Chemosphere 50 (2003) 1–7

www.elsevier.com/locate/chemosphere

Chemically reduced excess sludge production

in the activated sludge process
Yu Liu *

Environmental Engineering Research Centre, School of Civil and Environmental Engineering, Nanyang Technological University,
50 Nanyang Avenue, Singapore 639798, Singapore
Received 6 February 2002; received in revised form 4 September 2002; accepted 4 September 2002

Abstract

Excess sludge production from wastewater biological treatment process is highly, and the disposal of excess sludge
will be forbidden in a near future, thus increased attention has been turned to look into potential technology for sludge
reduction. Recently, some novel sludge reduction techniques have been developed based on chemical oxidation and
metabolic uncoupling. This paper attempts to review those chemical-assisted sludge reduction processes, including
sludge alkaline–thermal treatment, activated sludge-ozonation process, chlorination-combined activated sludge process,
sludge reduction by metabolic uncouplers and high dissolved oxygen activated sludge process. In these combined ac-
tivated sludge processes, excess sludge production can be reduced up to 100% without significant effect on process
efficiency and stability. This paper would be useful when one is looking for appropriate environmentally and eco-
nomically acceptable solutions for reducing or minimizing excess sludge production from wastewater biological
treatment process.
Ó 2002 Elsevier Science Ltd. All rights reserved.

Keywords: Activated sludge process; Excess sludge; Sludge reduction; Alkaline–thermal treatment; Chlorination; Ozonation;
Metabolic uncoupler; Dissolved oxygen

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Sludge reduction by sludge alkaline–thermal treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
3. Sludge reduction by ozonation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
4. Sludge reduction by chlorination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
5. Sludge reduction by metabolic uncouplers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
6. Effect of dissolved oxygen on sludge production. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
7. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5

*
Tel.: +65-6790-5254; fax: +65-6791-0676.
E-mail address: cyliu@ntu.edu.sg (Y. Liu).

0045-6535/03/$ - see front matter Ó 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 4 5 - 6 5 3 5 ( 0 2 ) 0 0 5 5 1 - 9
2 Y. Liu / Chemosphere 50 (2003) 1–7
1. Introduction
Activated sludge system has been employed to treat a
wide variety of wastewater, and over 90% of the mu-
nicipal wastewater treatment plants use it as the core
part of the treatment process. The basic function of a
wastewater biological treatment process is to convert
organics to carbon dioxide, water and bacterial cells.
The cells can then be separated from the purified water
and disposed of in a concentrated form called excess
sludge. Assuming that activated sludge has a growth
yield efficiency of 0.5 mg dry weight per mg biological
oxygen demand (BOD), 1 kg BOD removed will gener-
ate 0.5 kg dry excess sludge. It must be realized that the
excess sludge generated from the biological treatment
process is a secondary solid waste that must be disposed
of in a safe and cost-effective way. The ultimate disposal
of excess sludge has been and continues to be one of the
most expensive problems faced by wastewater utilities,
e.g. the treatment of the excess sludge may account for
25% up to 65% of the total plant operation cost (Zhao
and Kugel, 1997). So far, sludge production and dis-
posal are entering a period of dramatic change, driven
mainly by stringent environmental legislation. The re-
quirements of new European Union laws on municipal
wastewater treatment are creating a doubling in sludge
production by the end of 2005, while at the same time
placing additional restrictions on sludge disposal (Ro-
cher et al., 2001; Spinosa, 2001). Sludge disposal to all
the established outlets could become increasingly diffi-
cult or, in the case of sea disposal, will become illegal by
this year. Environmental pressures on sludge recycling
to land may lead to restrictions on applications in terms
of nitrogen content and more stringent limits for metals
in soils (EPA, 1999).
At least four technical approaches have been seri-
ously considered with respect to excess sludge handling.
One is to convert the excess sludge to value-added
construction materials or activated carbon (Pan and
Tseng, 2001; Tay et al., 2001). Second way is to recover
useful resources from sludge, e.g. production of fuel by-
products through sludge melting or sludge pyrolysis and
extraction of useful chemicals from sludge and so on
(EPA, 1999; Sachdeva et al., 2000; Stolarek and Led-
akowicz, 2001). Third way is to innovatively manage
existing outlets of sludge disposal (Hansen et al., 2000;
Englande and Reimers, 2001), while the last approach is
to reduce sludge production from the wastewater treat-
ment process rather than the post-treatment or disposal
of the sludge generated. Among these four approaches,
the development of innovative technology for reducing
excess sludge production is essential. Current technolo-
gies for sludge reduction can be roughly classified into
two major categories: microbiological and physico-
chemical methods. Microbiological methods mainly in-
clude enhanced hydrolysis of biomass in membrane
bioreactor (MBR) or in extended aeration process, and
use of protozoa and metazoa for decreasing sludge
production in aerobic wastewater treatment (Lee and
Welander, 1996; Rensink and Rulkens, 1997; Rocher
et al., 1999; Ghyooy and Verstraete, 2000). In addition,
the use of other terminal electron acceptors, e.g. nitrate
also reduces the sludge yield (Copp and Dold, 1998;
Koch et al., 2001). Sludge production is greatly reduced
in the MBR operated at a sludge age between 50 and 100
days (Manem and Sanderson, 1996; Visvanathan et al.,
2000). However, sludge reduction through manipulation
of the ecosystem seems difficult in full-scale aerobic
wastewater treatment process. Recently, the feasibility
of chemical manipulation in sludge reduction has been
investigated intensively. Current results show great po-
tential of the chemical technology in reducing excess
sludge production. Therefore, this paper reviews chemi-
cal-assisted techniques that can be applied for reducing
sludge production from industrial scale activated sludge
processes.
2. Sludge reduction by sludge alkaline–thermal treatment
Sludge reduction can be achieved by cryptic growth
of microorganisms, i.e. microbial growth on its lysates.
For this purpose, some cell breakage techniques have
been developed, such as sludge treatment by thermal,
alkaline, acid and their combination (Rocher et al.,
1999, 2001). It was found that in thermal–chemical hy-
drolysis, sodium hydroxide was the most efficient for
inducing cell lysis (Rocher et al., 1999). Further research
showed that the biodegradation of the soluble fraction
of the lysates by fresh sludge reached 75% and 90% after
48 and 350 h of incubation respectively, and a reduction
of 37% of the excess sludge was obtained without al-
tering the purification yield of the process (Rocher et al.,
2001).
Cryptic growth can also be amplified at an increased
sludge age through microbial endogenous respiration,
i.e. a longer sludge age would result in a lower sludge
production. In MBR biomass retention and separation
is achieved through a membrane module rather than a
conventional gravity settlement as used in activated
sludge processes, thus hydraulic and biosolids retention
times are completely separated, thus the sludge age can
be as long as desired. Sludge production in MBR is re-
duced by 28–68%, depending on the sludge age used
(Visvanathan et al., 2000). As compared to the MBR-
assisted sludge reduction process, sludge alkaline–ther-
mal treatment system has a number of operational
drawbacks. A 20 min alkaline sludge treatment at 60 °C
and pH 10 had been recommended to break up sludge
(Rocher et al., 2001). Even for such gentle conditions,
sodium hydroxide and energy input are required to
maintain and adjust system pH and temperature. Sludge
 Y. Liu / Chemosphere 50 (2003) 1–7
hydrolysis by chemical means produces high BOD/N
waste, and one can easily calculate the amount of
chemical oxygen demand (COD) and ammonia pro-
duced from each gram of dry biomass with an empirical
formula of C5 H7 NO2 . It should be pointed out that
complicated process operation/control and reactor cor-
rosion limit the application of this chemical-assisted
sludge reduction technique in full-scale wastewater treat-
ment plants.
3. Sludge reduction by ozonation
Ozone is a strong chemical oxidant and has been
commonly used in water disinfection process. Ozona-
tion-assisted sludge reduction process is based on the
idea that part of activated sludge is mineralized to car-
bon dioxide and water, while part of sludge is solubilized
to biodegradable organics that can be biologically trea-
ted. Many research works have been conducted with
respect to the ozonation-assisted sludge reduction pro-
cess (Yasui and Shibata, 1994; Sakai et al., 1997; Ka-
miya and Hirotsuji, 1998; Egemen et al., 1999; Deleris
et al., 2000; Dignac et al., 2000). A combined activated
sludge process and intermittent ozonation system had
been successfully developed (Yasui and Shibata, 1994;
Sakai et al., 1997; Kamiya and Hirotsuji, 1998). In this
combined system, excess sludge withdrawn from a con-
tinuous activated sludge system was subject to ozona-
tion, and then returned to the aeration tank. Results
showed that the excess sludge production was reduced
by 50% at an ozone dose of 10 mg g
1 mixed liquor
suspended solids (MLSS) d
1 in aeration tank, when the
ozone dose was kept as high as 20 mg g
1 MLSS d
1 , no
excess sludge was produced (Kamiya and Hirotsuji,
1998). In the study of Egemen et al. (1999), a similar
technical approach was used. Ozone is a strong cell lysis
agent. When sludge is kept contact with ozone in the
ozonation unit, most activated sludge microorganisms
would be killed and oxidized to organic substances.
There is evidence that more than 50% of the carbon
obtained after ozonation is readily biodegradable (Del-
eris et al., 2000). This is reason why those organic sub-
stances produced from the sludge ozonation can then be
degraded in the subsequent biological treatment.
Results from a 10-month full-scale ozonation-acti-
vated sludge system loaded with 550 kg BOD d
1
showed that no excess sludge was produced, and the
accumulation of inorganic solids in the aeration tank
is negligible, while effluent total organic carbon was
slightly higher than under the conventional activated
sludge process (Yasui et al., 1996). It had been reported
that the sludge settleability in term of sludge volumetric
index was highly improved as compared to control test
without ozonation (Kamiya and Hirotsuji, 1998). Ap-
parently, both operation and capital costs of the ozo-
3
nation-activated sludge process should be high due to
energy required for ozone production. However, eco-
nomical estimate suggests that the operation costs of the
whole process was lower than that of conventional ac-
tivated sludge process if the costs of sludge dewatering
and disposal were taken into account (Yasui et al.,
1996). Ozonation-combined activated sludge process
would be a useful technology for reducing excess sludge
production and further improving sludge settleability,
but there are still some problems associated with this
technique. Ozone is not a selective oxidant, it can react
with other reducing materials, and this may lower the
oxidation efficiency of activated sludge, while refractory
organic carbon can be released into the effluent after
ozonation. Sometimes, the toxicity of those released
refractory organic carbon might pose problem to efflu-
ent receptor. It was also found that the initial rate of
ozone consumption by sludge was extremely high and
reached 30 mg O3 g
1 volatile suspended solids (VSS)
min
1 (Deleris et al., 2000). On the other hand, it can be
easily understood that the effectiveness of ozonation is
strongly dependent upon the physical structure of acti-
vated sludge and system operation conditions. These
make the optimization of ozone dosage and dosing
mode much more difficult.
4. Sludge reduction by chlorination
As an alternative solution of sludge reduction, re-
cently a chlorination-combined activated sludge process
had been developed for minimizing excess sludge pro-
duction (Saby et al., 2002). This chlorination-combined
activated sludge process is similar to the ozonation-
activated sludge process, i.e. excess sludge was subject to
a chlorine dose of 133 mg g
1 MLSS d
1 , and the
chlorinated liquor was then returned to the aeration
tank. Compared to the control process without chlori-
nation, the sludge production could be reduced by 65%
in the chlorination-activated sludge system, which is
comparable with the cutting percentage of sludge pro-
duction in the ozonation-activated sludge process. In
the ozonation-activated sludge process, the improved
sludge settleability and less influence on the effluent
quality was observed (Kamiya and Hirotsuji, 1998), how-
ever, the chlorination treatment resulted in a poor sludge
settleability and significant increase of soluble COD in
the effluent (Saby et al., 2002). It is expected that these
potential problems can be minimized by using mem-
brane separation units instead of the conventional sed-
imentation tanks.
From the point of view of operation cost, the chlo-
rination-activated sludge process would have advanta-
ges over the ozonation-activated sludge system as
described earlier. Since chlorine is a weak oxidant as
compared to ozone, the dosage of chlorine used in the
4 Y. Liu / Chemosphere 50 (2003) 1–7
chlorination-activated sludge process is about 7–13
times higher than that of ozone applied in the ozona-
tion-activated sludge process. It is well known that
ozone has much higher oxidation power than chlorine,
releases limited by-products, and is non-reactive with
ammonia (Wojtenko and Stinson, 2001). However, in
the chlorination-activated sludge process, the formation
of undesirable chlorinated by-products would occur.
Previous research showed that when raw water was re-
acted with chlorine, the yield of trihalomethanes
(THMs) was increased as a function of the input amount
of chlorine (Park, 2001), while long-term chlorine de-
mand and the formation of THMs could follow a sec-
ond-order kinetics (Gallard and von Gunten, 2002).
Although the chlorination-activated sludge process
is cost-effective over the ozonation-activated sludge
system, chlorination-generated potential harmful by-
products would pose serious challenge to full-scale ap-
plication of this technique.
5. Sludge reduction by metabolic uncouplers
For most of aerobic bacteria, adenosine-50 -triphos-
phate (ATP) is generated by oxidative phosphorylation,
in which process electrons are transported through the
electron transport system from a source of electrons at
elevated energy levels (substrate) to a final electron ac-
ceptor (oxygen). The chemiosmotic theory shows that
the oxidative phosphorylation is driven by proton gra-
dient built up across cell membrane (Mitchell and
Moyle, 1965). However, the tight coupling of respiration
and phosphorylation can be disturbed by molecules
known as metabolic uncouplers. In the presence of
metabolic uncouplers, the energy generated from the
oxidation of organic substrate would be lost as heat
rather being captured in ATP. As a result, the growth
efficiency is much lowered in uncoupler-containing mi-
crobial culture.
Metabolic uncouplers include a diverse group of
molecules structurally, but they are all lipophilic weak
acids (Zubay, 1998). So far, many of them have been
used to reduce excess sludge production from the
activated sludge processes, such as nitrophenol, chlor-
ophenol, 3; 30 ,40 ,5-tetrachlorosalicylanilide (TCS), 2,4,
5-trichlorophenol (TCP), carbonylcyanide-p-trifluorome-
thoxyphenylhydrazone, cresol, aminophenol and so on
(Okey and Stensel, 1993; Low and Chase, 1998;
Mayhew and Stephenson, 1998; Chen et al., 1999,
2002; Strand et al., 1999; Liu, 2000a,b; Low et al.,
2000; Xie, 2002). In a laboratory scale continuous ac-
tivated sludge reactor, Low et al. (2000) reported that
biomass production was reduced by 49% when para-
nitrophenol (pNP) was added to the culture, while at
a pNP concentration of 120 mg l
1 , no excess sludge
was produced (Low and Chase, 1998). The observed
growth yield was reduced as high as 78% at a TCS
concentration of 0.8 mg l
1 as compared to control
culture free of TCS, with no significant effect on sub-
strate removal efficiency (Chen et al., 2002). These
results suggest that TCS is a stronger metabolic un-
coupler than pNP. Strand et al. (1999) tested the ca-
pability of 12 metabolic uncouplers in reducing excess
sludge production in biological wastewater treatment,
and found that the most effective uncoupler among the
tested chemicals was TCP and 50% of sludge reduction
was achieved with TCP addition of 5 mg l
1 . However,
based on a series of orthogonal testes, Xie (2002)
concluded that aminophenol is a much stronger met-
abolic uncoupler than chlorophenol and nitrophenol.
At an aminophenol concentration of 20 mg l
1 , no ex-
cess sludge was produced, but the COD removal effi-
ciency also reduces by 56% as compared to the control
test free of metabolic uncoupler (Xie, 2002). In fact, a
number of factors can influence the efficiency of meta-
bolic uncoupler in reducing excess sludge production,
such as culture medium, pH, the affinity of microbes to
different types of metabolic uncouplers and physio-
logical state and viability of microorganisms.
The dissipation of energy via uncoupling biochemical
processes can promote sludge reduction, and effective-
ness of metabolic uncouplers in reducing excess sludge
production has been proven. Industrial application of
metabolic uncouplers in two full-scale activated sludge
plants in Phoenix and Arizona had been reported by
Okey and Stensel (1993). However, it should be realized
that most metabolic uncouplers are xenobiotic and po-
tentially harmful to environment. Among the metabolic
uncouplers currently used for reducing excess sludge
production, TCS is more gentle and environmentally
sound. In fact, TCS has been often used as a component
in formulation of soaps, rinses, shampoos and so on
(Budavari, 1989).
Other technical problems associated with the appli-
cation of metabolic uncouplers are unexpected dissolved
oxygen consumption as well as the effect of microbial
acclimation to metabolic uncouplers. A rough estimate
based on the results by Zubay (1998) shows that the
dissolved oxygen consumption rate can increase by a
factor 50 after addition of a metabolic uncoupler to a
suspension of mitochondria. Similarity was also ob-
served in activated sludge systems (Mayhew and Ste-
phenson, 1998; Strand et al., 1999), e.g. the specific
oxygen utilization rates were increased from 8 g O2 g
1
VSS d
1 without TCP addition to approximately 20 g O2
g
1 VSS d
1 when TCP presented. The combined pure
oxygen aeration and metabolic uncouplers process
would be an ideal solution for uncoupler-induced oxy-
gen overconsumption. Meanwhile, increased biomass
concentration was found to reduce the effectiveness of
metabolic uncouplers (Liu, 2000b; Xie, 2002). Initially
non-acclimated activated sludge cannot degrade external
 Y. Liu / Chemosphere 50 (2003) 1–7
metabolic uncouplers, however in order to maintain a
lower sludge yield, metabolic uncouplers need to be
continuously dosed to aeration tank and microbial
acclimation to the uncouplers would occur. As Strand
et al. (1999) noted, long-term microbial acclimation
could eventually negate the effects of uncoupler addition.
6. Effect of dissolved oxygen on sludge production
Low sludge yield has been commonly observed in
pure oxygen aeration activated sludge process. This
implies that high dissolved oxygen concentration could
promote sludge reduction. Compared to conventional
air aeration activated sludge process, the growth yield
can be lowered by up to 54% in purified oxygenation
activated sludge system (McWhirter, 1978), while Boon
and Burgess (1974) found that for the similar sludge age,
the observed sludge yield in the pure oxygen system was
only 60% of that in the air system. In a fixed-film system
oxygenated by hydrogen peroxide, Roques et al. (1984)
reported that the observed growth yield was reduced to
about 0.37 mg MLSS mg
1 total oxygen demand when
dissolved oxygen concentration was increased to 10
mg l
1 . Recently a more detail study on the effect of
dissolved oxygen on excess sludge production was con-
ducted by Abbassi et al. (2000). Their results showed
that the excess sludge production decreased from 0.28 to
0.2 mg MLSS mg
1 BOD as the reactor dissolved oxy-
gen was increased from 1.8 to 6.0 mg l
1 in a laboratory-
scale conventional activated sludge reactor. These
support a basic idea that high dissolved oxygen could
promote sludge reduction. Additional benefits of high
dissolved oxygen biological process include repression of
filamentous growth, ability to maintain a higher biomass
concentration in the aeration tank; better sludge settling
and thickening; higher oxygen transfer efficiency and
more stable operation (Benefield and Randall, 1980). It
can be anticipated that with the development of more
cost-effective pure oxygen generation and membrane
aeration techniques, high oxygen process would have
great industrials potential in reducing excess sludge
production.
Two hypotheses had been proposed to inter-
pret high dissolved oxygen-induced sludge reduction.
McWhirter (1978) postulated that the high dissolved
oxygen concentration would produce a higher level of
active biomass, and hence, a lower true sludge loading
rate that would be measured relative to a low dis-
solved oxygen system. The lower true sludge loading
rate would result in a relatively lower sludge produc-
tion rate at the same apparent measured value of the
sludge loading rate. However, Abbassi et al. (2000)
considered that the increase of the oxygen concentra-
tion in the bulk liquid promoted a deep diffusion of
oxygen that subsequently led to an enlargement of the
5
aerobic volume inside the flocs. As a result, the hy-
drolysed biomass in the floc matrix could be aerobi-
cally degraded and sludge quantity is thus reduced.
Further study is still required to deeply look into the
mechanisms of high dissolved oxygen-induced sludge
reduction.
In the absence of dissolved oxygen, it was observed
that a significant fraction of the mixed heterotrophic
population in activated sludge could use nitrate as the
terminal electron acceptor instead of dissolved oxygen
(Copp and Dold, 1998). This mechanism is known as
anoxic respiration or denitrification. Copp and Dold
(1998) reported that the growth yield of activated sludge
under anoxic conditions was lowered by 38% as com-
pared to that under aerobic conditions. In fact, there is
strong evidence that less sludge production can be ex-
pected when anoxic denitrification occurs in a biological
system (Copp and Dold, 1998; Hao et al., 2001; Koch
et al., 2001; Peng et al., 2001). Therefore, it appears that
the electron acceptor has a significant effect on the
sludge production.
7. Summary
Compared to microbiological methods (e.g. the
manipulation of maintenance, endogenous respiration,
lysis, decay and predation), the chemical-combined
activated sludge processes would be more efficient for
excess sludge reduction. In addition, the chemical-
assisted sludge reduction processes have advantages of
easy control, stable performance, and high operation
flexibility. The relatively high operation cost of these
systems currently limits their application in industrial
practice. However, it is expected that the increased op-
eration and capital costs due to chemical addition can be
compensated from saving the cost of excess sludge post-
treatment. In this sense, the chemical-enhanced sludge
reduction techniques would be attractive and have great
industrial potentials, but have to be optimized eco-
nomically in future.
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