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Enzyme and Microbial Technology 33 (2003) 588595

Aerobic biological treatment of pre-treated landfill


leachate by fed-batch operation
Fikret Kargi , M. Yunus Pamukoglu
Department of Environmental Engineering, Dokuz Eylul University, Izmir, Turkey
Received 17 December 2002; accepted 21 May 2003

Abstract
Landfill leachate obtained from the solid waste landfill area contained high chemical oxygen demand (COD) and ammonium ions which
resulted in low COD and ammonium removals by direct biological treatment. COD and ammonium ion contents of the leachate were
reduced to reasonable levels by chemical precipitation with lime and air stripping of ammonia. The pre-treated leachate was subjected to
aerobic biological treatment in an aeration tank by fed-batch operation. The effects of the feed wastewater COD content and flow rate on
COD and ammonium ions removal were investigated. Nearly 76% COD and 23% NH4 -N removals were obtained after 30 h of operation
with a flow rate of 0.21 l h1 and the feed COD content of 7000 mg COD l1 . COD removal efficiency decreased with increasing COD
loading rates. A kinetic model for COD removal was developed and the kinetic constants were determined by using the experimental data.
2003 Elsevier Inc. All rights reserved.
Keywords: Biological treatment; Fed-batch operation; Landfill leachate

1. Introduction
Treatment of municipal landfill leachates presents unique
problems from engineering point of view mainly because of
high chemical oxygen demand (COD) (600015,000 mg l1 )
and ammonium ion (5003000 mg l1 ) contents, high
COD/BOD ratio and also due to the presence of toxic
compounds such as metal ions [15]. Landfill leachate
management has been given significant attention in recent
years especially for municipal areas [110]. Composition
of the landfill leachates present variations depending on the
nature of the landfilled solid wastes, the active microbial
flora, characteristics of the soil, the rainfall patterns and the
age of the landfill [11]. Usually young landfill leachates
are treated more easily as compared to the old ones. Therefore, the leachate should be characterized before a suitable
treatment strategy was developed.
Usually a combination of physical, chemical and biological methods are used for effective treatment of landfill
leachate, since it is difficult to obtain satisfactory results
by using anyone of those methods alone. Sedimentation,
air stripping, adsorption, membrane filtration are the major
physical methods used for leachate treatment [5,6,12,14].
These methods are usually used in combination with chemi

Corresponding author. Tel.: +90-232-4531143; fax: +90-232-4531153.


E-mail address: fikret.kargi@deu.edu.tr (F. Kargi).

0141-0229/$ see front matter 2003 Elsevier Inc. All rights reserved.
doi:10.1016/S0141-0229(03)00187-X

cal and biological methods. Coagulationflocculation [5,10],


chemical precipitation [14,15], chemicalelectrochemical
oxidations [4,1618] are the major chemical methods used
for the landfill leachate treatment. Biological treatment
methods used for the leachate treatment can be classified as
aerobic, anaerobic and anoxic processes which are widely
used for the removal of biodegradable compounds. Physicochemical methods are used along with the biological
methods mainly to remove non-biodegradable compounds
from the leachate [6,9,10,13].
A number of physiochemical methods such as nanofiltration, air stripping and ozonation have been used for
COD, ammonium and toxicity removal by Marttinen et al.
[18]. Nearly, 66% COD and 50% ammonia were removed
by nanofiltration. Air stripping at pH = 11 resulted in
89% ammonia removal at 20 C within 24 h. Ozonation
increased the concentration of rapidly biodegradable COD.
However, none of the tested methods were effective in toxicity removal. Physicochemical methods have been used
in combination with nanofiltration for treatment of landfill
leachate by Trebouet et al. [13]. pH modifications and coagulation with FeCl3 have been tested to remove foulants
from the surface of the membranes. Nanofiltration has been
found satisfactory for removal of refractory COD from the
leachate used.
Ammonium removal from landfill leachate by chemical precipitation was investigated by Li and coworkers

F. Kargi, M.Y. Pamukoglu / Enzyme and Microbial Technology 33 (2003) 588595

[14,15]. Ammonium ions were precipitated as magnesium


ammoniumphosphate (MAP) with the addition of
MgCl2 6H2 O and Na2 HPO4 12H2 O with a Mg/NH4 /PO4
ratio of 1/1/1 at pH of 8.59. Ammonium ion concentration
was reduced from 5600 to 110 mg l1 within 15 min by this
method. Chemical oxidation methods have been applied
to biologically pre-treated landfill leachate by Steensen
[17]. Non-biodegradable compounds were removed by
H2 O2 /UV, ozone and ozone/fixed bed catalyst methods to
achive desired effluent water quality.
Pressure-driven membrane techniques have been applied
to biological treatment of landfill leachate [6]. Several
hybrid processes such as activated sludgechemical oxidation, activated sludgeultrafiltrationchemical oxidation
and activated sludgeultrafiltrationreverse osmosis have
been tested for landfill leachate treatment. Activated carbon
adsorption process has been used along with biological
treatment for effective treatment of landfill leachate [12].
Non-biodegradable organics, inert COD and the colour
have been reduced to acceptable levels by activated carbon
column treatment of biologically treated landfill leachate.
High COD content and high COD/BOD ratio of the landfill leachate make anaerobic treatment more advantageous as
compared to aerobic process. Anaerobic biological treatment
of landfill leachate has been studied by many investigators
[2024]. Up to 92% COD removals have been obtained by
using upflow anaerobic sludge blanket reactors [22]. Anaerobic and sequential anaerobicaerobic reactors have been
used for landfill leachate treatment at different temperatures
such as 11 and 24 C [23]. Nearly 75% COD removals have
been achieved by anaerobic treatment at 24 C with a 10-h
HRT. The overall COD removal in the sequential process
was 8090% with nearly 80% ammonium removal.
Aerobic biological treatment of landfill leachate has
been studied by using both suspension and biofilm cultures
[1,2,7,2629]. Maehlum [27] used on site anaerobicaerobic
lagoons and constructed wetlands for biological treatment
of landfill leachate. Overall N, P and Fe removals obtained
in this system were above 70% for diluted leachate. Aerobic treatment of domestic leachates in a sequencing batch
reactor (SBR) with a residence time of 2040 days resulted
in nearly 99% NH4 -N removal [1]. Combined treatment
of landfill leachate and domestic sewage was investigated
by using an SBR consisting of filling, anoxic, oxic and
settling phases [7]. When the ratio of sewage to leachate
was 9/1, nearly 95% BOD and 50% nitrogen removals have
been obtained at the end of the daily cycles. Loukidou
and Zouboulis [26] have used moving bed biofilm processes by using polyurethane and granular activated carbon
(GAC) support particles in an SBR reactor. Nearly complete
removal of nitrogen and satisfactory removals of COD,
colour and turbidity have been achieved. A combination of
anaerobicaerobic and rotating biological contact (RBC)
processes have been used for leachate treatment by Park
et al. [2]. The effluent of the RBC process was subjected to
flocculationsedimentation, adsorption and finally reverse

589

osmosis processes and nearly 98% of the organic materials


of low MW have been removed.
Autotrophic denitrification of landfill leachate by using
elemental sulfur packed bed columns have been achieved
by Koenig and Liu [25]. Nitrate ions produced in nitrification process have been removed effectively by using
Thibacillus denitrificans in the column reactor. Imai et al.
[19] used activated carbon fludized bed reactors for removal
of refractory organics from landfill leachate. Nearly, 60 and
70% refractory organics and nitrogen have been removed by
adsorption-coupled biological treatment in activated carbon
fludized beds.
Combined chemical and biological treatment of landfill
leachate has also been investigated. Geenens et al. [9] used
ozone pre-treatment before biological treatment of landfill
leachate in an activated sludge unit. COD/BOD ratio was
decreased from 16 to 6 by ozonation which improved the
efficiency of the activated sludge treatment. Coagulation
by FeCl3 and zeolite treatment for ammonium removal
before biological treatment have been shown to improve
biological treatability of landfill leachate by Ahn et al. [10].
Chemical precipitation of ammonium present in landfill
leachate by addition of MgCl2 and Na2 HPO4 and formation of magnesiumammoniumphosphate (MAP) has also
improved biological treatment efficiency [15].
In neither one of the reported studies as listed above, biological treatment of pre-treated landfill leachate has been
studied in a fed-batch reactor for COD and ammonium
removal.
Fed-batch operation is especially used for biological
treatment of high strength wastewaters containing refractory/toxic compounds in order to overcome inhibition effects by slow addition and therefore dilution of inhibitory
compounds and also by high density microbial cultures
developed in the aeration tank. Therefore, it is the major
objective of this study to investigate aerobic biological
treatment of the pre-treated landfill leachate by fed-batch
operation. Coagulationflocculation of inert organic compounds by lime followed by ammonia stripping by air
have been used to improve the biological treatability of the
leachate. Pre-treated leachate was subjected to aerobic biological treatment by fed-batch operation in an aeration tank.
Effects of feed flow rate, feed COD content or COD loading
rate on COD removal have been investigated. A mathematical model was developed and the kinetic constants were
determined by using the experimental data.

2. Theoretical background
Fed-batch operation of an aeration tank involves slow addition of highly concentrated wastewater (or nutrient media)
into aeration tank with no effluent removal until the tank is
full. Aeration tank contains small volume of highly active
and dense organisms at the beginning of the operation. High
strength wastewater containing toxic compounds is diluted

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F. Kargi, M.Y. Pamukoglu / Enzyme and Microbial Technology 33 (2003) 588595

inside the reactor by slow feeding resulting in less inhibition


and relatively high COD removal rates as compared to classical batch or continuous operations such as the activated
sludge process.
Fed-batch operation is different from SBR operation. High
COD content feed wastewater is added slowly or intermittently into the aeration tank without effluent removal in
fed-batch operation. However, filling, aeration, sedimentation and effluent removal phases are applied in sequence in
a batch-operated reactor in sequencing batch operation. Certain amount of sludge was removed from the reactor everyday to adjust the sludge age. Theory of fed-batch operation
is presented in many texts [30,31] and is briefly summarized
below.
As the feed wastewater is added slowly, the liquid volume
in the reactor increases with time linearly according to the
following equation since no effluent is removed.
V = V0 + Qt

(1)

When the system was operated with controlled addition


of the feed, the substrate (COD) concentration remains at a
low level in the tank which is called the Quasi Steady-State
at which approximately dS/dt = 0 and dX/dt = 0. At quasi
steady-state,
=D =

1
m S
=
H
Ks + S

(2)

or
S=

Ks D
m D

(2a)

where D is the dilution rate (Q/V = 1/ H ).


As a result of increase in reaction volume, dilution rate
(D = Q/V) decreases with time in this type of operation
resulting in a decrease in specific growth rate (). Biomass
concentration (X) remains almost constant; however, total
amount of biomass (XT = XV) in the reactor increases as a
function of time according to the following equation:
XT = XT0 +QY(S0 S)t

(3)

where Y is the growth yield coefficient (g X/g S), S0 is the


feed substrate (COD) concentration (g S l1 ) and Q is the
flow rate (l h1 ).

3. Materials and methods


3.1. Experimental set-up
A plexiglass aeration tank of 20 cm diameter and 60 cm
height with a total volume of 18.8 l was used throughout the
studies. Wastewater in the tank was aerated with the aid of
an air pump and diffusers. Wastewater was fed to the reactor
by using a peristaltic pump with adjusted flow rates varying
between 0.05 and 0.6 l h1 . Feed wastewater was kept in a
deep refrigerator at 4 C in order to avoid any decomposition.

3.2. Wastewater composition


The synthetic wastewater used throughout the studies was composed of pre-treated leachate and KH2 PO4 .
COD concentration in the feed was varied between 1000
and 7000 mg l1 by dilution of the pre-treated leachate.
NH4 -N was reduced to the desired level by air stripping at
pH = 12. Total nitrogen and phosphorous concentrations
in the feed wastewater were adjusted to yield COD/N/P =
100/10/1.5.
3.3. Organisms
Activated sludge culture was obtained from the wastewater treatment plant of PAK-MAYA Bakers Yeast Company
(Izmir, Turkey). The activated sludge culture was adapted
to the leachate by cultivating the organisms in the diluted
leachate in aeration tanks. Pre-adapted cultures were used
in experimental studies.
3.4. Experimental procedure
Pre-treatment of the leachate consisted of coagulation
sedimentation followed by air stripping of ammonia at
pH = 12. Coagulationsedimentation experiments were
conducted by using a jar-test apparatus. Different coagulants (FeCl3 , lime and alum) were added in desired concentrations into the raw leachate in 1 litre beakers. The
contents were mixed fast at 200 rpm for 2 min followed by
a slow mixing at 20 rpm for about 30 min and were sedimented for about 1 h. The effluent of the flocculation step
was subjected to air stripping of ammonia at pH = 12 for a
desired period to adjust ammonium concentration to desired
level.
Biological treatment experiments were started batch wise.
About 5 l of pre-treated and diluted leachate was placed in
the aeration tank and inoculated with the activated sludge
culture pre-adapted to the leachate. The reactor content was
aerated for several days to obtain a dense culture. At the end
of batch operation, the organisms were sedimented, 2 litres
of the supernatant was withdrawn and continuous feeding
of the medium was started without any effluent removal.
Temperature, pH and dissolved oxygen (DO) of the medium
during operation were T = 20 2 C, pH = 8.2 0.3
and DO = 3 0.5 mg l1 , respectively. The reactor liquid
volume increased linearly with time depending on the flow
rate. Experiments continued for 30 h and were run twice to
test the reproducibility of the results. Since the results of the
replicates were almost the same, no further replicates were
run. Control experiments devoid of organisms were run under the same conditions for each experiment. Control experiment COD contents were used as the base for calculation of
COD removals in order to compensate for COD changes because of dilution in the aeration tank. In other words, percent
COD removals in the control experiment were considered
to be zero.

F. Kargi, M.Y. Pamukoglu / Enzyme and Microbial Technology 33 (2003) 588595

Percent COD removal

3.5. Analytical methods


Samples removed from the experimental and the control
reactors every hour were centrifuged at 6000 rpm for 30 min.
COD analyses were carried out on clear supernatants according to Standard Methods by using the closed reflux method
[32]. Ammonium ion concentrations were determined by
using the test kits (Merck spectroquant 14752) and a spectrometer.
Biomass concentrations were determined by filtering the
samples through 0.45-m Millipore filter and drying in an
oven at 105 C until constant weight. DO measurements
were made by using a WTW DO Analyser and a DO probe.

591

65
60
55
50
45
40
35
30
0.5

1.5

2.5

3.5

-1

Coagulant dose ( g l )
Fig. 1. COD removal efficiencies from landfill leachate for different
coagulating agents and concentrations. FeCl3 (); alum (); lime ().

4. Results and discussion


Percent COD removals increased with increasing coagulant
doses for alum and ferric chloride. However, COD removal
with lime addition decreased with the increasing lime dose.
The highest COD removal (60%) was obtained with 3 g l1
ferric chloride addition. COD removal performances of the
three coagulants at low doses (0.51.0 g l1 ) were comparable. Considering the problems associated with the use of
high coagulant doses such as more sludge formation and
high cost of coagulation, low doses of coagulants such as
1 g l1 were preferred. Percent COD removals for the three
coagulants at the dose of 1 g l1 were almost the same as
45%. Since lime coagulation was realized at pH = 12 which
was the most suitable pH for air stripping of ammonia used
after the coagulation and also because of limes disinfection affects, lime was selected as the most suitable coagulant for use in further studies. COD and NH4 -N contents of
the leachate dropped from COD0 = 9500 and NH4 -N0 =
1250 mg l1 to COD = 7200 and NH4 -N = 1200 mg l1 ,
respectively, after coagulation with 1 g l1 lime addition.
Supernatant solution after coagulation at pH = 12 with
lime of 1 g l1 dose was subjected to air stripping at pH = 12
to remove excess ammonia from the leachate. Ammonium
concentration after 45 min of air stripping was reduced to
nearly 700 mg l1 from 1250 mg l1 . The pH of the leachate
was adjusted to pH = 7 by alkaline addition (1 M NaOH)
after air stripping of ammonia and was used for biological
treatment in an aeration tank operated in fed-batch mode.
COD and NH4 -N contents of the pre-treated leachate after
air stripping were approximately 7000 and 700 mg l1 , respectively. Required amount of KH2 PO4 was added to the
pre-treated leachate to adjust COD/N/P ratio to 100/10/1.5,
before biological treatment.

4.1. Characterization of the landfill leachate


Typical composition of the landfill leachate obtained from
the Harmandali Landfill area in Izmir, Turkey is presented
in Table 1.
TOC/COD ratio in the leachate was nearly 0.4,
which is in agreement with the theoretical predictions.
COD/NH4 -N/PO4 -P ratio in the raw leachate was 100/13.4/
0.32 indicating high NH4 -N and low PO4 -P content. Since
COD/N/P ratio should be around 100/6/1.5 for the effective
biological treatment of wastewater, part of the ammonium
was removed by air stripping and extra PO4 -P was added
to the leachate for nutrient balancing in the experimental
studies.
4.2. Pre-treatment of the landfill leachate
Early biological treatment studies with the raw leachate
did not yield high COD and nitrogen removals, for this reason the leachate was subjected to pre-treatment by chemical coagulationflocculation followed by air stripping of
ammonia at pH = 12. Three different chemical coagulants, alum (Al2 (SO4 )3 ), FeCl3 and lime (CaO) were used
in different concentrations for COD and nitrogen removal
by coagulationflocculation.
The procedure used in coagulationflocculation experiments is presented in Section 3. The pH of the leachate was
adjusted to 6 for alum and ferric chloride and 12 for lime
addition. Concentrations of the coagulants varied between
0 and 3.5 g l1 . Fig. 1 shows COD removal efficiency as a
function of coagulant doses for the three coagulants tested.
Table 1
Characteristics of the landfill leachate used in experimental studies
Parameter
Concentration

(mg1 )

pH

COD

TOC

TN

NH4 -N

NO3 -N

TP

PO4 -P

TSS

Ni

Zn

Cu

Cr

8.15

9500

3750

1450

1270

7.3

33

31

21000

0.066

0.160

0.665

0.191

TN: total nitrogen; TP: total phosphorous; TSS: total suspended solids; TOC: total organic carbon; COD: chemical oxygen demand.

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F. Kargi, M.Y. Pamukoglu / Enzyme and Microbial Technology 33 (2003) 588595

4.3. Fed-batch biological treatment of the pre-treated


landfill leachate

iments were used as the base in calculation of COD removal


efficiencies.

Two sets of experiments were performed for the fed-batch


biological treatment of the pre-treated landfill leachate. The
landfill leachate was diluted with tap water to reduce the
COD contents to the desired level. In the first set of experiments, the feed flow rate was kept constant at Q =
0.18 l h1 and COD content of the feed was varied between
1000 and 7000 mg l1 . The COD loading rate (LCOD ) varied
between 180 and 1260 mg COD h1 with 30 h of operation
time, in this set of experiments. The COD content of the feed
wastewater was kept constant at approximately 7000 mg l1 ,
while the flow rate of the feed was varied between 0.05
and 0.6 l h1 , in the second set of experiments. The COD
loading rate varied between 350 and 4200 mg COD h1 with
10 h of operation time, in this set of experiments. The initial COD and biomass concentrations in the aeration tank
were nearly 300 mg l1 and 4200 200 mg biomass l1 , respectively. Vigorous aeration was supplied to the aeration
tank to keep the DO above 2 mg l1 . Simultaneous control
experiments devoid of microorganisms were run under the
same conditions as that of the biological treatment experiments. Percent COD removal in control experiments were
considered to be zero and COD content of the control exper-

4.3.1. Effect of feed COD concentration


Fig. 2 depicts typical variations of important process
variables with time for an experiment with the feed COD of
4170 mg l1 and the feed flow rate of 0.18 l h1 . Wastewater volume in the tank increased with time linearly as
expected. COD concentration in the control tank increased
with time due to accumulation of COD in the absence of
organisms. However, COD in the experimental tank increased slightly and remained constant at approximately
500 mg l1 throughout the experiment as a result of COD
removal by bio-oxidation. Percent COD removal based on
the difference in COD concentrations in the control and
the experimental tanks increased with time as a result of
increases in total biomass in the aeration tank. Total amount
of biomass also increased linearly with time as expected
theoretically.
Variation of percent COD removals with time are depicted in Fig. 3 for different feed COD contents while the
feed flow rate was constant. Percent COD removals were
calculated by using the control experiments COD contents
as the reference (ECOD = 1 CODe /CODc ). COD removal
efficiencies increased with time as shown in Fig. 3 for all

2800

8
2300
CODe ( mg l-1 )

Vt ( l )

7
6
5
4

1800
1300
800

3
300

2
0

10

20

25

30

Time ( h )

(a)

10

15

20

25

30

Time ( h )

80

26

70

24

60
22

50
40
30

20
18

20
16

10

14

0
0

(c)

(b)

Xt ( g )

Percent COD removal

15

10

15
Time ( h )

20

25

30

(d)

10

15

20

25

30

Time ( h )

Fig. 2. Variation of process variables with time in fed-batch treatment of landfill leachate for the feed COD0 of 4170 mg l1 and feed flow rate of
0.18 l h1 . (a) Wastewater volume in tank; (b) COD concentration: control (), experimental (); (c) percent COD removal; (d) total biomass in tank.

F. Kargi, M.Y. Pamukoglu / Enzyme and Microbial Technology 33 (2003) 588595

593

80

Percent COD removal

70
60
50
40
30
20
10
0
0

12

15

18

21

24

27

30

Time ( h )
Fig. 3. Variation of percent COD removals with time for different feed COD concentrations with the feed flow rate of 0.18 l h1 . Symbols for different
feed CODs are () 980 mg l1 , () 2800 mg l1 , () 5100 mg l1 , () 7050 mg l1 .

experiments. Final COD removals obtained at the end of


30 h of operation also increased with increasing feed COD
and levelled off at E = 0.76 for high feed COD contents
such as 7000 mg l1 . High COD removal efficiencies of
nearly 76% obtained with the high feed COD contents can
be attributed to high biomass concentrations in the aeration
tank when the feed COD was high.
Percent NH4 -N removals also varied with the feed NH4 -N
contents or NH4 -N loading rates. At low feed NH4 -N contents (200 mg l1 ), the removals were around 24% which
decreased to 18% at high feed NH4 -N levels (490 mg l1 ).
4.3.2. Effect of feed flow and COD loading rate
COD loading rate was varied by varying both the feed
COD and the feed flow rate. The effects of COD and NH4 -N
loading rates (Ls = QSo ) on the final COD levels and COD
removal efficiencies are depicted in Fig. 4. Final COD content in the aeration tank at the end of operation increased
while percent COD removals (E) decreased with the increasing COD loading rates. At low COD loading rates, the
effluent COD levels increased and percent COD removals
decreased more steeply. However, changes in both parameters slowed down at high COD loadings and levelled off
at COD loadings above 3.5 g COD h1 . In order to achieve
COD removal efficiencies above 75%, COD loading rate
should be kept below 1 g COD h1 .
Similarly, effluent NH4 -N concentrations at the end of
operation increased and percent removals decreased with
increasing NH4 -N loading rate. Changes in those parameters
with the NH4 -N loading rate were steeper at low loading

rates and slowed down as the loading rate increased. Percent


NH4 -N removals decreased from 26 to 18% as the NH4 -N
loading rate increased from 35 to 420 mg N h1 .
4.4. Kinetic analysis of the system
The following kinetic model was used in the analysis of
data obtained at the end of 30 h of operation which was
assumed to be the quasi steady-state as seen from the Figs. 2
and 3.
Rs =

Q(Si S)
kXS
Rm S
=
=
V0 + Qt
Ks + S
Ks + S

(4)

where, Q is the feed flow rate (l h1 ); Si is the feed COD


concentration (mg l1 ); S is the actual COD content in the
tank after 30 h of operation (mg l1 ); V0 is the initial wastewater volume in the tank (3 l); t is the operating time (h); k
is the maximum COD removal rate constant (h1 ); X is the
biomass concentration in the aeration tank at any time during
operation (mg l1 ); Ks is the saturation constant (mg l1 ) and
Rm is the maximum rate of COD removal (mg COD l1 h1 )
which is equal to kX.
In double reciprocal form, the Eq. (4) takes the following
form,
1
(V0 + Qt)
1
Ks 1
=
=
+
Rs
Q(Si S)
Rm
Rm S

(5)

A double reciprocal plot of 1/Rs versus 1/S yields a line


with a slope of Ks /Rm and and intercept of 1/Rm .

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F. Kargi, M.Y. Pamukoglu / Enzyme and Microbial Technology 33 (2003) 588595

1600

77
76
75
74

1200

73
1000

72
71

800

70
69

600

Percent COD removal

CODe ( mg l -1 )

1400

68
400
300

67
800

1300

1800

2300

2800

3300

3800

LCOD ( mg h-1 )

(a)

27
400

NH4-Ne ( mg l -1 )

25
350

24
23

300

22
21

250

20
19

200

Percent NH 4-N Removal

26

18
150

17
30

80

130

180

230

280

330

380

LNH 4-N ( mg h-1 )

(b)

Fig. 4. Variations of the effluent concentrations and percent removals for COD and NH4 -N at the end of the operation with COD and NH4 -N loading
rates. (a) COD; (b) NH4 -N: effluent COD or NH4 -N (), percent COD or NH4 -N removal ().

Experimental data with variable feed COD obtained at


the end of 30 h of operation (i.e. at the quasi steady-state)
were plotted in form of 1/Rs versus 1/S as shown in Fig.
5. From the slope and the intercept of the best-fit line, the

Rm = 82 mg COD l1 h1 , Ks = 380 mg l1 (r 2 = 0.90)


By using the equation of Rm = kX and considering the
average biomass concentration in the aeration tank as X =
2200 mg l1 , the rate constant was found to be in the order
of k = 0.037 h1 = 0.895 per day for the biological system
used. The rate constant (k) was found to be lower and the
saturation constant (Ks ) higher than those of the conventional
activated sludge systems probably due to the presence of
inhibitory compounds present in the leachate used.

28
26
1/Rs*103 ( L h mg-1)

following approximate values were found for the kinetic


constants:

24
22
20
18

y= 4.614x + 12.241

16

R = 0.9043

5. Conclusions

14
7.0

1.2

1.7

2.2
3

2.7

3.2

-1

1/Se*10 ( L mg )
Fig. 5. Double reciprocal plot of 1/Rs vs. 1/S at the quasi steady-state for
determination of kinetic constants for COD removal.

Due to high COD and NH4 -N content, direct biological


treatment of landfill leachate is usually realized with low
COD removals. In order to reduce the COD and NH4 -N
contents to the treatable levels, the landfill leachate was sub-

F. Kargi, M.Y. Pamukoglu / Enzyme and Microbial Technology 33 (2003) 588595

jected to preliminary treatment by coagulationflocculation


and air stripping of ammonia. COD and NH4 -N contents
of the leachate was reduced to nearly 7000 and 700 mg l1 ,
respectively, by coagulation with lime followed by air stripping of ammonia at pH = 12.
Pre-treated leachate was biologically treated in an aeration
tank by fed-batch operation. The effects of the feed COD
content (S0 ), feed flow rate (Q) and COD loading rate on
COD removals were investigated. COD removal efficiency
(E) decreased and the final COD levels in the tank increased
with the increasing feed COD content or COD loading rate.
Increasing COD loading rates (LCOD = QS0 ) resulted in
decreases in final COD removals. The system should be operated at COD loading rates of below 1 g COD h1 in order
to obtain high percent COD removals after 30 h of operation. Percent COD removals of 76% and NH4 -N removals
of nearly 23% were obtained by fed-batch biological treatment of pre-treated leachate.
Kinetic constants of the system were determined by using the quasi steady-state experimental data obtained at the
end of 30 h of operation and the following values were determined for the k and Ks :
Rm = 82 mg COD l1 h1 , k = 0.037 h1 = 0.895 per day,
Ks = 380 mg l1

Acknowledgments
This study was partly supported by the research funds of
Suleyman Demirel University in Isparta and Dokuz Eylul
University in Izmir, Turkey.
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