Chemosphere 59 (2005) 871–879

www.elsevier.com/locate/chemosphere

Effect of alkalinity on the performance of a simulated

landfill bioreactor digesting organic solid wastes
Osman Nuri Ağdağ, Delia Teresa Sponza *

Department of Environmental Engineering, Engineering Faculty, Dokuz Eylül University, Buca Kaynaklar Campus,
Tınaztepe-Izmir 35160, Turkey

Received 1 March 2004; received in revised form 27 October 2004; accepted 17 November 2004

Abstract

This study investigated the effects of alkalinity on the anaerobic treatment of the organic solid wastes collected from
_
the kitchen of Engineering Faculty in Dokuz Eylül University, Izmir, Turkey and the leachate characteristics treated in
three simulated landfill anaerobic bioreactors. All of the reactors were operated with leachate recirculation. One reactor
was operated without alkalinity addition. The second reactor was operated by the addition of 3 g l 1 d 1 of NaHCO3
alkalinity to the leachate and the third reactor was operated by the addition of 6 g l 1 d 1 NaHCO3 alkalinity to the
leachate. After 65 d of anaerobic incubation, it was observed that the chemical oxygen demand (COD), volatile fatty
acids (VFA) concentrations, and biochemical oxygen demand to chemical oxygen demand (BOD5/COD) ratios in the
leachate samples produced from the alkalinity added reactors were lower than the control reactor while the pH values
were higher than the control reactor. The COD values were measured as 18 900, 3800 and 2900 mg l 1 while the VFA
concentrations were 6900, 1400 and 1290 mg l 1, respectively, in the leachate samples of the control, and reactors con-
taining 3 g l 1 NaHCO3 and 6 g l 1 NaHCO3 after 65 d of anaerobic incubation. The total nitrogen (TN), total phos-
phorus (TP) and ammonium nitrogen (NH4-N) concentrations in organic solid waste (OSW) significantly reduced in the
reactor containing 6 g l 1 NaHCO3 by d 65. The values of pH were 6.54, 7.19 and 7.31, after 65 d of anaerobic incu-
bation, respectively, in the aforementioned reactors results in neutral environmental conditions in alkalinity added reac-
tors. Methane percentage of the control, reactors containing 3 g l 1 NaHCO3 and 6 g l 1 NaHCO3 were 37%, 64% and
65%, respectively, after 65 d of incubation. BOD5/COD ratios of 0.27 and 0.25 were achieved in the 3 and 6 g l 1
NaHCO3 containing reactors, indicating a better OSW stabilization. Alkalinity addition reduced the waste quantity,
the organic content of the solid waste and the biodegradation time.
Ó 2004 Elsevier Ltd. All rights reserved.

Keywords: Organic solid waste; Bioreactor; Anaerobic treatment; Leachate recirculation; Alkalinity addition

1. Introduction

*
Corresponding author. Tel.: +90 232 453 1008; fax: +90
232 453 1153.
E-mail addresses: o.agdag@deu.edu.tr (O.N. Ağdağ),
delya.sponza@deu.edu.tr (D.T. Sponza).
The bioreactor landfill provides a similar approach
and treatment to that utilized in organic solid waste
digestion. Factors affecting the treatment efficiency of
municipal solid waste (MSW) in bioreactors are leachate

0045-6535/$ - see front matter Ó 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.chemosphere.2004.11.017
872 O.N. Ağdağ, D.T. Sponza / Chemosphere 59 (2005) 871–879
recirculation, recirculation volume, waste shredding,
waste compaction, pH adjustment, aeration, and nutri-
ent and alkalinity additions (Reinhart et al., 2002).
The alkalinity of water is a measure of its capacity to
neutralize acids and is due primarily to the salts of weak
acids (Quasim and Chiang, 1994). If the acid concentra-
tions (H2CO3 and VFA) exceed the available alkalinity,
the landfilling bioreactor will ‘‘sour’’. This will be se-
verely inhibiting the microbial activity, especially the
methanogens. When methane production becomes
ceases the VFA may continue to accumulate. Methano-
gens prefer nearly neutral pH conditions with a gener-
ally accepted optimum range of approximately 6.5–8.2
(Anderson and Yang, 1992; Speece, 1996).
The continuous hydrolysis of solid waste, followed
by the microbial conversion of biodegradable organic
content resulting in the production of intermediate
VFAs at high concentrations. In the methane fermenta-
tion phase, the pH value is elevated, being controlled by
the bicarbonate buffering system (Reinhart and Al-You-
sfi, 1996). A balance between acid production and acid
consumption is essential for a stable anaerobic process
running at the highest possible rate. Plaza et al. (1996)
showed that, pH was controlled by the addition of so-
dium bicarbonate as a buffer at a minimum buffer/sub-
strate ratio of 0.06 kg kg 1 TS. Adequate alkalinity, or
buffer capacity, is necessary to maintain a stable pH in
the digester for optimal biological activity (Cobb and
Hill, 1990). An alkalinity level ranging from 1000 to
5000 mg CaCO3 l 1 was recommended by Tchobanog-
lous and Burton (1979). Alkaline pretreatment in the
anaerobic digestion of co-mingled municipal solid waste
significantly increases the biodegradability of the waste
mixture (Hamzawi et al., 1998).
Limited studies have been performed investigating
the effect of alkalinity on the anaerobic treatment of
the organic solid waste (OSW) in bioreactors. In the
study realized by Warith (2002) it was shown that the
highest pH was observed in the sludge added reactor
and a highly reduced COD was observed in the pH buf-
fered and nutrient added reactor. The study carried out
by San and Onay (2001) showed that a four times per
week recirculation strategy with a pH control provided
the highest degree of stabilization. Dinamarca et al.
(2003) studied the influence of pH on the anaerobic
digestion of the organic fraction of the urban solid waste
Table 1
Operating protocol for simulated landfill bioreactors in alkalinity study
1 1
Control reactor 3gl
Quantity of waste (g) 1000 1000
Recirculation vol. (ml d 1) 300 300
Alk. addition (NaHCO3) No 3 6
Operation time (d) 65 65
in a two phase anaerobic reactor. The higher degrada-
tion of total suspended solid (TSS) and volatile sus-
pended solid (VSS) were obtained in the reactors
operated at pH 7 and 8.
The effect of alkalinity addition has not been well re-
ported for simulated landfill anaerobic reactors treating
OSW in literature. This paper reports the results of an
examination of a landfill simulated anaerobic reactor
treating OSW at varying NaHCO3 alkalinity. The influ-
ence of bicarbonate alkalinity on leachate characteristics
and on the degradation of OSW was investigated.
2. Materials and methods
2.1. Lab-scale simulated landfill bioreactor
To treat the municipal solid wastes and to collect the
biogas, stainless-steel cylindrical bioreactors with a
10 cm diameter and 30 cm in height were constructed.
These bioreactors were operated in batch mode at a tem-
perature of 35–40 °C under anaerobic conditions. The
leachate was collected at the bottom section of the solid
waste reactor and the effluent was recycled to the top of
the reactor with a peristaltic pump. There were three
separate ports on the top of the reactor for the addition
of simulated rain water, measurement of the methane,
total gas productions, percentage of methane and for
recirculation of the leachate.
2.2. Operating conditions for simulated anaerobic
landfill reactors
All the reactors were loaded with solid waste but with
different operational modes. The first reactor was oper-
ated with leachate recirculation (control-no alkalinity
addition), the second reactor was operated with recircu-
lation 3 g l 1 NaHCO3 alkalinity was added and the
third was operated with leachate recirculation and
6 g l 1 NaHCO3 alkalinity was added. Fifty milliliters
of anaerobic sludge was added to all the reactors and
mixed in order to provide methanogenic conditions.
Approximately 20 ml of NaHCO3 was added on the
top of the reactors daily. Table 1 shows the operating
protocol for the all reactors. The organic solid wastes
alkalinity added reactor 6gl alkalinity added reactor
1000
300
65
 O.N. Ağdağ, D.T. Sponza / Chemosphere 59 (2005) 871–879 873

collected were from the kitchen of the Engineering Fac- 50000

ulty in Dokuz Eylül University Campus. (a)
40000

COD conc. (mg.l-1)

2.3. Analytical procedure 30000

20000
Organic matters, water content in OSWs were mea-
10000
sured by the method proposed by Kocasoy (1994). Car-
bon (C) in OSWs was measured following the method 0
developed by Sorgun (1987). The COD concentrations
25000
in leachate samples were detected by using closed reflux
(b)
colorimetric method following standard methods 20000

VFA conc. (mg.l -1)

(APHA, 1992). BOD5 in leachate samples was measured
15000
using the WTW Oxi Top IS 12 system. TN, TP in OSWs
were measured using spectroquant kits numbered 14 537, 10000

14 543 in a photometer Merck SQ 300 after OSW was 5000

dried at 100 °C and crashed. In this process 20 g of
0
OSW was mixed with 200 ml distilled water and was
kept through 48 h in distilled water (USEPA, 1986). 8
Ammonia-nitrogen in leachate samples was measured 7
using spectroquant kit numbered 14 752 in a photometer 6
Merck SQ 300. The pH in leachate samples was deter- 5
mined immediately after sampling to avoid any change
pH

4
due to CO2 stripping, using a pH meter, type NEL pH 3

890. Total volatile fatty acid (TVFA) concentrations in 2

1 (c)
the leachate samples were measured using Anderson
0
and Yang (1992) method. Gas productions were mea-
sured by liquid displacement method. Total gas was 1000
Ammonium conc. (mg.l -1)

measured by passing it through a liquid containing 2%

800
(v/v) H2SO4 and 10% (w/v) NaCl (Beydilli et al.,
1998). Methane gas was detected using a liquid solution 600

containing 3% NaOH (w/v) (Razo-Flores et al., 1997). 400

Methane percentage was monitored with a digital meth- 200
ane meter (Drager Pac Ex). (d)
0
0 10 20 30 40 50 60 70
Operation time (d)
3. Results and discussion
Fig. 1. Trends in COD, VFA, pH and NH4-N concentrations
3.1. COD variations in leachate samples produced from (a–d) in leachate from the control (—d—), 3 g l 1 (—m—) and
the control and alkalinity supplemented simulated 6 g l 1 (——) NaHCO3 containing reactors.
landfill bioreactors

The initial COD concentration in leachate samples
collected from the control, and reactors containing
3 g l 1 and 6 g l 1 NaHCO3 were approximately
16 000 mg l 1, respectively (Fig. 1a). The COD value of
the leachate in the control reactor increased to 40 700
mg l 1 until d 21, and then started to decrease. The
COD values of the leachate taken from the 3 g l 1 and
6 g l 1 NaHCO3 containing reactors increased to
30 000 and 23 000 mg l 1 until d 7. After d 7, the COD
concentrations in these reactors started to decrease.
The reason for this decrease in COD level may possibly
have been the quick degradation of solid wastes in the
lab-scale anaerobic OSW reactor and the positive effect
of alkalinity on anaerobic degradation. The COD values
of the leachate from the control, and reactors containing
3 g l 1 and 6 g l 1 NaHCO3 were approximately 19 000,
3900 and 3000 mg l 1 respectively, on d 65 (Appendix
A). This indicates that the addition of alkalinity to the
solid waste bioreactors has a positive effect on the anaer-
obic degradation of organic solid wastes. The organic
matter easily converts to methane through the methano-
genesis. However, the degradation process occurred
slowly in the control reactor, because of unsuitable alka-
linity for methanogen bacteria. The time required for
stabilization of COD was shortened by the addition of
alkalinity.
Inadequate alkalinity/leachate COD ratio in the
anaerobic reactors may cause minimum pH in the anaer-
obic reactor to fall below 6.2 which can lead to failure
of the system. Speece (1996) and Anderson and Yang
874 O.N. Ağdağ, D.T. Sponza / Chemosphere 59 (2005) 871–879
(1992) reported that if the acid concentrations exceed the
available alkalinity, a drop in pH could occurs, When
methane production becomes ceases the VFA may con-
tinue to accumulate. Methanogens prefer nearly neutral
pH conditions with a generally accepted optimum
range of approximately 6.5–8.2. Alkalinity addition
was used in numerous studies to neutralize the pH the
anaerobic treatment of MSW (San and Onay, 2001;
Warith, 2002).
Souza et al. (1992) and Moosbruger et al. (1993)
found that an alkalinity/COD ratio 0.5 in the influent
decreased the pH to 6.6, which is considered as the lower
limit value recommended for anaerobic digestion pro-
cesses. In our study, these ratios were 0.22, 0.98 and
1.3 in the control, 3 g l 1 and 6 g l 1 NaHCO3 supple-
mented reactors, respectively. Since 6 g l 1 of NaHCO3
concentration provided an optimum buffering capacity
to convert effectively the leachate COD to methane
and VFA, it could be suggested as an optimum bicar-
bonate alkalinity concentration in influent to maintain
the pH above 6.6. This value corresponds to an Alk./
COD ratio of 1.3 for optimum operation which is higher
than the ratio proposed by Gonzales et al. (1998) (0.4),
Souza et al. (1992) and Moosbruger et al. (1993) (0.5)
and Speece (1996) (1.2).
3.2. VFA variations in leachate samples produced from
the control, 3 g l 1 and 6 g l 1 NaHCO3 alkalinity
supplemented reactors
The initial VFA concentrations in leachate samples
were approximately 10 000 mg l 1 in all reactors (Fig.
1b). A strong linear correlation between COD and
VFA concentrations was obtained in all reactors (r =
0.96, 086, and 0.85 in control and reactors containing
3 g l 1 and 6 g l 1 NaHCO3). The VFA values of the
reactors containing 3 g l 1 and 6 g l 1 NaHCO3 in-
creased to 30 000 and 23 000 mg l 1 on d 7. However,
they were down to about 1400 and 1300 mg l 1 by d
65 (Appendix A). The VFA measurements showed that
organic solid wastes in control reactor (no alkalinity
addition) degraded slowly.
Adequate alkalinity, or buffer capacity, is necessary
to maintain a stable pH in the digester for optimal bio-
logical activity (Cobb and Hill, 1990). An alkalinity
varying between 1000 and 5000 mg CaCO3 l 1, was rec-
ommended for anaerobic treatment depending on COD
and VFA produced (Tchobanoglous and Burton, 1979).
Traditionally, the total alkalinity in an anaerobic diges-
ter includes all the bicarbonate alkalinity and approxi-
mately 80% of the VFA (Anderson and Yang, 1992).
When the system is in balance, the methanogens could
be inactivated by unfavorable environmental conditions,
e.g., pH drop, accumulation of VFA, intermetabolites
and toxicity of aromatic amines due to their toxic prop-
erties (Kuai et al., 1998).
Behling et al. (1997) reported that, if an UASB reac-
tor is stable, the TVFA/B.Alk. ratio should be between
0.4 and 0.8. In our study, TVFA/B.Alk. ratios were
3.00, 1.20, 1.00, 0.70 and 0.50 on d 5, 28, 31, 65 and
100 in control reactor. TVFA/B.Alk. ratios were 2.00,
0.70, 0.30, 0.40, 0.40 and 0.50 on d 5, 28, 31, 52, 65
and 100 in reactor containing 3 g l 1 NaHCO3 while
the same ratios were 1.50, 1.10, 0.30, 0.40, 0.60 and
0.50 in reactor containing 6 g l 1 NaHCO3 on the afore-
mentioned d. The low TVFA/B.Alk. ratios could be
attributed to the deficient of B. alkalinity on d 31 and
52 in reactors containing 3 g l 1 and 6 g l 1 NaHCO3.
The B. Alk. neutralize the CO2/H2CO3 with only the ex-
cess available for neutralizing an increase in VFA.
3.3. pH variations in leachate samples produced from
the control, 3 g l 1 and 6 g l 1 NaHCO3 alkalinity
supplemented reactors
During the first two weeks, the pH of the leachates
from the control, and reactors containing 3 g l 1 and
6 g l 1 NaHCO3 were approximately 5.30, respectively,
on the acidic side of the pH scale (Fig. 1c). In the control
reactor, the pH values decreased to 5 within 7 d. This
caused an the extension of the time required for the sta-
bilization of organic fraction of the waste to stabilize
since methane forming anaerobes are known to be very
sensitive to low pH (Bolzonella et al., 2003). The meth-
ane gas productions were 3900, 5900 and 6900 ml d 1 on
d 5 (see Fig. 2a–c). The methane gas productions at a pH
as low as 5 could be attributed to hydrogenotrrophic
methanogens present in OSWs (Paulo et al., 2003).
The so-called ‘‘acid habituation’’ or the ‘‘adaptive acid
tolerance response’’ phenomenon, described by Hall
et al. (1995) might explain the resistance of anaerobic
microorganisms in OSWs. Lens et al. (2003) found that
the lack of bicarbonate delayed the conversion of OSWs
to methane resulting in low methane productions and
percentages in control reactor. The other reason for
methane production at pH 5 in control reactor could
be attributed to ammonium bicarbonate alkalinity
which in turn maintained a pH close to neutral inside
cells (Speece, 1996). This called ‘‘metabolism generated
alkalinity’’ inside cells. The degradation of cation releas-
ing nitrogenous organics (proteins) would double the
alkalinity concentration generated during biodegrada-
tion of proteins in OSWs (Speece, 1996). On the other
hand, VFA alkalinity contributes to the buffering of
H2CO3, but is transient since the VFA varies and there-
fore cannot be consistently relied upon. The pH level of
the control reactor was 6.54 on d 65 (Appendix A). The
conversion of fatty acids caused an increase in the pH
levels within the alkalinity supplemented reactors. In
this study the measured pH levels was found to be higher
than the data obtained by Plaza et al. (1996) which used
CaCO3 for alkalinity.
 O.N. Ağdağ, D.T. Sponza / Chemosphere 59 (2005) 871–879 875

18000 70 nitrogenous organic substances could be attributed to

16000 ammonium bicarbonate alkalinity, which in turn main-
Cumulative methane (ml)

60

Methane percent (%)

14000 tained a pH close to neutral in the anaerobic solid waste
50
12000
bioreactor (Speece, 1996; Jokela et al., 2002b). NH4-N
10000 40
loss through stripping was considered to be negligible
8000 30
because the pH in the reactors containing 3 and 6 g l 1
6000
4000
20 NaHCO3 was below 8 (Diamadopoulos, 1996; Yılmaz
2000 (a)
10 and Öztürk, 2001).
0 0 Since the NH4-N concentration in the leachate sam-
ples is high, the generated ammonium bicarbonate alka-
25000 70
linity contributes to total alkalinity in effluent samples as
Cumulative methane (ml)

20000
60 reported by Dinamarca et al. (2003). On the other hand,

Methane percent (%)

50 since the reserve alkalinity is the bicarbonate alkalinity
15000 40 maintaining pH above 6.2–6.6 in the anaerobic simu-
30
lated reactor; it can be assumed that this alkalinity was
10000
provided in reactors containing 3 and 6 g l 1 NaHCO3
20
5000 since the lower pH was recorded as 6.4 apart from the
10
(b) initial pHs.
0 0

30000 70 3.5. Methane gas productions and methane percentages

Cumulative methane (ml)

60 in simulated anaerobic solid waste bioreactors

Methane percent (%)

25000
20000
15000
10000
5000
0 0
0 20 40 60 80
Operation time (d)
Fig. 2. Cumulative methane gas productions (—d—) and
methane percentage (—h—) of control reactor (a), 3 g l 1 (b)
and 6 g l 1 (c) NaHCO3 containing reactors.
3.4. NH4-N variations in leachate produced from the
control and alkalinity supplemented simulated landfill
reactors
The highest NH4-N concentrations were measured to
be 770, 760 and 660 mg l 1 in control, and reactors con-
taining 3 g l 1 and 6 g l 1 NaHCO3 on d 20, 30 and 25
through the mineralization of organic nitrogenous com-
pounds (Fig. 1d). The NH4-N concentrations were 750,
720 and 650 mg l 1 in the aforementioned reactors after
65 d of operation period (Appendix A). In this study, it
was observed that there were no significant differences in
NH4-N concentrations among the control, and reactors
containing 3 g l 1 and 6 g l 1 NaHCO3. The low NH4-N
removals between d 20–30 and 65 could be attributed to
the utilization of NH4-N through assimilation of anaer-
obic bacteria (Yılmaz and Öztürk, 2001). As reported by
Jokela et al. (2002a) a small amount of ammonium
nitrogen released through degradation of proteinic and
nitrogenous compounds may be incorporated into cell
biomass. The decreases of NH4-N released from the
50
40
The maximum cumulative methane gas production
was recorded as 12 l, 19 l and 23 l in control, and reac-
30
tors containing 3 g l 1 and 6 g l 1 NaHCO3, respectively
20
at the end of 65 d, while the maximum cumulative meth-
10
(c) ane gas productions were measured at 16 l, 20 l and 24 l
after 100 d of operation period (Fig. 2a–c). In order to
100 120
compare the stability of the control reactor the methane
gas productions and methane percentages were given for
100 d. The reason for the high cumulative methane in
6 g l 1 reactor is the fast degradation of municipal or-
ganic solid wastes in this reactor through rapid metha-
nogenesis on d 65. The methane gas percentages were
58%, 60% and 61% on d 65 while the methane percent-
ages were measured to be 30% after 100 d of anaerobic
incubation in control, and reactors containing 3 g l 1
and 6 g l 1 NaHCO3. It was observed that the anaerobic
degradation terminated since the methane gas produc-
tions decreased significantly by d 65 in the reactors con-
taining 3 g l 1 and 6 g l 1 NaHCO3. The biodegradation
rate was higher in reactors containing 3 and 6 g l 1
NaHCO3. It is important to note that the increases per-
centages of cumulative methane gas productions was
lower in reactors containing 3 and 6 g l 1 NaHCO3
(E = 5.00% and 6.20%, respectively) while the increase
in the percentages of cumulative methane gas produc-
tions were higher in control reactor (E = 36%) between
d 65 and 100. This shows that the ultimate mineraliza-
tion of OSW in the control reactor was carried out be-
tween d 65 and 100. In this study, the methane
percentages measured in alkalinity added reactors were
higher than the study realized by San and Onay (2001).
Methane gas productions and methane percentages
in simulated anaerobic solid waste bioreactors show
that the alkalinity addition has a positive effect on
876 O.N. Ağdağ, D.T. Sponza / Chemosphere 59 (2005) 871–879
Table 2
Comparison of characteristics of the simulated landfilling bioreactors
Initial
1 1
Control 3 g l NaHCO3
added R.
Water content (%) 90 90
Organic matter (%) (in DS) 97 97
% C (in DS) 54 54
TN (mg g 1) (in waste) 4350 4350
TP (mg g 1) (in waste) 1050 1050
NH4-N (mg g 1) (in waste) 155 155
Waste quantity (g) 1000 1000
biodegradation of municipal solid waste in simulated
bioreactors due to high methane gas productions and
high methane percentages.
3.6. BOD5 concentrations and BOD5/COD ratios in the
leachate samples from the simulated anaerobic solid
waste bioreactors
In order to study in greater detail the proportion of
biodegradable organic carbon in the leachate it was
decided to determine the BOD5/COD ratios. The
BOD5 values decreased substantially by 69%, 95% and
96% in the aforementioned reactors, respectively (data
not shown). The experimental results indicate that a
higher MSW stabilization rate was achieved in the reac-
tor containing 6 g l 1 NaHCO3 than that of control and
3 g l 1 NaHCO3 containing reactors. Initially, all the
reactors had high BOD5/COD ratios such as 0.9, indi-
cating the high degradability of leachate (Quasim and
Chiang, 1994) (data not shown). On d 52, BOD5/COD
ratio decreased to approximately 0.25 from 0.78 in the
reactor containing 6 g l 1 NaHCO3. This ratio implies
a low biodegradable leachate. As the biodegradation
of organic content of OSW occurred, the BOD5/COD
ratio decreased. Low BOD5/COD ratio in 6 g l 1 alka-
linity added reactor shows that MSW converted rapidly
to methane via methanogenesis.
If the BOD5/COD ratio was between 0.02 and 0.13,
this implies that the leachate has a low biodegradability
through anaerobic phase. When this ratio is between 0.4
and 0.8, this implies the high biodegradability of the
leachate (Otieno, 1994). The BOD5/COD ratio measured
in the study shows similar data to the findings of Led-
akowicz and Kaczarek (2002).
3.7. Comparison of characteristics of the simulated
anaerobic landfilling reactors
The initial organic matter content of OSWs were 97%
in all reactors while the organic matter ratios of OSWs
were 65%, 58%, 51% organic in control, and reactors
Final
6 g l NaHCO3 Control 3 g l 1 NaHCO3 6 g l 1 NaHCO3
added R. added R. added R.
90 91 92 92
97 65 58 51
54 36 32 28
4350 610 220 213
1050 53 46 43
155 38 36 35
1000 213 140 120
containing 3 g l 1 and 6 g l 1 NaHCO3, respectively, at
the end of anaerobic incubation (Table 2). The reduc-
tions in the organic matter were 33%, 40% and 47%, in
control, reactors containing 3 g l 1 and 6 g l 1 NaH-
CO3, respectively, through 65 d of operation period.
The results showed that more organic material is trans-
ferred into the gaseous phase in the reactor containing
6 g l 1 NaHCO3 under methanogenic conditions. The
lack of NaHCO3 dropped the methane produced and
the conversion of organic matter in OSWs. If the acid
concentration (H2CO3 and VFA) exceeds the available
alkalinity, this severely inhibits the microbial activity,
especially the methanogens in OSWs.
The reduction in C content of OSW in the reactor
containing 6 g l 1 NaHCO3 was higher than the other
reactors. The alkaline conditions considerably increased
the carbon conversion rates in OSWs. On d 65, the grad-
ual decline of the carbon content of OSWs in the reactor
containing 6 g l 1 NaHCO3 can most probably be
attributed to the absence of un-ionized acids since the
buffer capacity of the reactor is high. In the absence of
NaHCO3 the total carbon content in OSWs was not suc-
cessfully used by the methanogens through the low con-
version rate of organic substances compared to
alkalinity containing anaerobic simulated reactors. It
was observed that the reduction of waste quantity was
high in the reactor containing 6 g l 1 NaHCO3. Seventy
eight percent, 99% and 99.9% reductions in OSWs quan-
tity were observed in control, and reactors containing
3 g l 1 and 6 g l 1 NaHCO3. This parameter is very
important since it would optimize the land utilization.
A depletion of high volume in OSWs would reduce the
landfilling sites and could be used for the management
of anaerobic degradation of OSWs in simulated bioreac-
tors. TN removal efficiencies of OSWs were 86%, 95%
and 96% in control, and reactors 3 g l 1 and 6 g l 1
NaHCO3 while TP removal efficiencies were 95%, 96%
and 96% in the same reactors, respectively. The proteins
and organic substances in OSW degraded to NH4-N and
were released to the leachate. The organic phosphorus
and phosphate in OSW were used by the acetogenic
 O.N. Ağdağ, D.T. Sponza / Chemosphere 59 (2005) 871–879
and methanogenic bacteria as nutrient and energy
source through anaerobic metabolism.
3.8. COD mass balance and degree of stabilization of
solid wastes
As the waste stabilization is directly related to the
amount of methane produced and methane percentage
of the total gas, the amount of methane generated per
kg of organic matter stabilized is taken to be an indica-
tor of waste stabilization degree. About 12, 19 and 23 l
of methane was regenerated from the control, and reac-
tors with added 3 g l 1 NaHCO3 and 6 g l 1 NaHCO3,
respectively, on d 65. These results are comparable high
with the study performed by San and Onay (2001) and
Ledakowicz and Kaczarek (2002).
In order to determine the stabilization degree, the
maximum mass of COD released was determined by
taking into consideration the maximum released COD
and the available moisture in all the reactors for d 57.
It was found that the maximum mass of COD released
from the OMS to the leachate was equal to 40, 30 and
23 g in the control, and in the reactors added 3 g l 1
NaHCO3 and 6 g l 1 NaHCO3, respectively. Twenty
eight percent of COD removed in OSW from the control
reactor was converted into methane while 44% and 65%
of COD removed in OSW was converted to methane in
the reactors added 3 g l 1 NaHCO3 and 6 g l 1 NaH-
CO3, respectively, on d 57. In our study the COD
amount converted to into methane was comparably
higher in the reactor with added 6 g l 1 NaHCO3 com-
pared to the study performed by San and Onay (2001).
As the alkalinity supplemented reactors have a higher
capacity for extracting the COD from the OSW
compared to control reactor, addition of alkalinity
increased the specific methane yield to about 0.19 and
0.23 m3 kg 1 TSadded waste in 3 g l 1 NaHCO3 and
6 g l 1 NaHCO3 added reactors, respectively, whereas
the methane yield in the control reactor was
0.13 m3 kg 1 TS on d 65. The specific methane yield in
the control reactor was low since the biodegradation
of OSWs and therefore the methane gas production were
not completed by d 65. The specific methane yield in-
creased to 0.19 m3 kg 1 TS in the control reactor on d
100 indicating the anaerobic degradation of remaining
organic substances through methanogenesis. The spe-
cific methane yields were 0.36 and 0.50 m3 kg 1 TS in
reactors containing 3 g l 1 NaHCO3 and 6 g l 1 NaH-
CO3 depending to CH4-COD remaining and TS in sim-
ulated anaerobic reactors after 100 d. These results are
significantly higher than the studies performed by
Chugh et al. (1998) and Mata-Alvarez et al. (2000).
The methane production rates were 0.033 l d 1,
0.102 l d 1 and 0.155 l d 1 in control, and the reactors
with added 3 and 6 g l 1 NaHCO3 on d 5 while the same
parameter were 0.118 l d 1, 0.290 l d 1 and 0.349 l d 1
877
in the aforementioned reactors on d 65. Maximum
methane production rates were reached on d 75 and 35
in control and the other two reactors. On d 100 the
methane gas production rates decreased to 0.199 l d 1
and 0.238 l d 1 in the reactors with added 3 and
6 g l 1 NaHCO3, respectively.
4. Conclusions
The alkalinity addition to OSWs has a positive effect
on the rate of biological degradation in anaerobic simu-
lated recycled reactors through the degradation of
organic fraction of solid wastes collected from the
kitchen of the Engineering Faculty in Dokuz Eylül
_
University Campus, Izmir, Turkey.
The findings of this study showed that the anaerobic
digestion of OSW in a simulated landfill reactor corre-
late with bicarbonate alkalinity. The alkalinity is lost
through NH4-N conversion of organic nitrogen, the buf-
fering of H2CO3 acidity by CO2 and VFA generation by
the acidogen microorganisms. VFA build up with VFA
generated, increased the acidity and reduced the alkalin-
ity. The VFA converted into methane by methanogens
particularly in the lower and upper zone of simulated
anaerobic OSW reactor and in the whole reactor since
the leachate was recirculated from the bottom to the
top of the reactor. In other words, the leachate was par-
tially accumulated in the lower part and the upper parts
of OSW reactor, resulting in VFA conversion to meth-
ane which the medium part of the reactor mostly exhib-
its only under methanogenic conditions.
The alkalinity requirement is 1.4 g NaHCO3 alkalin-
ity/g influent COD providing 87% COD, 87% VFA rem-
ovals with a methane gas production of about
100 ml d 1 and methane percentage of 59 at a pH 7.31
on d 65 through degradation of OSW in a simulated
landfill anaerobic reactor.
The observed COD removal efficiencies in reactors
containing 3 and 6 g l 1 of NaHCO3 could be due to
no-VFA accumulation resulting in activation of metha-
nogenic bacteria at pH around 7.0. The acidogenic
phase would generate acids, but this was buffered by suf-
ficient alkalinity in reactors containing alkalinity.
When 3 and 6 g l 1 NaHCO3 was added to the feed
this alkalinity was not completely consumed. Utilization
of anaerobic simulated bioreactor with an alkalinity en-
hances the feasibility of degradation of OSWs through
methanogenesis. As a result, more organic material is
transferred into the gaseous phase. Anaerobic simulated
bioreactors reduce the landfilling sites since a reduction
in the volume of the leachate as well as solid volume was
obtained in OSWs.
Because degradation of OSWs and leachate produced
through the degradation of organic substances is a most
important subject in terms of pollution emissions,
878 O.N. Ağdağ, D.T. Sponza / Chemosphere 59 (2005) 871–879

besides the cost-effective anaerobic treatment process, Appendix A (continued)

the additional alkalinity requirement should be kept in Days Control 3gl 1
NaHCO3 6gl 1
NaHCO3
mind in terms of financial costs.
21 5.16 6.98 7.02
24 5.13 7.07 7.13
Acknowledgments 28 5.26 7.07 7.08
31 5.34 7.07 7.08
This study was executed as a part of the research 42 5.85 6.94 6.99
activities of the Environmental Microbiology Labora- 52 6.04 7.04 7.19
tory of Environmental Engineering Department and 65 6.54 7.19 7.31
the project was partially funded by the Dokuz Eylül Uni- Ammonium
versity Research Foundation. The authors would like to 1 388 370 406
thank this body for the financial support to projects with 3 416 376 464
grant numbers Fen 021, 051 and 03.KB.Fen.017. 7 584 524 528
10 604 612 593
14 736 652 608
Appendix A 17 750 664 603
21 764 672 600
1 1 24 704 732 636
Days Control 3gl NaHCO3 6 g l NaHCO3
28 713 750 604
COD
31 740 760 548
1 16 004 16 121 16 200
42 752 762 602
3 18 936 17 009 16 768
52 763 750 650
7 36 618 30 353 22 850
65 750 713 650
10 35 712 27 549 20 459
14 38 102 26 065 16 749
17 39 304 22 405 13 269
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