Post-Treatment of Anaerobically
Treated Medium-Age Landll
Leachate
Ebru Akkaya, Ahmet Demir, Dogan Karadag, Gamze Varank, M. Sinan Bilgili, and Bestamin Ozkaya
Department of Environmental Engineering, Yildiz Technical University, Esenler, Istanbul 34220, Turkey; ekoca@yildiz.edu.tr
(for correspondence)
Published online 1 May 2009 in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/ep.10362
This study focused on the removal of COD and
NH41 from medium-age leachate. Experiments were
performed in a laboratory-scale upow anaerobic
sludge blanket (UASB), a membrane bioreactor
(MBR), and using magnesium ammonium phosphate
(MAP) precipitation. MBR and MAP were used for the
post-treatment steps for anaerobically treated leachate
to increase the removal of organics and ammonium.
The UASB reactor removed nearly all biodegradable
organics and supplied constant efuent COD for all
concentration ranges of inuent leachate. Ammo-
nium removal efciency in the UASB reactor was rel-
atively low and the average value was 7.9%. Inte-
gration of MBR to the efuent of UASB reactor
increased the average COD removal efciency from
51.8 to 65.6% and maximum removal efciency
increased to 74.3%. MAP precipitation was applied as
a nal step to decrease the ammonium concentration
in the efuent of UASB1MBR reactors. The effect of
pH and the molar ratio of MAP constituents on the
removal of ammonium were evaluated. At optimal
conditions (pH: 9.0 and Mg/NH4/PO4: 1/1.2/1.2),
96.6% of ammonium was removed and MAP pro-
vided additional COD and turbidity treatment.
Consequently, the combined system of MBR and MAP
precipitation could be used as an appropriate post
treatment option for the anaerobically treated
medium-age landll leachate. 2009 American Institute
of Chemical Engineers Environ Prog, 29: 7884, 2010
Keywords: ammonium, leachate, magnesium am-
monium phosphate precipitation, membrane bioreac-
tor, upow anaerobic sludge blanket reactor
2009 American Institute of Chemical Engineers
78 April 2010 Environmental Progress & Sustainable Energy (Vol.29, No.1) DOI 10.1002/ep
INTRODUCTION
Sanitary landlling is the most widely used method
for the nal treatment of municipal solid wastes
(MSW). It is estimated that more than 70% of global
MSW is disposed in landll sites [1]. Physical, chemi-
cal, and biological processes occur within a landll
site to promote degradation on MSW. These proc-
esses result in the production of leachate for a very
long time [2]. Leachate is a high-strength wastewater
due to high content of organic and inorganic com-
pounds such as COD, BOD5, and ammonium, and
discharging leachate without efcient treatment may
result in serious environmental problems for receiv-
ing water bodies.
Ammonium and organics are the most signicant
pollutants of leachate in the long term and these
components should be treated efciently before dis-
charging. In the technical literature, many biological,
chemical, and physiochemical technologies have
been used for the removal of organics and nitrogen
from leachate. Among biological technologies, anaer-
obic treatment methods are more suitable due to
advantages of higher organic loading rates (OLRs),
lower operating costs, and production of usable bio-
gas [3]. In spite of these advantages, anaerobic treat-
ment does not generally produce efuent quality that
meets strict discharge limits. Therefore, the efuents
from anaerobic reactors usually require a post-treat-
ment before discharging into water bodies [4].
The membrane bioreactor (MBR) is a compact sys-
tem that combines biological treatment with mem-
brane ltration. Recently, MBR-based systems have
been increasingly used for wastewater treatment [5
7]. Among alternative treatment methods, magnesium
ammonium phosphate (MAP) precipitation has been
proven as an excellent treatment process to eliminate
high levels of ammonium ions in leachate [8]. Addi-
tionally, MAP sludge is accepted as a valuable fertil-
izer because of its nitrogen, phosphorus, and magne-
sium constituents and low solubility [9, 10].
In the light of the above evaluations, it can be
seen that the applications of cascaded treatment
methods are a crucial and necessity for leachate treat-
ment. Hence, the aims of the present work were to
perform an experimental study investigating MBR sys-
tem and MAP precipitation as a post-treatment of
anaerobically treated landll leachate. Pretreatment of
raw leachate was carried out in an upow anaerobic
sludge blanket (UASB) reactor in the lab scale. Raw
leachate samples were obtained from the Odayeri
Sanitary Landll Site. The landll site receives munici-
pal waste from a population of about 10 million and
is a medium-age landll (12 yr). To our knowledge,
many researchers have generally been focused on the
treatment of young leachate of Odayeri landll [11,
12], but there is no study for leachate having me-
dium-age characteristics. Furthermore, with the
implementation of the mentioned post treatment
methods, the changes in COD and ammonium re-
moval of pretreated leachate samples were observed.
The effects of each method on the treatment perform- Figure 1. Simplied UASB/MBR/MAP system layout
ance are determined and discussed in detail. for leachate treatment.

MATERIALS AND METHODS

Leachate Sample
Leachate used in this study was obtained from
Odayeri Sanitary Landll Site located in the European
side of Istanbul, Turkey. Leachate was being col-
lected in a pond within a landll site. Samples were
transferred to the laboratory once a week and kept at
48C in a refrigerator before usage. The leachate was
treated by using UASB, MBR, and MAP precipitation
methods. Raw leachate was pumped to the UASB re-
actor without pretreatment applications such as pH
adjustment, particle separation, etc. A diagram of
treatment system is shown schematically in Figure 1.
Leachate Treatment System
Upow Anaerobic Sludge Blanket Reactor
The UASB reactor was made of Plexiglas with an
internal diameter of 10 cm and a height of 125 cm.
The working volume of UASB reactor was 9.0 L. The
raw leachate was fed continuously through the bot-
tom of the reactor using peristaltic pump and the gas
liquid separator was equipped at the top of the reac-
tor. The temperature of the reactor was maintained at
mesophilic conditions (358C) by pumping water from
an external thermostat through a water jacket sur-
rounding the reactor. The UASB reactor was seeded
with anaerobic sludge supplied from a full-scale an-
aerobic reactor treating brewery wastewater. During
the 120 operational days, hydraulic retention time
(HRT) was kept constant as 3 days and OLR changed
in the range of 1.844.03 kg COD/m3-day due to the
uctuations in COD content of the leachate. The
COD concentration of raw leachate varied between
5500 and12,070 mg/L, and BOD5 values ranged from
1250 to 5830 mg/L.
Membrane Bioreactor
The MBR was used as a rst post-treatment step
following anaerobic treatment in order to remove the
residual organics and ammonium ion. The efuent
from UASB was fed simultaneously to the MBR and
these two systems were operated in continuous
mode. MBR consisted of an activated sludge bioreac-
tor, which was lled with biomass-supported material
supplied from a domestic wastewater treatment plant
(Pasakoy), and a membrane unit submerged into the
bioreactor. The reactor was made of a cylindrical
Plexiglas vessel with an internal diameter of 20.0 cm
and a height of 50.0 cm. Therefore, its working vol-
ume was 9.0 L. A circular air diffuser, which was
placed under the membrane module, maintained aer-
obic conditions and homogeneous distribution in
order to avoid membrane fouling. A cartridge lter
membrane module made of polypropylene with a
pore size of 1.0 lm and a ltration area of 0.5 m2
was used. The efuent was withdrawn by a pump.
During the experimental studies, MBR reactor has the
same ow rate with the UASB reactor and HRT was
constant at 3 days. Inuent COD of MBR reactor was
ranged from 3675 to 7056 mg/L in the rst 30 days of
operation and average value was 4250 mg/L during
the experimental course.
MAP Precipitation
Treatment performance of MAP process depends
primarily on the pH and ratio of magnesium, ammo-

Environmental Progress & Sustainable Energy (Vol.29, No.1) DOI 10.1002/ep April 2010 79
nium, and phosphate ions in solution. In the litera-
ture, there are some articles dealing with the opti-
mum pH for MAP precipitation. Zhang et al. studied
in the pH range of 8.511.0 for the treatment of land-
ll leachate and maximum ammonium removal was
obtained at pH 9.5, whereas Gunay and coworkers
[12, 13] achieved the lowest residual ammonium con-
centration in the efuent at pH 8.5. Ozturk et al. [14]
applied MAP precipitation to anaerobically pretreated
efuent and the highest removal efciency was
observed at pH 9.2. Similarly, Li et al. [15] indicated
that pH 8.59.0 is the optimum range for ammonium
removal by chemical precipitation. According to these
results, the effect of pH on the MAP process was
studied in the range of 8 to 10 at the stoichiometric
molar ratio (Mg:NH4:PO4:1/1/1). Furthermore, the
effect of the molar ratios of MAP constituents was
investigated while pH was kept constant as pH 9.0.
MAP experiments were performed in batch mode
using the efuent of MBR reactor. Experimental stud-
ies were carried out in 500 mL beakers using analyti-
cal grade magnesium chloride (MgCl2
6H2O) and so-
dium hydrogen phosphate (Na2HPO4
12H2O) as the
magnesium and phosphate source. The leachate solu-
tion was mixed for 3 min rapidly after adding the
magnesium and phosphate chemicals and pH adjust-
ment was made using 10.0 M NaOH. Following the
slow mixing for 10 min, the solution was precipitated
for 30 min to separate the MAP sludge from the bulk
liquid. Results of ammonium, phosphate, magnesium,
color and turbidity measurements, and settled sludge
volume were used to evaluate the efciency of the
MAP process.
Analytical Methods
The performance of each system was monitored
using the experimental analysis of COD, ammonium
(NH14 ), phosphorus, and turbidity. Measurement of
pH was carried out with Jenway Ion Electrode
(Model 3040). Biogas production was measured volu-
metrically using a wet-type Ritter 14724 Gerate-
nummer gas ow meter. Magnesium analyses were
performed using a Unicam Atomic Absorption Spec-
trophotometer (Unicam, Model No. 929A). All mea-
surements were conducted according to Standard
Methods [16].
RESULTS AND DISCUSSION
Characteristics of the Leachate
The leachate used throughout the study was col-
lected from the Odayeri Sanitary Landll located on
the European side of Istanbul. Table 1 shows the
composition of raw leachate used during the experi-
mental period. The COD concentration varied
between 5500 and 12,070 mg/L, and BOD5 values
ranged from 1250 to 5830 mg/L. The BOD5/COD
ratios ranging from 0.23 to 0.48 values indicate the
biodegradability for the medium-aged samples. When
comparing these values with those of young leachate,
it is seen that BOD5/COD ratios of the medium-aged
samples are lower. In fact, young landll leachates
80 April 2010 Environmental Progress & Sustainable Energy (Vol.29, No.1) DOI 10.1002/ep
Table 1. Characteristics of raw leachate used in the
study period.
Mean
Parameter Value range value Unit
COD 5,50012,070 9,134 mg/L
BOD5 1,2505,830 3,510 mg/L
BOD5/COD 0.230.48 0.38
TKN 2,2183,260 2,280 mg/L
NH4 2,0832,980 2,514 mg/L
Alkalinity 14,40017,120 15,920 mg CaCO3/L
Color 3,0205,540 4,013 Hazen
Turbidity 1,3203,840 2,428 NTU
pH 7.88.4 8
are characterized with high amounts of readily biode-
gradable organics and ratio of BOD5/COD is over 0.5
in the literature [1719]. However, the biodegradabil-
ity of the leachate reduces and ammonium concentra-
tion in leachate increases along with landll age. The
medium-aged leachate usually contains COD ranging
from 5000 to 10,000 mg/L and BOD5/COD is
between 0.1 and 0.5 [7, 2022].
Values in Table 1 indicated that the leachate was
relatively stable and well buffered with alkaline pH.
High concentrations of nitrogen compounds in leach-
ate ranged from 2083 to 2980 mg/L for NH1 4 and
2217 to 3260 mg/L for total Kjeldahl nitrogen (TKN),
respectively. NH1 4 was dominant among the nitrogen
concentrations and small differences between NH1 4
and TKN designate the scarcity of organic nitrogen
content in the raw leachate. These concentrations are
typical values given in the technical literature for the
characteristics of medium-aged leachate [6, 23, 24].
Anaerobic Treatment of Leachate
Raw leachate was anaerobically treated in the
UASB reactor. The operation duration of 120 days
during the treatment process was taken into account
in this study for evaluation. Inuent and efuent
COD concentrations of UASB reactor and the OLR as
a function of COD content of the raw leachate are
given in Figure 2. It is seen from this gure that dur-
ing the rst 50 days, organic loadings rates are rela-
tively high and variable. This situation can be
explained with variable COD concentrations which
resulted from raw leachate characterizations and cli-
mate conditions within those times.
During the rst 30 days, COD removal rates of
UASB reactor remained relatively low due to the high
organic loadings. However, performance of subse-
quent days was not adversely affected by variation of
organic loading, and COD removal rates changed lin-
early with the variation of inuent COD. This circum-
stance is clearly observed in Figure 3. For example,
the lowest removal efciency obtained was 32% for
the inuent COD of 5500 mg/L and as the COD of
raw leachate increased to 12,070 mg/L, the removal
efciency of COD in the UASB reactor reached a
maximum value of 71%. During the last 90-day pe-
riod for the performance of UASB reactor, the efuent
Figure 2. COD removal in the UASB reactor.
Figure 3. Comparing the COD removal performances
of reactors.
COD values were very similar although the inuent
COD values varied widely. A possible explanation for
these observations may be related to the degradation
of biodegradable organics by anaerobic microorgan-
isms. Similar results were observed for the anaerobi-
cal treatment of leachate elsewhere [24]. Over the
course of the experiment, COD removal efciencies
of UASB were changed between 32.2 and 71.0% and
average value occurred as 51.8%. This low COD re-
moval with the UASB reactor was due to the lower
rate of biodegradable material in the leachate, but it
is comparable with those reported for medium-age
leachate [23].
It can be seen in Figure 4 that the removal of am-
monium ion in the UASB reactor ranged from 3.8 to
14.2%, and the average efciency was  7.9%. In a
study, Kettunen et al. [25] observed low ammonium
reduction in the UASB reactor. In the same study,
they stated that this situation could be attributed to
utilization of NH1 4 through assimilation of anaerobic
bacteria. Further, Tuyluoglu [26] obtained 20% for
NH1 4 removal in the UASB reactor. Similarly, Agdag
and Sponza [24] obtained 1327% NH1 4 removal in
the UASB reactor, which was in good agreement with
the other studies.
Effect of MBR
The efuent of the UASB reactor was fed to the
MBR for the rst post treatment. The COD removal in
Environmental Progress & Sustainable Energy (Vol.29, No.1) DOI 10.1002/ep
Figure 4. Effect of membrane fouling on the COD
removal of MBR.
the MBR occurred in two different stages. The data in
Figure 3 shows that the MBR was very effective for
COD removal during the rst 30 days of operation.
After that the COD removal decreased. A higher re-
moval efciency in the earlier stage could be due to
the higher COD content of UASB efuent. The sec-
ond stage started after the 30 operational days, and
the COD removal efciency of the MBR decreased
gradually. Although the inuent COD of the MBR
remained constant in the second stage, the treatment
performance decreased linearly with the reduction
of permeate ux caused by membrane fouling (see
Figure 4).
Membrane fouling is the major obstacle for
decreasing of treatment efciency, and the phenom-
enon of the fouling mechanism is very complex and
difcult to understand because the MBR system
includes living microorganism and their metabolites.
Several investigators have reported that membrane
fouling occurring in MBR-activated sludge is attribut-
able to three aspects such as sludge particle deposi-
tion, adhesion of macromolecules to the membrane
surface, and pore clogging by small molecules. How-
ever, some agreement has been reached on the fact
that sludge particle deposition makes signicant
effect on membrane fouling in MBR system using
activated sludge [2730].
Comparing the performance of treatment systems
in terms of the individual and combined performan-
ces of the MBR indicates that the major part of the
COD was removed by the UASB reactor and integra-
tion of the MBR reduced variations and improved the
quality of the UASB efuent (see Figure 3). It is
observed that the COD removal efciency of both
systems varied between 39.5 and 82.1%, with an aver-
age value of 65.6%. Moreover, our results obtained in
this study show good performance comparable to
previous studies for the combined treatment of leach-
ate [31, 32]. The NH14 removal efciency of the MBR
alone remained 35.0% for the entire duration of the
experiment (see Figure 5). Integration of the MBR
increased total NH1 4 removal to between 32.7 and
50.4%, with an average value of 41.1%. The main
mechanism for NH1 4 removal was nitrication and a
slight reduction was maintained by stripping of
April 2010 81
Figure 5. Ammonium removal in the UASB and MBR
reactors.
Figure 6. Effect of pH on the removal of ammonium
in MAP.
gaseous ammonia due to vigorous aeration. Similar
results were reported in the technical literature for
the treatment of wastewater by MBR reactor [33, 34].
MAP Precipitation
The ammonium level of leachate decreased about
41.1% in the combined treatment of the UASB reactor
and MBR, and the residual concentration was about
1500 mg/L in the efuent. The MBR was inefcient
and the necessity of NH1 4 elimination from the leach-
ate entailed application of additional methods. There-
fore, MAP precipitation was used as a nal step to
decrease the ammonium ion in leachate efuent of
the UASB reactor and MBR.
The effect of pH on the MAP process was
investigated at the stoichiometric molar ratio
(Mg:NH4:PO4:1/1/1). It was observed that after add-
ing chemicals, MAP crystals rapidly formed and set-
tled quickly to the bottom of beakers. Solution pH
decreased from 9.2 to 5.9 and only 50% of the NH1 4 stoichiometric ratio to 38.2% at the maximum ratio
was removed without pH adjustment. To increase the
NH1 4 removal, the solution pH was adjusted between
8 and 10 using 10.0 M NaOH. Visible size of MAP
crystals and NH1 4 removal efciency were increased
rapidly after pH adjustment because MAP crystals are
82 April 2010 Environmental Progress & Sustainable Energy (Vol.29, No.1) DOI 10.1002/ep
Figure 7. Effect of molar ratios on the performance of
MAP.
highly insoluble at alkaline pH [35]. A maximum NH1 4
removal of 93.9% was obtained at pH of 9.0 whereas
the lowest removal efciency was 86.6% at pH of 8.0,
as shown in Figure 6. The optimum pH for ammo-
nium removal obtained in this study was in agree-
ment with other studies in literature [36].
To improve further the performance of MAP pre-
cipitation, the molar ratios of Mg and PO4 were
increased while the pH was kept at pH 9.0. Figure 7
shows the effect of the molar ratios as functions of
NH4, COD, color and turbidity removal, and settled
sludge volume. Increasing the magnesium and phos-
phate concentrations had a slight effect on the re-
moval of NH1 4 from the leachate. Ammonium re-
moval was enhanced in all cases and the maximum
efciency obtained was 96.6% at the molar ratio of 1/
1.2/1.2. Following MAP precipitation, the overall am-
monium removal efciency of the combined system
was achieved as 98.0%.
MAP precipitation also provided additional re-
moval of color, turbidity, and COD. Leachate color
decreased with the increasing of molar ratio and the
removal efciency increased from 18.5% at the stoi-
chiometric ratio to 22.5% at the ratio of 1/1.4/1.4.
Increasing of PO4 and Mg amounts slightly decreased
the turbidity and COD of the leachate solution. Maxi-
mum COD and turbidity removals obtained were 25.7
and 36.4%, respectively. However, Yangin et al. [37]
and Ozturk et al. [14] obtained about 50% COD re-
moval with MAP precipitation of anaerobically treated
leachate [24, 37]. Kapdasli et al. [38] stated that COD
removal in MAP process is due to the adsorption of
organics onto the surface of MAP crystals, so the dif-
ferences in the COD removal efciencies could be
attributed to the different physical properties of crys-
tals formed during MAP precipitation.
The effect of magnesium and phosphate addition
was observed on the volume of the settled MAP
sludge. Sludge volume increased from 15.6% at the
studied. Additional Mg and PO4 increased the sludge
volume and lowered NH41removal due to increasing
the size of MAP crystals and settling velocity. These
data show that MAP precipitation is very effective for
eliminating NH1 4 from leachate and provided further
COD and color removal from the leachate. The main
drawback to this approach is that chemicals used in
the MAP process are the main cost of the treatment
but economic value of MAP sludge will help to
reduce the costs.
CONCLUSION
To improve the treatment efciency of highly con-
centrated leachate, a combined post treatment of
MBR and MAP precipitation is applied to the anae-
robically pretreated efuent. During the anaerobic
treatment, COD removal of 51.8% and NH4 removal
of 7.9% were achieved by UASB reactor alone. Inte-
gration of MBR process reduced variations in the per-
formance of the UASB reactor, and COD and NH1
removal efciencies reached 65.6% and 40.1%,
respectively. MAP precipitation was applied as a nal
step to enhance the removal of ammonium and
96.6% of ammonium was treated successfully at opti-
mal pH and molar ratios. Moreover, MAP provided
further improvements in COD and turbidity removal.
The overall balance of treatment processes indicated
that total COD and NH4 removal efciencies of 74.4%
and 98.0%, respectively, achieved by the combined
system. Finally, integration of MBR and MAP precipi-
tation to the UASB reactor appears to be a promising
treatment to achieve a satisfactory efuent.
ACKNOWLEDGMENTS
This research has been supported by the Yildiz
Technical University Scientic Research Projects Coor-
dination Department. Project Number: 26-05-02-02.
The authors would also like to thank the ISTAC, Man-
agement Ofce of Odayeri Landll site for providing
the leachate samples.
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