8)
Cathode: 2 H 2O(l ) + 2e − 
→ H 2 ( g ) + 2OH − (aq ) (9)
Overall: Fe( s ) + 2 H 2O(l ) 
→ Fe(OH ) 2 ( s ) + H 2 ( g ) (10)
Al 3+ + 3H 2O → Al (OH )3 + 3H + (11)
In the EC application with Fe or Al anodes, it is hoped that the reactions presented in Equation 1-11
occur. The other electrochemical treatment method performed this study, Electrooxidation (EO)
process, direct anodic oxidation is dominant in this process, does not need to add large amount of
chemicals to wastewater or to feed O2 to cathodes with no tendency of producing secondary pollution
and fewer accessories required. These advantages make anodic oxidation more attractive than other
electrooxidation processes (Chen, G., 2004). The important part of an anodic oxidation process is
obviously the anode material. Anode materials investigated include glassy carbon [Gattrell and Kirk,
1990 ], Ti/RuO2, Ti/Pt–Ir [Murphy et al, 1992], fiber carbon [Szpyrkowicz et al, 1994], MnO2 [Rao et
al., 2001], Pt–carbon black [Boudenne and Cerclier, 1999], porous carbon felt [Polcaro and Palmas,
1997], stainless steel [Abuzaid et al, 1999], and reticulated vitreous carbon [Hofseth and Chapman,
1999].
In this study, electrocoagulation (EC) electrooxidation (EO) processes which the advanced
treatment methods was compared with each other and classical chemicalcoagulation (CC) process via
main organic pollutants existing in leachate. The sample of leachate was supplied from Odayeri
Landfill Site in Istanbul. At the beginning of the study, electrocoagulation ( with Aluminum
electrodes) electrooxidation (with Ti/Pt and Ti/RuO2 electrodes) and chemicalcoagulation were
compared to each other via COD and NH3-N removal rate.

MATERIALS AND METHODS

In the experimental study, leachate from the Odayeri Landfill in Istanbul was used. The
Odayeri Landfill was founded in 1995, and has served 75 ha area for 8000 ton municipal solid waste
(MSW) a day since that date. The properties of the leachate were analyzed and average values were
given in Table 1.

Table 1 The properties of leachate from Odayeri Sanitary Landfill

Analysis Units Concentration
pH - 8.2
COD mgL-1 12860
BOD5 mgL-1 5270
BOD5 / COD - 0.41
TKN-N mgL-1 2580
Ammonia-N mgL-1 2240
Suspended Solids mgL-1 345
Turbidity NTU 1340
Sulphate mgL-1 32
Chloride mgL-1 3100
Alkalinity mg CaCO3 L-1 8700
Conductivity mS 19.62 (at 23 ºC)
 All the experimental analysis was made according to Standard Methods [APHA, 1998]. COD
tests were performed as recommended in the open reflux method, and ammonia nitrogen tests using
the titration method. Merck analytical quality chemicals were used in the preparation of reagents. All
the runs were performed at room temperature.In the study, a digital DC power supply (GW Instek,
GPS 3030 DD, 0–30.0V, 0.0–3.0 A) was used in order to give a regulated electricity current to the
electrochemical cell. The pH was measured by a Jenway 3040 brand a pH-meter. Experiments were
run in a batch reactor consisting of a 0.6 L glass beaker equipped with a cathode and an anode, both
made of iron or aluminum for EC process and Ti/Pt and Ti/RuO2 for EO process and installed in
parallel. The distance between the electrodes was 6.5 cm. The dimensions of electrodes in 2.0 mm
thickness were 5.0 cm×15.0 cm. The total effective electrode area is calculated to be (9 cm x 5 cm)
45.0 cm2. The electrodes were dipped into the beaker containing leachate with a 0.5 L working
volume. Iron or aluminum ions dissolved by electrical charge in the cell acted as coagulants. The
experimental set-up used in the present study is presented in Figure 1.

A V

+ 1 -

1. D.C power Supply

2. Cathode
(Aluminum, Iron,
SS)
4 3 2
3. Anode (Ti/Pt,
Ti/RuO2,
Aluminum, Iron)
6 cm
4. Electrolityc cell

Figure 1 Experimental setup

In order to get a comparison of Electro Coagulation (EC) and Electrooxidation (EO)

processes, two different batch studies were done. Both methods were tested for COD removal, NH3-N
removal, and sludge amount, pH and temperature changes.

RESULTS AND DISCUSSION

In this section, results obtained during the study are given and discussed. Leachate treatment
performance was determined by both EC and EO processes. This section deals with some
considerations about the processes such as pH, temperature, COD removal, etc..
pH and temperature: In this section, the changes of pH and temperature are examined for
both EC and EO processes. According to the results, pH increases based on reaction time in EC
process. Reason for that situation can be due to dominant cathode reactions where OH- ions come into
being. Furthermore, temperature increases from 24.2 oC to 26.4 oC. However, it is obtained that pH of
the EO process fluctuates during reaction time and in order to dominant anode reaction and pH do not
increases significantly. Beginning of the study, pH increases gradually, and than it decreases after in
the end of 3rd hours. Moreover, temperature in EO process increases up to 50 oC.
COD: In this section, COD removal efficiencies were determined for chemicalcoagulation
(CC), EC and EO processes. EC was performed with Al-electrodes for 30 min. After reaction time for
30 min, example was left in order to precipitation for 30 min. Al2(SO)3.18H2O was added as coagulant
chemical in CC process. Mixing operations was performed for CC process as 200rpm for 1 min and
50rpm for 29 min. Moreover, it was performed a sedimentation process for 30 min. Moreover, EO
process was performed in the same situations for 300 min. Studies were performed in the same
situations for all different processes. The results obtained from CC, EC and EO processes are
presented in Figure 2 (Current density for EC, EO processes is 40mA/cm2, and Equivalent coagulant is
used in CC process based on Coulomb Law).

Figure 2 The removal efficiency of COD for different treatment process

The removal efficiency of COD is higher EC process than EO process. Moreover, in order to attain the
same COD removal efficiency in EO process is necessary a 300 min of reaction time. The removal
efficiency of COD for EC and EO processes were obtained between %37.8-49.8 and % 37.8-52.9,
respectively. Furthermore, the amounts of sludge as volume for CC, EC and EO processes are
obtained as %25.1, %17.2 and %0, respectively (Current Density for EC and EO processes was
40mA/cm2). Pollutant removal efficiencies of the processes are different each other. So, the removal
efficiencies of COD for EC and EO process are examined this study based on different electrode
types.
In EC process (Current Density was 40mA/cm2), the removal efficiency of COD is obtained
as 49.8% at the end of the 30 min with Al-electrodes (efficiency is 29.7% at the end of the first 5 min).
In EO process (Current Density was 40mA/cm2), the removal efficiency of COD is obtained as 39.6%
and 52.8% at the end of the 120 min and 360 min, respectively, with Ti/Pt-SS-electrodes. Furthermore,
the removal efficiency of COD is obtained as 12.6% and 41.7% at the end of the 120 min and 360
min, respectively, with Ti/RuO2-SS-electrodes.
Ammonia Nitrogen: One of the most important problems in leachate is nitrogenous
compounds. The treatment of this type of wastewater is difficult due to very high ammonia content.
The problems are especially related to fluctuations in nitrogenous compounds depending on landfill
age. When a leachate treatment plant is designed and constructed, these fluctuations in nitrogenous
content of leachate should also be considered. The removal efficiency of Ammonia is presented in
Figure 3 for EC and EO processes.
 Figure 3 The removal efficiency of Ammonium Nitrogen for EC and EO processes

The removal efficiencies of Ammonia Nitrogen are different significantly each other for different
treatment processes. In the EO process, the removal efficiencies of Ammonia were obtained as 74.2%
with Ti/Pt-SS-electrodes and 83.9% with Ti/RuO2-SS-electrodes (Current Density: 40mA/cm2). In the
EC process, however, the removal efficiencies of Ammonia Nitrogen were obtained as 7.4% with Fe-
electrodes and 9.8% with Al-electrodes.
It is known that reaction time has huge important for electrochemical processes. So, the
removal efficiency of Ammonia Nitrogen was examined that study and presented in Figure 4 and
Figure 5.
15
The efficiency of Ammonia Nitrogen, %

12 Al - Al
Fe - Fe

0
0 5 10 15 20 25 30
Reaction Time, min Fi
Figure 4 The removal efficiency of Ammonium Figure 5 The removal efficiency of Ammonium
Nitrogen for EC process Nitrogen for
According to Figure 4, in EC process (Current Density was 40mA/cm2), the removal efficiency of
Ammonia Nitrogen is obtained as 9.8% at the end of the 30 min with Al-electrodes. Moreover, the
removal efficiency of Ammonia Nitrogen is obtained as 7.4% at the end of the 30 min with Fe-
electrodes. From Figure 5, in EO process (Current Density was 40mA/cm2), the removal efficiency of
Ammonia Nitrogen is obtained as 34.5% and 74.2% at the end of the 120 min and 360 min,
respectively, with Ti/Pt-SS-electrodes. Furthermore, the removal efficiency of Ammonium is obtained
as 34.5% and 83.9% at the end of the 120 min and 360 min, respectively, with Ti/RuO2-SS-electrodes.
CONCLUSIONS
 This study demonstrates that electrochemical processes can be applied effectively to remove
the pollutants such as COD, NH3-N, etc. from leachate. EC and EO processes can be used as
pretreatment stage for leachate treatment. The pollutant removal efficiencies of EC and EO processes
were obtained better than CC process. Furthermore, the amount of sludge was also lower in
electrochemical processes than CC process. In EC process with Al-electrodes, the unit energy
consumptions were obtained 3.09 kWh/kg COD and 11.16 kWh/kg NH3-N removal for 30
min of reaction time. In EC process with Ti/Pt-electrode, unit energy consumptions were
obtained as 33.16 kWh/kg COD and 135.73 kWh/kg NH3-N removal per treated leachate for
360 min of reaction time. The results of the study revealed that electrocoagulation and
electrooxidation methods can be used as pre-treatment method for leachate treatment.
ACKNOWLEDGEMENT
The research was supported by TUBITAK (The Scientific and Technological Research Council of
Turkey) (Project name: TUBITAK CAYDAG-106Y083).
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