Chemosphere 41 (2000) 297302

Aerobic thermophilic treatment of sewage sludge contaminated

with 4-nonylphenol
Fawzi A. Banat

a,*

, Stephan Prechtl b, Franz Bischof

Department of Chemical Engineering, Jordan University of Science and Technology, Box 3030, Irbid 22110, Jordan
ATZ-EVUS, Department of Environmental Process Technology, Applikations-und Technikzentrum, Kropfersrichter Strabe 6-8, D92237 Sulzbach-Rosenberg, Germany
Received 12 July 1999; accepted 15 October 1999

Abstract
4-Nonylphenol (4-NP) occurs in sewage sludge as a result of the breakdown of detergents which contains nonylphenol ethoxylates (NPEs). 4-NP is of environmental concern because of its toxicity to biological systems. The present
paper reports results of aerobic treatment under thermophilic conditions of sewage sludge articially contaminated with
4-NP. Experiments were carried out using three parallel laboratory-scale batch reactors operating with blank, 50 and
100 mg/l of 4-NP concentration. For the two studied concentrations up to 66% 4-NP reduction was achieved at a
specic air ow rate of 16 l/(l.h) and a thermophilic temperature of 60C, within 10 days of operation. The presence of
4-NP has minor eect on the rate of sludge oxidation and the nitrogen and phosphorous content in the sludge. 2000
Elsevier Science Ltd. All rights reserved.
Keywords: Nonylphenol; Sludge treatment; Thermophilic; Aerobic; Biodegradation; Digestion

1. Introduction
In recent years, the expansion in both industrial and
municipal wastewater treatment and the increasingly
stringent regulations have markedly increased the volume of sludges generated and the complexity of disposal
requirements. Selection of treatment processes for
sludges depends upon the nature of the sludge, environmental factors, and ultimate disposal options. Ideally, ultimate disposal should not pollute the
environment, should conserve resources in the sludge
and should be economical. With the prohibition of
sewage sludge disposal at sea, the choice rests between
land application and incineration. Application of sludge
to land, where feasible, is the most desirable attractive

Corresponding author. Tel.: +962-2-295111x2380; fax:

+962-2-295123.
E-mail address: banatf@just.edu.jo (F.A. Banat).

because it uses sludges in a natural cycle (Sommers,

1977). Some of the options for ultimate disposal on
land are landll, land reclamation and crop fertilization. The sludge in fact is a rich source of nutrients and
soil conditioning substances, and therefore, may be
suitable for use as a fertilizer or supplement to other
fertilizers. However, although the use of sewage sludge
as a fertilizer is an appealing option, the presence of
pathogenic organisms and toxic chemicals may limit the
application of sludges to agricultural land if not properly handled.
Surfactants are very common water pollutants which
are generally distributed into cationic, anionic and
nonionic surfactant. Nonylphenol ethoxylates (NPEs)
are broadly used non-ionic surfactants which are only
biodegraded partially in the environment (Jones and
Westmoreland, 1998; Lee and Peart, 1998). Under anaerobic conditions, NPEs biodegrade into 4-nonylphenol (4-NP) which is persistent, lipophilic and tend to
bioaccumulate more than the parent compounds

0045-6535/00/$ - see front matter 2000 Elsevier Science Ltd. All rights reserved.
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F.A. Banat et al. / Chemosphere 41 (2000) 297302

(Kirchman et al., 1991; Ekelund et al., 1993; Ahel et al.,

1994; Lee and Peart, 1995). Sewage sludge applied to
agricultural land may contain NP, and when discharged
to waterways, NP can enter the food chain. NP are
suspected to have hormone mimic properties and suspected endocrine disrupters. Male sh downstream
sewage treatment plants have been observed to have
confused hormone systems (Lee and Peart, 1995).
Anaerobic mesophilic digestion has long been the
process of choice for treatment of sludges that are to be
disposed of on agricultural land. However, traditional
mesophilic treatment under anaerobic conditions does
not remove either noxious chemical such as detergent
residues or pathogenic organisms to a satisfactory degree (Ponti et al., 1995a). To accelerate the biodegradation of chemicals that are recalcitrant to anaerobic
treatment and to thermally inactivate pathogenic microorganisms autothermal aerobic thermophilic digestion processes have been introduced as a complementary
treatment stage (Hawash et al., 1994; Ponti et al.,
1995a). The aerobic thermophilic digestion process has
some attractive features such as a high disinfection capacity and a high sludge treatment rate. Moreover, it has
been reported that aerobically digested sludge has higher
fertilizer content than that usually from anaerobic digestion (Adams and Eckenfelder, 1981).
As NPEs are toxic to the environment there is a
considerable amount of research dealing with the fate
and metabolites of these chemicals. However, little is
known about the biodegradability of sewage sludge
when contaminated with relatively high concentrations
of 4-NP (Tanghe et al., 1998). The purpose of this paper
is to present the main results obtained from a laboratory
work carried out to investigate the feasibility of treating
sewage sludge contaminated with 4-NP under aerobic
thermophilic conditions.

Three temperature controlled Plexiglass reactors

with a volume of 1 l each were fed with the pre-thickened articially polluted sewage sludge. The reactor
temperature was kept constant using a controlled water
heating bath (POLYSTAT E, Huber Kaltemaschinenbau GmbH). To maintain aerobic conditions oxygen
was supplied to the reactor via a surge pump (16 l/h).
To produce small air bubbles air was injected in the
reactor via a boiling capillary tube. A high speed
magnetic stirrer was used for intermixing of the sludge
and to assure homogeneous distribution of the reactor
content. To collect possible entrained water and escaped gasses from the reactor vessel, a cooling condenser connected in series with a gas-washing bottle
(lled with NaOH solution) and an active carbon lter
were used.
The 4-NP concentration within the reactor was
monitored over time by continuously withdrawing
samples and analyzing them. The duration of the
conducted experiments lasted 10 days. Concentration of
4-NP in the sludge samples was measured from methanol extract of dry mass using high performance liquid
chromatography (HPLC) equipped with UV-detector. A
methanol, acetic acid mobile phase was delivered at
1 ml/min. Dry mass of the whole sludge sample and the
volatile part (organic matter) of the dry mass were analyzed as described in DIN 38 414 S 2 and S 3, respectively. Both raw and ltered (with 0.45 lm membrane
lter) sludge samples were analyzed for COD. NH4 -N
concentrations were measured in the liquid phase of the
sludge, using cell tests analogous to DIN 38409 H 41
and DIN 38406 E 5. PO3
4 -P was determined photmetrically with phosphomolibedenum blue (PMB) as a
colored product. Filtered samples were analyzed for
UV254 . An pH-mV Analyzer (Model 325 WTW, Weilheim) was used to measure pH in reactors. Dry mass and
volatile solids of activated sludge were determined by
gravimetric method.

2. Materials and methods

Lab-scale batch experiments with activated sludge
articially contaminated with 4-NP were performed to
asses the feasibility of treating such a sludge under aerobic thermophilic conditions. The sewage sludge used in
the conducted experiments came from the municipal
sewage treatment plant of Sulzbach-Rosenberg
(Germany). The solid content of the activated sludge
was less than 0.3% therefore samples were pre-concentrated up to 3% by centrifugation (SUPRAFUGE-22,
Heraeus Sepatech) and homogenized with Ultra-turrax
(ULTRA-TURRAX T25, Janke & Kunkel GmbH, only
3000 rounds/min to prevent lysis of bacteria cells).
Certain amount of 4-NP was dissolved in methanol and
then added to the sludge in a drop-wise manner to assure
homogenous distribution.

3. Results and discussion

In the following, the results of the three laboratoryscale batch reactors are discussed. The kinetics of biodegradation were studied by monitoring changes in the
4-NP concentration, chemical oxygen demand (COD),
and organic dry solid matter content (oDS). The environmental conditions such as pH and nitrogen and
phosphorus concentrations in the sludge were also
monitored.
3.1. 4-NP concentration
The concentration of 4-NP in the reactor, as a measure
of 4-NP biodegradability, was monitored during the ex-

F.A. Banat et al. / Chemosphere 41 (2000) 297302

299

perimental time which lasted for 240 h. The three reactors

were operated in parallel with dierent initial concentration of 4-NP; blank, 50 and 100 mg/l. As illustrated
in Fig. 1, increasing the aeration time increase the
reduction of the 4-NP concentration. This phenomenon indicates that the added 4-NP was biologically
degraded when the reactors were operated at 60C and
16 l/(h.l) specic aeration rate. The major reduction of
the 4-NP concentration occurred during the rst seven
days of operation. At the end of the experiment the
reduction of the 4-NP concentration was about 66%
irrespective of the initial 4-NP concentration.

3.2. Sludge oxidation

The major objective of aerobic digestion is to destroy
the biodegradable content of the sludge and subsequently to convert it to a less obnoxious sludge prior to
land disposal. The sludge stabilization is highly aected
by the aeration time, and therefore it is an objective in
any treatment process to achieve the highest degree of
sludge stabilization within as short as possible incubation time (Ponti et al., 1995b). During digestion, the
sludge acts as a food supply for the microorganisms. As
time proceeds the food to microorganism ratio decreases
and the readily biodegradable content of the sludge becomes exhausted. This will be reected on microorganisms growth and activity.
The reduction of oDS occurred mainly during the
rst four days of aeration as shown in Fig. 2. Thereafter
no signicant reduction was noticed. The eect of the 4NP concentration on the reduction of sludge oDS was
minimal as depicted in Fig. 2.

Fig. 1. Chronological destruction of 4-NP in the batch reactor.

Fig. 2. Chronological variation of the organic dry solid matter

content reduction.

With the parameter COD oxidizable chemical compounds of the sludge can be measured. Under aerobic
thermophilic conditions up to 30% of the sludge COD
was eliminated in the blank sample. However, increasing
the 4-NP initial concentration in the sludge decreased
the reduction of COD. In the case of a 100 mg/l initial
4-NP concentration the reduction was 25%. The marked
dependency of COD reduction on the reactor retention
time is obvious as illustrated in Fig. 3.

Fig. 3. Chronological variation of the chemical oxygen demand

reduction.

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F.A. Banat et al. / Chemosphere 41 (2000) 297302

3.3. Nitrogen (N) and phosphorus (P)

One of the advantages of operating the reactors in
the thermophilic range (5060C) is to achieve a high
degree of pathogen destruction where heat sensitive
microorganisms tend to die. In large scale digesters
Kelly et al. (1993) found that no additional heat source
was required to maintain temperatures in the range of
5570C. Because a heterogeneous population of microorganisms is present in the sludge various microbial
species on top of the ones which have died may serve as
food for other members of the population. Eventually,
some microorganisms undergo cellular lysis, releasing
protoplasm into the environment which is then used by
other microorganisms (Haner et al., 1994). The cellular
destruction can produce nitrogen in the form of ammonia. Ammonia is highly soluble in water, establishing an equilibrium of un-ionized ammonia (NH3 ),

ionized ammonium (NH

4 ) and hydroxyl ions (OH ). In
the presence of oxygen ammonium ion can be oxidized
further to nitrate (NO
3 ). This phenomenon is strongly
supported by the observed signicant increase of ammoniumnitrogen concentration, particularly during
the rst 24 h, as shown in Fig. 4. The reduction of
ammonium ion concentration afterward can be attributed to the stripping of nitrogen in the form of ammonia, oxidation of ammonium ion to nitrate (Fig. 5),
and the utilization of this nutrient by the process
culture.
As noted above the thermophilic and starved conditions in the reactor cause death and lysis of cells. Consequently, some phosphorus will be released during

digestion. The principal form in which phosphorous is

present in sewage sludge is orthophosphate (PO3
4 )
(Horan, 1996). The marked increase of orthophosphate
concentration during the rst four days, as shown in
Fig. 6, points out to an intensied digestion and decomposition of biomass. In Figs. 46 the eect of 4-NP
concentration on the level of N and P seems to be
marginal. It is of importance to mention here that the

Fig. 4. Chronological variation of ammoniumnitrogen concentration.

Fig. 6. Chronological variation of orthophosphatephosphorous concentration.

Fig. 5. Chronological variation of nitratenitrogen concentration.

F.A. Banat et al. / Chemosphere 41 (2000) 297302

301

In the laboratory-scale batch experiments which lasted

for 10 days up to 66% reduction of the 4-NP concentration was achieved. Varying the concentration of 4-NP
slightly aected the rate of sludge oxidation and the nitrogen and phosphorous sludge content.

References

Fig. 7. Chronological variation of pH.

fertilizer value of sludge is mainly based on the content

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3.4. Alkalinity and pH
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monitoring and proper pH control are very important.
The sludge pH was monitored in the reactors and the
recorded values are shown in Fig. 7. As shown, the pH
variation can be divided into two stages; in the rst stage
the pH increased and in the second stage the pH decreased. The decomposition of proteins during digestion
caused the release of ammonia which is responsible for
alkalinity increase in the rst stage. The drop in pH in
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4. Conclusions
The aerobic treatment of sewage sludge contaminated
with dicult biodegradable organic substances such as
4-NP under thermophilic conditions has been proven
successful. The sewage sludge was articially contaminated with 4-NP up to concentrations of 50 and 100 mg/l.

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