Chemosphere 41 (2000) 297±302

Aerobic thermophilic treatment of sewage sludge contaminated
with 4-nonylphenol
Fawzi A. Banat


, 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

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 arti®cially 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
speci®c air ¯ow rate of 16 l/(l.h) and a thermophilic temperature of 60°C, within 10 days of operation. The presence of
4-NP has minor e€ect on the rate of sludge oxidation and the nitrogen and phosphorous content in the sludge. Ó 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:
E-mail address: (F.A. Banat).

because it uses sludges in a natural cycle (Sommers,
1977). Some of the options for ultimate disposal on
land are land®ll, 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 Ó 2000 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 4 5 - 6 5 3 5 ( 9 9 ) 0 0 4 9 5 - 6

and when discharged to waterways. To collect possible entrained water and escaped gasses from the reactor vessel. as a measure of 4-NP biodegradability. Sewage sludge applied to agricultural land may contain NP. Results and discussion In the following. The environmental conditions such as pH and nitrogen and phosphorus concentrations in the sludge were also monitored. The duration of the conducted experiments lasted 10 days. Banat et al. and organic dry solid matter content (oDS). 1993. 2. Heraeus Sepatech) and homogenized with Ultra-turrax (ULTRA-TURRAX T25.. Weilheim) was used to measure pH in reactors. 1994. The kinetics of biodegradation were studied by monitoring changes in the 4-NP concentration. Dry mass and volatile solids of activated sludge were determined by gravimetric method. little is known about the biodegradability of sewage sludge when contaminated with relatively high concentrations of 4-NP (Tanghe et al. 3. Lee and Peart. was monitored during the ex- .. a cooling condenser connected in series with a gas-washing bottle (®lled with NaOH solution) and an active carbon ®lter were used. A methanol. 3.1. Three temperature controlled Plexiglass reactors with a volume of 1 l each were fed with the pre-thickened arti®cially polluted sewage sludge. The solid content of the activated sludge was less than 0. An pH-mV Analyzer (Model 325 WTW. Ponti et al. 1995). 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. Filtered samples were analyzed for UV254 . 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. respectively.. 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. Ahel et al. The aerobic thermophilic digestion process has some attractive features such as a high disinfection capacity and a high sludge treatment rate. 1995a). Materials and methods Lab-scale batch experiments with activated sludge arti®cially contaminated with 4-NP were performed to asses the feasibility of treating such a sludge under aerobic thermophilic conditions. 1998). As NPEs are toxic to the environment there is a considerable amount of research dealing with the fate and metabolites of these chemicals. 4-NP concentration The concentration of 4-NP in the reactor. 1994. NP can enter the food chain.A. PO3ÿ 4 -P was determined photmetrically with phosphomolibedenum blue (PMB) as a colored product. To produce small air bubbles air was injected in the reactor via a boiling capillary tube. / Chemosphere 41 (2000) 297±302 (Kirchman et al. Moreover. 1991. To maintain aerobic conditions oxygen was supplied to the reactor via a surge pump (16 l/h).. it has been reported that aerobically digested sludge has higher fertilizer content than that usually from anaerobic digestion (Adams and Eckenfelder. However. 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. Both raw and ®ltered (with 0. chemical oxygen demand (COD). Janke & Kunkel GmbH. Ekelund et al.3% therefore samples were pre-concentrated up to 3% by centrifugation (SUPRAFUGE-22. NH4 -N concentrations were measured in the liquid phase of the sludge. However.. The 4-NP concentration within the reactor was monitored over time by continuously withdrawing samples and analyzing them.45 lm membrane ®lter) sludge samples were analyzed for COD. The sewage sludge used in the conducted experiments came from the municipal sewage treatment plant of Sulzbach-Rosenberg (Germany). 1995). 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. Anaerobic mesophilic digestion has long been the process of choice for treatment of sludges that are to be disposed of on agricultural land. Huber Kaltemaschinenbau GmbH). acetic acid mobile phase was delivered at 1 ml/min. The reactor temperature was kept constant using a controlled water heating bath (POLYSTAT E... the results of the three laboratoryscale batch reactors are discussed. NP are suspected to have hormone mimic properties and suspected endocrine disrupters. only 3000 rounds/min to prevent lysis of bacteria cells). A high speed magnetic stirrer was used for intermixing of the sludge and to assure homogeneous distribution of the reactor content. using cell tests analogous to DIN 38409 H 41 and DIN 38406 E 5. 1981). Male ®sh downstream sewage treatment plants have been observed to have confused hormone systems (Lee and Peart. Certain amount of 4-NP was dissolved in methanol and then added to the sludge in a drop-wise manner to assure homogenous distribution.298 F.

3. The reduction of oDS occurred mainly during the ®rst four days of aeration as shown in Fig. 1. At the end of the experiment the reduction of the 4-NP concentration was about 66% irrespective of the initial 4-NP concentration. In the case of a 100 mg/l initial 4-NP concentration the reduction was 25%.. Banat et al. This will be re¯ected on microorganisms growth and activity.2.l) speci®c aeration rate. 50 and 100 mg/l. increasing the aeration time increase the reduction of the 4-NP concentration. Chronological variation of the chemical oxygen demand reduction. the sludge acts as a food supply for the microorganisms. Thereafter no signi®cant reduction was noticed. 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. 1. The major reduction of the 4-NP concentration occurred during the ®rst seven days of operation. As illustrated in Fig. Under aerobic thermophilic conditions up to 30% of the sludge COD was eliminated in the blank sample. Fig. Chronological variation of the organic dry solid matter content reduction. 2. Chronological destruction of 4-NP in the batch reactor. 1995b). However. 3. The three reactors were operated in parallel with di€erent initial concentration of 4-NP. The sludge stabilization is highly a€ected by the aeration time. / Chemosphere 41 (2000) 297±302 299 perimental time which lasted for 240 h. . 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. 2. 3. Fig. The marked dependency of COD reduction on the reactor retention time is obvious as illustrated in Fig. The e€ect of the 4NP concentration on the reduction of sludge oDS was minimal as depicted in Fig. With the parameter COD oxidizable chemical compounds of the sludge can be measured. During digestion. This phenomenon indicates that the added 4-NP was biologically degraded when the reactors were operated at 60°C and 16 l/(h.F. increasing the 4-NP initial concentration in the sludge decreased the reduction of COD. As time proceeds the food to microorganism ratio decreases and the readily biodegradable content of the sludge becomes exhausted. Fig.A. blank. 2.

5). particularly during the ®rst 24 h. 1996). / Chemosphere 41 (2000) 297±302 3. The marked increase of orthophosphate concentration during the ®rst four days. 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.3. 4±6 the e€ect of 4-NP concentration on the level of N and P seems to be marginal. Chronological variation of orthophosphate±phosphorous concentration. The reduction of ammonium ion concentration afterward can be attributed to the stripping of nitrogen in the form of ammonia. some microorganisms undergo cellular lysis. As noted above the thermophilic and starved conditions in the reactor cause death and lysis of cells. Fig. and the utilization of this nutrient by the process culture. some phosphorus will be released during digestion. It is of importance to mention here that the Fig. The cellular destruction can produce nitrogen in the form of ammonia. releasing protoplasm into the environment which is then used by other microorganisms (Haner et al. Banat et al. Eventually.. Nitrogen (N) and phosphorus (P) One of the advantages of operating the reactors in the thermophilic range (50±60°C) is to achieve a high degree of pathogen destruction where heat sensitive microorganisms tend to die. 4. 1994). 5. Chronological variation of ammonium±nitrogen concentration. . establishing an equilibrium of un-ionized ammonia (NH3 ).A. 6. In Figs. as shown in Fig. (1993) found that no additional heat source was required to maintain temperatures in the range of 55±70°C. as shown in Fig. This phenomenon is strongly supported by the observed signi®cant increase of ammonium±nitrogen concentration. Consequently. In large scale digesters Kelly et al. The principal form in which phosphorous is present in sewage sludge is orthophosphate (PO3ÿ 4 ) (Horan. Ammonia is highly soluble in water. oxidation of ammonium ion to nitrate (Fig. In the presence of oxygen ammonium ion can be oxidized further to nitrate (NOÿ 3 ). ÿ ionized ammonium (NH‡ 4 ) and hydroxyl ions (OH ). 6. Chronological variation of nitrate±nitrogen concentration. 4. Fig. points out to an intensi®ed digestion and decomposition of biomass.300 F.

UK. Degradation of nonylphenol ethoxylates during the composting of sludges from wool scour e‚uents. 28. Peart.. Behaviour of alkylphenol polyethoxylate surfactants in the aquatic environment 1. 37±47/Otheraref.. Chem. 1987. D. Res. Sonnleitner. H. Kelly. Wiley. 22... Biomass & Bioenergy 6. 28. C. UK. J. The sludge pH was monitored in the reactors and the recorded values are shown in Fig.. Sci.. A...W.. Pollut. Biodegradation of 4-nonylphenol in seawater and sediment. Hawash. 38. 1995. Biotechnol. 7. Ponti. 863±869. Hamad. T. H.B. H..G. Kinetic study of thermophilic aerobic stabilization of sludge. M. 67. Sludge Treatment. The sewage sludge was arti®cially contaminated with 4-NP up to concentrations of 50 and 100 mg/l. 1996. H. Bhargava.. 182±183. Civil Eng.. Autothermal thermophilic aerobic digestion of municipal sludges: a one year full scale demonstration project.S. 1993. Horan.. Kirchman. Determination of 4-nonylphenol in e‚uent and sewage sludge from sewage treatment plants.. Progress and kinetics of aerobic digestion of secondary sludges. fertilizer value of sludge is mainly based on the content of nitrogen and phosphorous. A.. Adams... Granmo. 59±61.F.. However maintaining a pH in the range of 7±8. F.A. Haner. Death and lysis during aerobic thermophilic sludge treatment: characterization of recalcitrant products.J. C. Wastewater Treatment Systems. T. B. G. 389±402. W. 1994. 65. Environ. W. the pH variation can be divided into two stages. 32..S.. Unit Treatment Processes in Water and Wastewater Engineering. Eckenfelder. 1997. C. Santhanam. initial assessment of pilotscale studies. Anderson. Aerobic thermophilic treatment of sewage sludge at pilot plant scale 2: technical solutions and process design.. Ponti.. K. Koch. D. G. The drop in pH in the second stage is not surprising since there is a natural decrease in pH as digestion proceeds because of nitri®cation. in the ®rst stage the pH increased and in the second stage the pH decreased. Can.. 477±484. Melcer. 79.. The nitri®cation process generates H‡ and thus exerts a substantial alkalinity demand (7. Westmoreland.. Casey. Fiechter. 1995b. Sonnleitner. 849±861. Mason. C... Alkalinity and pH As the pH a€ects the growth and activity of microorganisms which degrade the organic components monitoring and proper pH control are very important. 1991. 1998. Aerobic thermophilic treatment of sewage sludge at pilot plant scale 1: operating conditions. Biol. occurrence and transformation in sewage treatment.. H. Ekelund. J. T.. M. as in the experiments. Water Qual. Lee.. 14. B. J. H. . 38. 1997). N. Magnusson. Bhargava and Datar. El Diwani.B.. Wiley.. Varying the concentration of 4-NP slightly a€ected the rate of sludge oxidation and the nitrogen and phosphorous sludge content. C. Aerobic digestion of wastewater sludges. In: Eckenfelder. Water Res. D. Mavinic. 1988.. Berggren.. G. 21. Banat et al.A. El Ibiari.J. Organic pollutants in sewage sludge. Res. 173±182.. S. M. A. provides the maximum rate of aerobic digestion (Anderson and Mavinic. 4. F. R.E. Technol.. Can. Datar. The decomposition of proteins during digestion caused the release of ammonia which is responsible for alkalinity increase in the ®rst stage. Agric. Jones.1 mg alkalinity as CaCO3 per mg NH4‡ -N) (Casey. Giger. 1995a. 1993.H. M. 1998. Conclusions The aerobic treatment of sewage sludge contaminated with dicult biodegradable organic substances such as 4-NP under thermophilic conditions has been proven successful. Dekker. Water Environ. Fiechter.E. 1988). D. Swedish J. Environ. 1131±1142. W. 2623± 2627. Chronological variation of pH. 1976±1980. Water Res.J.. Aly. 1994..J. 1987. As shown.4. References Fig. Lee.C.. 283±286. Res. 1994. Water Res. A. 33. This inevitably reduces pH.. Hamer. 107±113.. Improvements in aerobic digestion through pH control. N. B.W.W. Peart. Mavinic. Anal.. / Chemosphere 41 (2000) 297±302 301 In the laboratory-scale batch experiments which lasted for 10 days up to 66% reduction of the 4-NP concentration was achieved. Biotechnol. J. 3.A. Jonsall. 1981. 7. New York. Occurrence and elimination of nonylphenol ethoxylates and metabolites in municipal wastewater and e‚uents. Astrom. Ahel.E.S.

/ Chemosphere 41 (2000) 297±302 Sommers. G.. 2889±2896.. W.. 32. L.A. Verstraete. Nonylphenol degradation in lab-scale activated sludge units is temperature dependent. Devriese. Chemical composition of sludges and analysis of their potential as fertilizers. Tanghe.E. Qual.. Water Res. 6. T. 225±232. . Banat et al. Environ.302 F. 1998. 1977. J.