International Journal of Scientific Research in Knowledge, 2(8), pp.

362-369, 2014
Available online at http://www.ijsrpub.com/ijsrk
ISSN: 2322-4541; 2014 IJSRPUB
http://dx.doi.org/10.12983/ijsrk-2014-p0362-0369


362
Full Length Research Paper

Performance of Ozone Reactor in Treating Stabilized Landfill Leachate: Efficiencies
and Limitations

Salem S. Abu Amr
1*
, Hamidi Abdul Aziz
2
, Mohammed J.K. Bashir
3


1
Environmental Health Directorate, Ministry of Health, Palestine
2
School of Civil Engineering, Engineering Campus, Universiti Sains Malaysia, 14300 Nibong Tebal, Penang, Malaysia
3
Department of Environmental Engineering, Faculty of Engineering and Green Technology, UniversitiTunku Abdul Rahman,
31900 Kampar, Perak,Malaysia
*Corresponding Author: sabuamr@hotmail.com

Received 01 June 2014; Accepted 06 July 2014

Abstract. Ozone has a high oxidation level and is typically used to improve the removal of organic and inorganic components.
In this study, we investigated the performance of ozone in the removal of COD and color from mature landfill leachate with
low concentration of COD and different volumes of samples (2, 5, and 10 L). The highest removal of COD (22%) and color
(88.3%) was obtained in the lowest volume of ozonated sample. We studied ozone decomposition during 1 h of reaction time
and found increases in ozone decay with increasing sample volume. Ozone consumption for COD removal was calculated, and
the highest amount of consumed ozone (0.54 Kg/ Kg COD) corresponded to the highest removal of COD in the lowest sample
volume. Biodegradability, as measured by lab scale aeration, increased from 23% to 42% after ozonation of dilute leachate.
Findings indicate that the performance of ozone improves with decreasing sample volume, and that biodegradability of
stabilized leachate is improved by ozonation.

Keywords: ozonation, sanitary landfill, leachate treatment, biodegradability

1. INTRODUCTION

Continuous population growth and industry
development have led to an increase in waste
generation. To date, land filling is the preferred option
for the disposal and management of solid urban
wastes (Tengrui et al., 2007). Despite the advantages
of this disposal method, however, the highly polluted
industrial wastewater produced elicits significant
concern, especially with land filling being the most
common solid waste disposal technique (Ghafari et
al., 2005). Landfill leachate is defined as liquid that
seeps through solid waste in a landfill, producing
extracted, dissolved, or suspended materials
(Christensen et al., 2001). It is a potential pollutant
that may cause harmful effects on groundwater and
surface water that surround a landfill site unless
returned to the environment in a carefully controlled
manner (Scottish Environment Protection Agency
(SEPA 2003). Leachate contains high amounts of
organic compounds, ammonia, heavy metals, a
complex variety of materials, and many other
hazardous chemicals; it is recognized as a potential
source of groundwater and surface water
contamination (Christensen et al., 2001; SEPA 2003;
Schrab et al., 1993). Regardless of changes in the
concentration of landfill leachate, its complexity can
be categorized on the basis of four major groups of
pollutants, depending on a complex set of interrelated
factors: dissolved organic matter, inorganic macro-
components, heavy metals, and xenobiotic organic
compounds (Aziz et al., 2004).
One of the main problems encountered in landfill
management is the establishment of efficient
treatment methods for large quantities of polluted
leachate. The environmental effect of leachate is
influenced by leachate strength, proper leachate
collection, and efficiency of leachate treatment.
Leachate requires treatment to minimize the amount
of pollutants to an acceptable level prior to discharge
into water sources (Aziz et al., 2010). A number of
leachate treatment techniques, including biological,
physical, and chemical processes, have been applied
(Goi et al., 2009; Baig et al., 2001). Ozonation is one
of the chemical processes used in the treatment of
stabilized landfill leachate to reduce leachate strength
and the amount of non-biodegradable organics. This
method increases the biodegradability of high
Abu Amr et al.
Performance of Ozone Reactor in Treating Stabilized Landfill Leachate: Efficiencies and Limitations
363
molecular weight organic compounds through the
decomposition of large organic molecules, thereby
increasing treatment effectiveness and converting
these compounds into types that are easily assimilated
biologically (Bila et al., 2005). In recent years, some
ozone applications and techniques have been applied
in the removal of organics from stabilized landfill
leachate (Tizaoui et al., 2007; Chaturapruek et al.,
2005; Rivas et al., 2003). Ozone is a strong oxidizer
with high reactivity and selectivity for organic
pollutants (Bila et al., 2005). The performance of
ozone in removing the chemical oxygen demand
(COD) and color of different volumes of diluted
leachate is not well documented in the literature.
Furthermore, a review of literature has shown that the
ozonation process is rarely employed in the treatment
of a semi-aerobic landfill leachate, particularly, in a
tropical county such as Malaysia. Thus, the present
study investigated the performance of ozone in
removing contaminants in different organic
concentrations from a semi-aerobic stabilized landfill
leachate. To address this problem, the present study
investigated the performance of ozone in contaminant
removal at different organic concentrations. The
specific objectives of this study are the following:
(1) To elucidate ozone decomposition and decay at
different volumes of diluted leachate;
(2) To investigate the performance of ozone
reactor in removing COD and color from semi-aerobic
stabilized landfill leachate, and at different leachate
concentrations.
(3) To evaluate the performance of ozone in
enhancing the biodegradability of low-concentration
leachate; and
(4) To determine the amount of ozone
consumption for COD removal at different volumes of
diluted leachate.

2. MATERIALS AND METHODS

2.1. Sampling

Leachate samples were taken from a leachate aeration
pond of a semi-aerobic stabilized landfill leachate at
Pulau Burung Landfill Site (PBLS) located in Byram
Forest Reserve in Penang, Malaysia. PBLS has an
area of 62.4 ha, of which 33 ha is currently
operational and receives about 2200 tones of
municipal solid waste daily. It is equipped with a
natural marine clay liner and three leachate collection
ponds (Bashir et al., 2011). About 20 L of leachate
was manually collected and placed into plastic
containers on 14 February 2011. The characteristics of
the undiluted leachate used in the experiments are
summarized in Table 1. Sample collection and
preservation were performed in accordance with the
Standard Methods for the Examination of Water and
Wastewater (Standard Methods for the Examination
of Water and Wastewater, APHA (2005).

Table 1: Characteristics of semi aerobic landfill leachate from PBLS
Parameters Value
COD (mg/l) 2000
BOD (mg/l) 74
NH
3
-N mg/l 1170
Color (PL Co.) 5320
pH 8.5

2.2. Experimental Procedure

Figure 1 shows the schematic of the ozone reactor,
which has a height of 65 cm and an inner diameter of
16.5 cm. It is supported by a cross column ozone
chamber for enhancing ozone gas diffusion. Ozone
was produced using a BMT 803 generator (BMT
Messtechnik, Germany) fed with pure dry oxygen.
The concentration of gas ozone input and output (in
g/m
3
NTP) was measured before and after the
ozonation process using an ultraviolet gas ozone
analyzer (BMT 964). The gas flow rate was
500 mL/min10%, and the concentration of ozone
input was 54 g/m
3
NTP0.5%. Ozone was applied on
leachate diluted with an initial COD of 250 mg/L at
varying sample volumes (2, 5, and 10 L). Moreover,
ozone was applied at different leachate concentrations
and a 2 L sample volume. The Initial COD was
adjusted using the following formula:
C
1
V
1
= C
2
V
2
(1)
Where C
1
is the original concentration of COD
before it was watered down or diluted, C
2
denotes the
final COD concentration after dilution, V
1
is the
volume to be diluted, and V
2
represents the final
sample volume after dilution


All the experiments were conducted at room
temperature (203 C) at the environmental laboratory
of the School of Civil Engineering, University Sains
Malaysia.

International Journal of Scientific Research in Knowledge, 2(8), pp. 362-369, 2014
364

Fig. 1: schematic diagram of Ozone equipment.
1: Oxygen tank, 2: O3 Generator (BMT803), 3: O3 analyzer (BMT 964), 4: O3 reactor (Stainless steel), 5: Sample in, 6: Sample Out, 7: Cooling System (<
15
0
C), 8: O3 Catalyzing cartridge, 9: Activated Carbon, 10: Water bath, 11: O3 inlet chamber.

2.3. Analytical Method

Concentration of Chemical Oxygen Demand (COD),
color, ammonia, and pH were tested before and after
each experiment. All the tests were conducted
according to the Standard Methods for the
Examination of Water and Wastewater (APHA 2005).
COD concentration was measured using a DR/2500
spectrophotometer based on the closed reflux and
colorimetric method of Method No. 5220D (Bashir et
al., 2011; APHA 2005). Color concentration was
measured as apparent color by a DR 2010 Hach
spectrophotometer based on Method No. 2120C. The
concentration of NH
3
-N was measured byNessler
Method (Method: 8038) using a Hachs DR2500
spectrophotometer. pH was measured by a portable
digital pH/Mv meter. BOD
5
was measured according
to Standard Methods. Biodegradability was
determined by the initial COD of 1 L aerated sample;
an air pump was used and COD was gradually
measured until a constant value, serving as the final
COD concentration, was reached. The sample size
was maintained at 1 L during aeration. Water loss in
the sample was compensated by distilled water. The
following equation was used to calculate
biodegradability:
COD
(Sbi)
= (COD
i
) - (COD
f
) (2)
Where COD
(Sbi)
is the biodegradability, COD
i
represents the initial total COD in the sample, and
COD
f
denotes the constant amount of COD after
optimal aeration.



3. RESULTS AND DISCUSSIONS

3.1. Decay of Ozone Input and Off-gas Ozone
Concentration

Ozone decomposition reaction in aqueous solution has
been widely investigated since ozone has been paid
considerable attention as an alternative
oxidant/disinfectant in drinking water processing.
Figure 2 shows the changes in off-gas ozone
concentration with time. The overlapping graphs for
the different experiments indicate the reproducibility
of the results and validity of the experimental
procedure. For tap water, ozone concentration at the
outlet of the reactor gradually increased for the first
10 min, a behavior characteristic of a fast kinetic
regime of ozone reactions at the beginning of
experiments (Tizaoui et al., 2007; Chaturapruek et al.,
2005; Rivas et al., 2003; Benbelkacem et al., 2003).
During the first 5 min, ozone concentration in the
water sample was equal to zero. Ozone was degraded
to oxygen and free radicals at first contact with water,
and the potential of water for oxidizing chemical
species increased.
O
3
+ H
2
O OH + 2O
2
(3)


Abu Amr et al.
Performance of Ozone Reactor in Treating Stabilized Landfill Leachate: Efficiencies and Limitations
365

Fig. 2: Ozone level in tap water and diluted leachate.
Exp. Condition: (Samples source: tap water & diluted leachate (COD 250 mg/l), sample vol. 5 L, Gas flow dosage: 500 ml/min, O
3
input: 54.4 g/m
3
, 1 h
Retention time)

Change to an intermediate kinetic regime occurred
because of the decrease in pollutant concentration
after the dissolved ozone exponentially increased.
After approximately 50 min of ozonation, ozone
concentration began to level off at a value lower than
the concentration of ozone input. This result is an
indication that ozone reactions continue to place,
probably with products from initial reactions. A
similar behavior was observed in diluted leachate
(COD 250 mg/L), although the first period of fast
kinetics took longer (up to 5 min) with the gradual
increase in ozone concentration. The off-gas ozone
concentration for diluted leachate was lower than that
of tap water; nevertheless, this result indicates that
increasing the amount of pollutants contributes to
ozone consumption, thereby inhibiting a proportion of
the ozone from reacting with target compounds
(Tizaoui et al., 2007).
In general, ozone is consumed in two steps when
added to natural water: rapid ozone consumption and
slow decay. The amount of ozone consumed during
the first stage can be represented by the instantaneous
ozone demand, which corresponds to the difference
between administered ozone and the amount of ozone
measured after a few seconds. The rapid reaction step
is followed by a moderate or slow ozone decay stage
(Hoigne et al., 1994). Figure 3 shows ozone
consumption at different volumes of diluted leachate.
The first kinetics of the rapid ozone consumption
phase was equal to zero for the first 10 min of reaction
at different liquid volumes. In the second stage of
reaction, decay increased with rising liquid volume.
Maintaining a 2 L sample volume resulted in higher
removal efficiency. Ozone decay was assessed during
the ozonation of raw leachate and compared with that
observed in diluted leachate (Figure 4). The ozone
level in raw leachate was lower than that in the diluted
sample. Accordingly, ozone decomposition increased
under excessive organic concentrations.


Fig. 3: Input and off Ozone level in different volumes of diluted leachate.
Exp. Condition: (Samples source: diluted leachate (COD 250 mg/l), sample vol. 2, 5 and 10 L, Gas flow dosage: 500 ml/min, O
3
input: 54.4 g/m
3
, 1 h
Retention time)

International Journal of Scientific Research in Knowledge, 2(8), pp. 362-369, 2014
366
The efficiency of ozone in the treatment of
different concentrations of stabilized leachate was
assessed. Three experiments with ozone input fixed at
55 g/m
3
for varying volumes of diluted leachate were
performed. Figure 5 shows that the COD and color
removal efficiencies increased with decreasing sample
volumes. The highest removal levels for COD (25%)
and color (88.3%) were achieved at the lowest sample
volume (2 L). The increase in parameter elimination
with decreasing sample volumes of considerable
dissolved ozone in the aqueous phase at the beginning
of the process indicates the development of
accelerated reactions (Figure 3) with increased ozone
loss at greater sample volumes. Maintaining the
lowest sample volume, ozone was applied at different
leachate concentrations (Figure 5). The removal
efficiencies for COD and color improved from 15%
and 44% in raw leachate to 25% and 88.3% in diluted
leachate. Similar results were reported by recent
experiments: Cortez et al. (2011) obtained 28% COD
removal after the ozonation of 1 L of two-fold diluted
leachate while Silva et al. (2004) obtained 87% color
reduction following leachate ozonation.



Fig. 4: COD and Color removal in different volumes of diluted leachate


Fig. 5: Removal efficiency of COD and Color in different leachate concentration

3.2. Ozone Consumption

Ozone consumption (OC) is an important parameter in
ozone processes because it can be correlated with
energy conservation in the treatment process. It is
defined as the amount of ozone gas consumed in
removing a certain amount of COD during ozonation
under experimental conditions, and is expressed by
( ) COD COD
dt
C
C
V
Q
OC
t
AG
AG
G

|
|
.
|

\
|

=
}
0
0 0
1
(4)

where QG is the gas flow rate, V is the sample
volume, C
AG
denotes the off-gas ozone concentration,
C
AG0
represents the concentration of ozone input, t is
time, and COD
0
and COD correspond to the initial
and final COD.
Table 2 presents the evolution of OC and compares
different liquid volumes, leachate concentrations, and
COD removal levels. OC increased when liquid
volume decreased. Moreover, the highest OC value
with the highest COD removal was obtained at the
lowest sample volume. When ozonation was
performed at different leachate concentrations while
maintaining the lowest sample volume (2L), the
Abu Amr et al.
Performance of Ozone Reactor in Treating Stabilized Landfill Leachate: Efficiencies and Limitations
367
lowest OC value (2.1 KgO
3
/Kg COD) was reported at
15% COD removal at higher leachate concentrations
(Table 3). Previous studies reported OC values of 16
(Wang et al., 2003), between 2 and 3 (Geissen 2005;
Tizaoui et al., 2007), and approximately less than
1 KgO
3
/Kg COD (HO et al., 1974). The differences in
ozone consumption in literature are mainly due to the
wide variations in experimental conditions and
leachate characteristics [e.g., O
3
dosage, sample
volume, pH variance, and oxidants (H
2
O
2
, UV)].

Table 2: Comparison of Ozone Consumption in different volume of samples and different leahate concentrations
Sample volume 10Liter 5 Liter 2 Liter
COD removal (%) 10% 15% 25%
OC(kgO
3
/kgCOD) 6.55 8.27 8.5
*Initial COD 250 1125 2000
COD removal (%) 25% 21% 15%
OC(kgO
3
/kgCOD) 8.5 3.18 2.1
*(2L) Volume of sample

3.3. Biodegradability

Biodegradable COD can be removed from leachate
through aeration. Control over the process depends on
the regulation of aeration to satisfy oxygen
requirements, which are closely linked to organic
matter biodegradability and biodegradation kinetics.
Thus, better knowledge of biodegradation kinetics
enables the prediction of composting time. Waste
characteristics and aeration rate are also key
parameters that affect the emission of gases from
composting. Table 3 presents the effects of ozone on
COD and biodegradability. Biodegradability is
defined as CODi CODf during lab-scale aeration
(Eq. 2). Several studies have been conducted to
compare the performance of different aeration
methods, such as convective or forced aeration, up- or
down-flow technique, continuous or intermittent
aeration, and methods with or without air recirculation
Lau et al., 1992; Sesay et al., 1998; Bari et al., 2000;
Ekinci; 2004). The influence of aeration rate has been
studied primarily as a function of residual oxygen in
ventilated air or within composting media.
Table 3 presents the COD removal by aeration of
raw and diluted leachate at 15 d before and after
ozonation. Biodegradability increased after 1 h of
ozonation from 24% to 28% in raw leachate and from
25% to 34% in diluted leachate. BOD
5
/COD ratio also
obtained and increased from 0.03 to 0.04 in raw
leachate and from 0.037 to 0.052 in diluted leachate
(Table 3). These findings indicate greater applicability
in understanding the applicability of biological
treatment after the ozonation of different
concentrations of semi-aerobic stabilized leachate.

Table 3: Comparison of Biodegradability in raw and diluted leachate before and after Ozonation
Item Biodegradability
CODi (mg/l) CODf (mg/l) mg/l % BOD
5
/COD
Raw leachate before Ozone 2000 1524 476 24% 0.03
Raw leachate After Ozone 1700 1224 476 28% 0.04
Diluted leachate before Ozone 250 188 62 25% 0.037
Diluted leachate after Ozone 188 124 64 34% 0.052
Exp. Condition (aeration of diluted leachate at 15 days, Vol.1 L, COD tested after 24 h gradually until constant).

4. CONCLUSION

This study investigated the performance of ozone in
the treatment of different concentrations of semi-
aerobic stabilized landfill leachate of different sample
volumes. The lowest amount of off-gas ozone was
obtained at the largest sample volume, indicating that
ozone decay increases with the rising liquid volume.
Under experimental conditions, the removal
efficiencies for color and COD gradually increased
with decreasing sample volume. Moreover, the
removal efficiencies for COD and color improved
from 15% and 44% in raw leachate to 25% and 88.3%
in diluted leachate. As indicated by COD removal
through aeration, biodegradability improved from
24% to 28% in raw leachate and from 25% to 34% in
diluted leachate, suggesting the enhancement of the
applicability of aeration during the biological
treatment of leachate after ozonation.

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Abu Amr et al.
Performance of Ozone Reactor in Treating Stabilized Landfill Leachate: Efficiencies and Limitations
369





Dr.Salem Abu Amr is an Expert in environmental sciences and health at Palestinian Ministry of Health,
Environmental health department. He received his PhD degree in Environmental Engineering at
University of Malaysian sciences, school of civil Engineering, Malaysia. He has long experience in
water and waste water treatment and management, he worked several years for Governmental, local as
well as international consultancy firms, and he has an international award in the field of water and
agriculture. The research interests of Dr Salem encompass subjects related to Water and Environmental
Engineering, and focus on water quality monitoring and its relation to human health. Also Dr. Salem is
one of the leading research experts in the field of landfill leachate treatment using advanced oxidation
processes.







Dr Aziz is a Professor in environmental engineering at the School of Civil Engineering, Universiti Sains
Malaysia. Dr. Aziz received his Ph.D in civil engineering (environmental engineering) from University
of Strathclyde, Scotland in 1992. He is the Editor-in-chief of CJASR, IJSES and the Managing Editor of
IJEWM, IJEE. He has published over 200 refereed articles in professional journals/proceedings and
currently sits as the Editorial Board Member for 8 International journals. Dr Aziz's research has focused
on alleviating problems associated with water pollution issues from industrial wastewater discharge and
solid waste management via landfilling, especially on leachate pollution. He also interests in
biodegradation and bioremediation of oil spills.






Dr Mohammed J.K. Bashir is an Assistant Professor in environmental engineering at the faculty of
engineering and green technology, Universiti Tunku Abdul Rahman (UTAR), Malaysia. Dr. Bashir
received his B.Sc. degree in Civil Engineering from Islamic University of Gaza, Palestine. He received
M.Sc and Ph.D in Environ. Eng. from School of Civil Engineering, Universiti Sains Malaysia. He
received several award and has published many refereed articles in professional journals/proceedings.
Dr. Bashir's research has focused on wastewater treatment, solid and hazardous waste management,
environmental sustainability.