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Treatment of pharmaceutical wastewater containing antibiotics by O3 and O3/H2O2 processes

Is l Akmehmet Balcolu *, Merih Otker g
Institute of Environmental Sciences, Boazici University, Bebek-Istanbul 80815, Turkey g Received 19 November 2001; received in revised form 29 August 2002; accepted 29 August 2002

Abstract Ozonation of three dierent synthetic pharmaceutical formulation wastewater containing two human antibiotics and a veterinary antibiotic has been studied to enhance the their biodegradability. The eects of pH and initial chemical oxygen demand (COD) value as well as addition of hydrogen peroxide on ozonation process were investigated. Total organic carbon (TOC), COD, biochemical oxygen demand (BOD), and aromatic content (UV254 ) were the parameters followed to evaluate the performance of ozonation process. Comparison of the biodegradability of selected wastewaters containing dierent antibiotics conrmed that the variation of biodegradability was associated with the target compound. While BOD5 /COD ratio of veterinary antibiotic formulation wastewater was increased from 0.077 to 0.38 with an applied ozone dosage of 2.96 g/l, this ratio for human antibiotic I and human antibiotic II was increased from 0 to 0.1 and 0.27 respectively. Moreover the results of this investigation showed that the ozonation process is capable of achieving high levels of COD and aromaticity removals at about their natural pH values. 2002 Elsevier Science Ltd. All rights reserved.
Keywords: Antibiotic formulation wastewater; Advanced oxidation processes; Biodegradability enhancement; Ozonation

1. Introduction Recent studies indicated that antibiotics, which are specially designed to control bacteria in humans and animals, have been found in surface water (Stan et al., 1994; Meyer et al., 1999) and sewage treatment plant euents (Richardson and Brown, 1985; Halling-Srensen et al., 1998; Kmmerer et al., 2000). These results u inferred that antibiotics cannot be completely eliminated during biological treatment and they are emitted into receiving water systems. In an environmental aspect, the most prominent eect of antibiotics is the exerting toxic eects to aquatic organisms that would upset the ecological balance (Lansky and Halling-Srensen, 1997; Migliore et al., 1997). Moreover, the presence of anti* Corresponding author. Tel.: +90-212-385-15-40; fax: +90212-257-50-33. E-mail address: balciogl@boun.edu.tr (I. Akmehmet Balcolu). g

biotics in natural systems leads to the development of multi-resistant strains of bacteria. Hence, it is necessary to treat the euents containing antibiotics adequately before discharging into biological treatment process and receiving water systems. The sources of antibiotics in natural water systems may be manufacturing operations in pharmaceutical industry and therapeutical use of them for human and animals. High amount of antibiotics have also been used as growth promoters in intensive farming. After administration to human and animals up to 90% of antibiotics may be excreted through urine and feces into sewage. Therefore signicant amount of antibiotics may pass through target organisms and become spread in the terrestrial and aquatic environment. Consequently, the concentration of antibiotics in surface and groundwater may rise to lg/l and ng/l range respectively (HallingSrensen et al., 1998). Activities in pharmaceutical industry may also be responsible for the presence of antibiotics in natural water

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systems. Pharmaceutical industry, which includes four dierent type of manufacturing processes, fermentation, chemical synthesis, extraction and formulating (EPA, 1991), often generates high strength wastewater changing in character and quantity depending upon the used manufacturing processes and season (Nemerow, 1978). Among the wastewaters from dierent operations in this industry, formulation euent that rises from washing of equipment is characterized by small euent ow and low pollution load. However the euents originated from the formulation of antibiotics have low biodegradability since they contain almost only active substance. Hence a chemical pretreatment is necessary for pharmaceutical euents, like antibiotic formulation, containing high concentrations of bioinhibitory compounds. During the last two decades, in order to augment the biodegradability and also increase the ecacy of subsequent treatment, advanced oxidation processes (AOPs) have been applied to refractory organic pollutants and xenobiotics found in groundwater, surface water and industrial wastewater (Takahashi et al., 1994; Scott and Ollis, 1995; Alvares et al., 2001). These processes involve the generation of highly free radicals, mainly hydroxyl radical (HO ) via chemical (O3 /OH , O3 /H2 O2 , Fe2 /H2 O2 ), photochemical (UV-C/H2 O2 , UV-C/O3 ) and photocatalytic reactions (UV-A/TiO2 ). Although AOPs are expensive to install and operate, their application is unavoidable for the treatment of refractory organic pollutants. Numerous researches have evaluated on the treatment of refractory compounds by dierent AOPs. However, few studies reported in the literature dealt with pharmaceuticals (Rey et al., 1999; Zwiener and Frimmel, 2000) and pharmaceutical euents (Gulyas et al., 1995; H et al., 1997). o Considering the above mentioned facts, the present investigation was aimed to study the pretreatment of euents originated from three dierent antibiotic formulation process by O3 and O3 /H2 O2 AOPs for the improvement of biodegradability. Cephalosporine, penicillin, and quinolone group antibiotics were chosen due to their high consumption rates in Turkey. The effect of initial pollution load of wastewater, pH, and H2 O2 concentration on the performance of ozonation was evaluated in terms of conventional wastewater measures such as chemical oxygen demand (COD) and biochemical oxygen demand (BOD)5 . Moreover spectrophotometric measurements were performed for the evaluation of aromaticity removal.

nished product and composition of formulation wastewater is known. Synthetic wastewaters of human antibiotic I (ceftriaxone sodium, cephalosporine group; Roche) and human antibiotic II (penicillin VK, penicillin group; Aventis) contain only active substance, whereas that of veterinary antibiotic (enrooxacin, quinolone group; Bayer) includes 10% active substance and inorganic additives. Depending upon the studies carried out on actual antibiotic formulation wastewaters initial COD values of synthetic wastewaters were chosen between 250 and 1400 mg/l. Since the limited solubility of veterinary antibiotic at pH 3 and 7, its formulation mixture with having COD values up to 900 mg/l was used in the experiments. The chemical structures of active substances found in synthetic wastewaters are elucidated in Fig. 1. Distilled deionized water was used for the preparation of all analytical solutions and synthetic wastewaters. Since the experiments indicated that during ozonation signicant changes were observed in pH value of wastewater, buer solutions were used in order to obtain pH control. The ozonation of synthetic wastewaters was performed at three dierent pH values, which were adjusted by phosphate buer solutions (KH2 PO4 , H3 PO4 for pH 3; KH2 PO4 , Na2 HPO4 for pH 7; Na2 HPO4 , Na3 PO4 for pH 10:6) (Christian, 1994). 2.2. The ozone reactor Ozonation experiments were performed in a 1500 ml capacity ozone bubble column for 1 h at semi-batch mode with counter current recirculation of the liquid to the gas ow (Arslan and Akmehmet Balcolu, 2000). g Fisher OZ 500 model ozone generator was used for the production of ozone from dry and pure oxygen. The oxygen ow rate to the generator was maintained at 100 l/h and monitored with a rotameter incorporated into the ozone generator. The diusion rate of the ozone oxygen mixture, introduced from the bottom of the reactor through a sintered glass diusing plate, was 2.96 g/ l h. Excess ozone was passed into gas absorption bottle containing 2% KI solution. All tubes from the ozone generator to the reactor and the gas absorption bottles were made of Neoprene and the ttings from Teon. In experiments conducted by O3 /H2 O2 process, hydrogen peroxide addition was carried out just before the ozone containing gas entered the reactor. All experiments were performed at ambient temperature (20 C 2). 2.3. Analytical methods 5 ml treated samples were taken at appropriate time intervals from ozone reactor to analyze COD and

2. Materials and methods 2.1. Synthetic antibiotic formulation wastewater Synthetic wastewaters were used throughout the study since the formulation wastewater contains only the

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Fig. 1. Chemical structure of active substances.

absorbance at dierent wavelengths. Any residual H2 O2 was destroyed by the enzyme catalase from bovine liver (176 000 A.U.; 1 A.U. destroys 1 lmol of H2 O2 /min at pH 7 at 25 C) whenever residual H2 O2 in the treated sample was not determined. Total organic carbon (TOC) content was measured by Shimadzu TOC-5000 A analyzer. Absorbance values recorded by Shimadzu UV-1208 model spectrophotometer were measured at wavelength of maximum absorption, kmax of active substances and 254 nm wavelength; UV254 representing the aromatic content of wastewater (Ravikumar and Gurol, 1994). After appropriate dilutions spectrophotometric measurements were performed by using 1 cm quartz cuvette. In separate experiments, BOD5 values of synthetic wastewaters were measured manometrically to evaluate whether changes in biodegradability occurred after ozonation. In the BOD5 measurements municipal sewage supernatant was used as bacterial seed. Inlet and outlet gas ozone and aqueous ozone concentrations were determined iodometrically and by the indigo method (Bader and Hoign, 1981), respectively. The amount of e ozone consumed within the reactor was determined from the dierence between the inlet and outlet concentrations. The remaining H2 O2 concentration in the reacting solution was determined by the molibdate-catalyzed iodometric method (IOA, 1997). COD was measured in accordance with the dichromate method (APHA, 1989).

3. Results and discussion Three dierent synthetic wastewater having initial COD value of 450 mg/l were subjected to ozonation at an applied rate of 2.96 g/l h in buered solution at pH 7. Fig. 2 shows the normalized COD, TOC and aromaticity values of three dierent wastewater during 1 h ozonation process and Fig. 3 represents the absorption spectra of these wastewaters. As expected all parameters decrease with elevated values of applied ozone dosage. Compare to aromaticity and COD removal the destruction of TOC is obviously delayed for all wastewaters. Among the investigated wastewaters higher COD and TOC removals were achieved for the ozonation of veterinary antibiotic wastewater. The destruction of aromaticity was very effective for human antibiotic I and veterinary antibiotic wastewater and only a specic ozone dosage (O3 g/TOCi g) of 1.4 g/g is needed to obtain an aromaticity removal of 44%. Although COD and TOC values steadily decreased throughout the ozonation process, the absorbance of the human antibiotic II wastewater at 254 nm and characteristic wavelength increased rapidly to a maximum then declined as shown in Fig. 3. This increase in absorbance suggests the formation of one or more intermediates of incomplete oxidation during the early stages of ozonation. This phenomenon was also observed during the ozonation of some organic compounds (Kuo

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Normalized TOC, COD, and UV254

1.2 1 0.8 0.6 0.4 0.2 0 0

1.6 1.4 1.2 1 0.8 0.6 0.4 0.2 0 0 10 20 30 40

TOC

UV254

COD

Human antibiotic I
CODi = 450 mg/l TOCi = 167 mg/l UV254i = 19.425

10

20

30

40

50

60

70

Normalized TOC, COD, and UV254

Human antibiotic II
CODi = 450 mg/l TOCi = 162 mg/l UV254i= 0.456

50

60

70

Normalized TOC, COD, and UV254

1.2 1 0.8 0.6 0.4 0.2 0 0 10 20 30 40 50 Ozonation time (min) 60 70 Veterinary antibiotic
CODi = 450 mg/l TOCi =165 mg/l UV254i = 11.025

Fig. 2. Variations in normalized TOC, COD, and UV254 values of synthetic wastewaters as a function of ozonation time (buered solution at pH 7).

and Huang, 1995). For human antibiotic I wastewater 50% TOC and 74% COD removal were achieved with 2.96 g/l h applied ozone rate however UV254 value of wastewater was still high (UV254 1:325) compare to other wastewaters (UV254 0:327 for human antibiotic II wastewater; UV254 0:45 for veterinary antibiotic wastewater). 3.1. Eect of pH To elucidate the eect of pH on ozonation process, synthetic wastewaters were subjected to ozonation in buered solutions at pH 3, 7 and 11 for 1 h. Table 1

displays overall COD and UV254 removals of wastewaters at three dierent pH values. With the increment of the solution pH from 3 to neutral value, overall COD abatement was enhanced for all formulation wastewaters as expected. In general, ozone reacts with organic compounds found in water and wastewater via two dierent pathways namely direct molecular and indirect radical chain type reaction depending upon pH and composition of water. It is expected that molecular ozone is the major oxidant at acidic pH, whereas less selective and faster radical oxidation (mainly hydroxyl radical) becomes dominant at pH > 7 as a consequence of OH accelerated ozone

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Fig. 3. Absorbance behavior of wastewaters during ozonation (buered solution at pH 7; CODi 450 mg/l).

decomposition (Langlais et al., 1991). Since the oxidation potential of hydroxyl radicals is much higher than that of ozone molecule, direct oxidation is slower than radical oxidation and furthermore causes incomplete oxidation of organic compounds as observed in this study. However the eect of ozonation pH on the overall COD and aromaticity removal values exhibited a different trend for each formulation wastewater (Table 1). The overall COD removal of human antibiotic II wastewater increased from 24% at pH 3 to 69% at pH 7

and remained almost unchanged (71%) at pH 11. The eect of pH on the overall COD removal of other wastewaters was less pronounced. For veterinary antibiotic wastewater the lower values of overall COD removal (79%) at pH 11 compared to that of pH 7 (88%) could be explained by the fact that the veterinary antibiotic formulation contained inorganic additives, which may act as radical scavengers at pH 11. These observations indicated that COD removal could be simply achieved via both reaction pathways of ozone whereas

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Table 1 Eect of pH on the overall COD and aromaticity removal rates of wastewaters (CODi 450 mg/l) in 1 h ozonation process Human antibiotic I COD removal pH 3 pH 7 pH 11 UV254 removal pH 3 pH 7 pH 11 (%) 53 74 82 (%) 75 93 90 Human antibiotic II 24 69 71 70 29 25 Veterinary antibiotic 65 88 79 82 96 95

the reaction pH had to be at least 7 to enhance ozone decomposition for higher COD reduction. The overall aromaticity removal of human antibiotic II wastewater decreased by increasing pH value from 3 to 11 since the increase in UV254 absorbance was more pronounced at higher pH values. In order to indicate importance of pH control during ozonation process, separate ozonation experiments were carried out by using nonbuered solution of human antibiotic I wastewater. At pH 7 by the application of ozone to nonbuered solution of human antibiotic I, pH rapidly dropped to 2.8 (data not shown) indicating the formation of acidic reaction intermediates. Low pH is known to suppress the formation of hydroxyl radicals from ozone and ozone is reacting directly by an electrophilic attack that led to 16% lower overall COD removal than that obtained in buered solution. Reaction products formed at acidic pH were resistant to oxidation by ozone whereas in case of ozonation in buered solution at pH 7 both OH radicals and ozone are the oxidizing agents hence a signicant portion of COD was removed by ozonation process. Additionally, in buered solutions even at high pH reaction rates slowed down by the progress of ozonation. This result may suggest that the generated intermediates and the acids become increasingly important scavengers of hydroxyl radicals (Beltran et al., 1999). 3.2. Eect of initial COD Due to the uctuation in the wastewater quality it is of practical interest to examine how the initial wastewater COD value aects the ozonation treatment. In Fig. 4 overall COD and aromaticity removals obtained in 1 h are summarized for various initial COD concentrations at pH 7, which is about natural pH of formulation wastewaters. In terms of COD elimination, the treatment eciency of synthetic wastewaters is seen to decrease with an increase in the initial COD value (Fig. 4). From the obtained results it can be speculated that when the initial

COD is high, more intermediates are generated during the initial period of ozonation. Hence they consume more ozone either by decomposition or reaction. Consequently, the lower ozone concentration in liquid phase leads to reduction in overall COD and UV254 with similar results observed in previous studies conducted with textile industry wastewater (Wu et al., 1998; Balcolu g Akmehmet and Arslan, 2001). However the total COD removal of human II antibiotic wastewater decreased while overall UV254 elimination exhibited an increasing trend by increasing CODi (Fig. 4). Since higher UV254 absorbance values in initial stages of ozonation were observed by increasing the initial COD value of wastewater it was expected that reaction products of human antibiotic II wastewater exerted higher ozone demand. The contradiction between the obtained results for human II antibiotic wastewater and other wastes can be explained by the fact that the ratio of chemicals having absorbance values at UV254 to the organic chemicals exerting COD was low in antibiotic II wastewater. 3.3. Eect of hydrogen peroxide Combining ozone with hydrogen peroxide to enhance oxidizing ability has been extensively researched recently and is considered to be a promising alternative for refractory organics removal from aqueous solutions (Glaze et al., 1987; Masten and Davies, 1993). It was shown that the conjugate base of H2 O2 at milimolar concentrations could initiate the decomposition of ozone much more rapidly into hydroxyl radicals than with the hydroxide ion (Staehelin and Hoign, 1982). e With the above mentioned facts in mind, ozonation of synthetic wastewater was performed in the presence of H2 O2 up to 100 mM. A lower limit for the eectiveness of the H2 O2 /O3 AOP is in a pH range of 5 to 7 based on results by Staehelin and Hoign (1982), therefore H2 O2 / e O3 process was applied to synthetic wastewaters at pH 7. The total COD and UV254 removal percentages obtained with an applied dose of 2.96 g/l h are represented in Fig. 5 as a function of H2 O2 concentration. Additionally, wastewaters were treated with mere hydrogen peroxide at same concentrations for 1 h and during the experiment no changes of parameters (COD and UV254 absorbance) were observed since the hydrogen peroxide alone is not a strong oxygen transfer agent (data not shown). The results obtained by H2 O2 /O3 process for human I and veterinary antibiotic wastewaters indicated that during the 1 h reaction period the COD and absorbance results paralleled those without the added hydrogen peroxide. These similarities may be due to the high reactivity of compounds to ozonation and the presence of high ozone concentration. Consequently, increasing hydrogen peroxide concentration up to an optimum concentration slightly enhanced the oxidation rate in the

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Fig. 4. Eect of initial COD on the ozonation of synthetic human antibiotic I, human antibiotic II and veterinary antibiotic formulation wastewater. Experimental conditions: buered solution at pH 7; treatment time 1 h.

case of human antibiotic I and veterinary antibiotic wastewaters. However for human antibiotic II, COD and aromaticity removals were enhanced from 69% and 29% to 95% and 90%, respectively, in the presence of 20 mM hydrogen peroxide with an applied ozone dosage of 2.96 g/l h. These results conrmed that the oxidation of human antibiotic II proceeded mainly by hydroxyl radicals as accordance with the results obtained at pH 3 and 11. When the applied hydrogen peroxide dose is above the optimum value at which H2 O2 tended to accumulate in water, it acted as radical scavenger (Glaze et al., 1987) and suppressed the removal of COD and UV254 . 3.4. Biodegradability enhancement Regarding ozonation as a pretreatment process for conventional treatment methods, it is important to examine its inuence to properties of organic substances like biodegradability. It is known that mostly biodegradable fraction of wastewater can be increased

by ozonation, which, leads to the formation of low molecular weight oxygenated byproducts that are more amenable to biodegradation (Hoign, 1988; Heinzle e et al., 1995; Stockinger et al., 1995). Hence BOD/COD ratios can be increased from 0 to 0.15 and 0.5 under optimum ozone conditions (Scott and Ollis, 1995; Alvares et al., 2001). Aromaticity removal was also used as a parameter for the evaluation of ozonation performance of wastewater (Jochimsen et al., 1997; Arslan et al., 1999; Benitez et al., 1999) and higher removal rates in aromaticity resulted in higher BOD/ COD ratio (Balcolu Akmehmet and Arslan, 1998; g Balcolu Akmehmet and Cecen, 1999; Beltran et al., g 1999). In this study in order to assess the eect of ozonation on the biodegradability of the wastewater, BOD5 measurements were conducted and biodegradability of wastewater was represented as BOD5 /COD ratio. BOD5 value of untreated veterinary antibiotic wastewater (CODi 900 mg/l) was 70 mg/l whereas untreated human I and human II antibiotic wastewaters were determined as nonbiodegradable. Initially, the

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Fig. 5. Eect of initial H2 O2 concentration on the ozonation of synthetic human antibiotic I, human antibiotic II and veterinary antibiotic formulation wastewater. Experimental conditions: buered solution at pH 7; CODi 450 mg/l; treatment time 1 h.

BOD5 /COD ratio for all synthetic wastewater was noticeably low and changes in BOD5 , BOD5 /COD and UV254 /COD ratios as a function of ozonation time are presented in Fig. 6. It has been previously suggested that increasing the ozone contact time rst produces more biodegradable intermediates, and that upon extension of the ozonation period biodegradability levels o (Balcolu Akg mehmet and Arslan, 2001), decrease (Takahashi et al., 1994; Jochimsen and Jekel, 1997; Imai et al., 1998) or in some cases even further increase (Gilbert, 1987; Benitez et al., 2001) depending upon the specic pollutant type in question. In this study, while the biodegradability of human antibiotic I levelled o, that of human antibiotic II and veterinary antibiotic indicated further increase with an increasing contact time. Although signicant aromaticity removal was achieved at initial period of ozonation for all wastewaters, the UV254 /COD ratio of human antibiotic I wastewater was

still high at the end of ozonation period. Correspondingly only for this wastewater BOD5 was comparably low. Specic ozone consumption represented as a function of time (Fig. 7) indicated that this value increased depending upon the initial reactivity of substances found in wastewater to ozonation. Although higher amount of COD removal was achieved for human antibiotic I wastewater than that of human antibiotic II wastewater, the biodegradability of reaction products was signicantly low.

4. Conclusions The results of the present study have clearly delineated that ozonation at natural pH values provides a promising technique for the treatment of antibiotic formulation wastewater. Results revealed that pH

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Fig. 6. Variations in BOD5 /COD, UV254 /COD ratios and BOD5 value of ceftriaxon sodium (CODi 1400 mg/l), human antibiotic II (CODi 1400 mg/l) and veterinary antibiotic (CODi 900 mg/l) formulation wastewater as a function of treatment time.

Fig. 7. Specic ozone consumption of ceftriaxon sodium (CODi 1400 mg/l), human antibiotic II (CODi 1400 mg/l) and veterinary antibiotic (CODi 900 mg/l) formulation wastewater.

control was essential to obtain ecient COD and UV254 removal. Although the O3 /H2 O2 combination had no advantage for COD removal kinetics over the direct O3 application at pH 7 the higher total removal rates of COD and UV254 were achieved by O3 /H2 O2 process once

adjusted for optimum H2 O2 concentration. Presence of 20 mM hydrogen peroxide in the ozonation process provided almost 100% of COD and UV absorbance removal for human antibiotic II wastewater (CODi 450 mg/l). Biodegradability represented in terms of

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I. Akmehmet Balcolu, M. Otker / Chemosphere 50 (2003) 8595 g Benitez, F., Beltran-Heredia, J., Torregrosa, J., Acero, J.L., 1999. Treatment of olive mill wastewater by ozonation, aerobic degradation and the combination of both treatments. J. Chem. Technol. Biotechnol. 74, 639646. Christian, G.D., 1994. Analytical Chemistry, 5th edition John Wiley and Sons, USA. EPA, 1991. Guides to Pollution Prevention: The Pharmaceutical Industry. US Environmental Protection Agency, Cincinnati, Ohio, 59. Gilbert, E., 1987. Biodegradation of ozonation products as a function of COD and DOC elimination by example of substituted aromatic substances. Water Res. 21, 12731278. Glaze, W.H., Kang, J.W., Chapin, D.H., 1987. The chemistry of water treatment processes involving ozone hydrogen peroxide and ultraviolet radiation. Ozone Sci. Eng. 9, 335351. Gulyas, H., von Bismarck, R., Hemmerling, L., 1995. Treatment of industrial wastewaters with ozone/hydrogen peroxide. Water Sci. Technol. 32, 127134. Halling-Srensen, B., Nors Nielsen, S., Lankzky, P.F., Ingerslev, F., Holten Ltzhft, H.C., Jrgensen, S.E., 1998. u Occurrence, fate and eects of pharmaceutical substances in the environmentA review. Chemosphere 36, 357393. Heinzle, E., Stockinger, H., Stern, M., Fahmy, M., Kut, O.M., 1995. Biological and combined ozonation biological treatment of chlorinated guajacols. J. Chem. Technol. Biotechnol. 62, 241252. H , C., Sigl, G., Specht, O., Wurdack, I., Wabner, D., 1997. o Oxidative degradation of AOX and COD by dierent advanced oxidation processes: a comparative study with two samples of a pharmaceutical wastewater. Water Sci. Technol. 35, 257264. Hoign, J., 1988. The Chemistry of Ozone in Water. In: Stucki, e S. (Ed.), Process Technologies for Water Treatment. Plenum, New York, pp. 121143. Imai, A., Onuma, K., Inamori, Y., Sudo, R., 1998. Eects of pre-ozonation in refractory leachate treatment by the biological activated carbon uidized bed process. Environ. Technol. 19, 213221. IOA Standardization CommitteeEurope, 001/87 (F), 1987. Iodometric Method for the Determination of Ozone in a Process Gas. Brussels. Jochimsen, J.C., Jekel, M.R., 1997. Partial oxidation eects during the combined oxidative and biological treatment of separated streams of tannery wastewater. Water Sci. Technol. 35, 337345. Jochimsen, J.C., Schenk, H., Jekel, M.R., Hegemann, W., 1997. Combined oxidative and biological treatment for separated streams of tannery wastewater. Water Sci. Technol. 36, 209 216. Kuo, C.H., Huang, C.H., 1995. Aqueous phase ozonation of chlorophenols. J. Haz. Mat. 41, 3145. K mmerer, K., Al-Ahmad, A., Mersch-Sundermann, V., 2000. u Biodegradability of some antibiotics, elimination of the genotoxicity and aection of wastewater bacteria in a simple test. Chemosphere 40, 701710. Langlais, B., Reckhow, D.A., Brink, D.R., 1991. Ozone in Water Treatment: Application and Engineering. Lewis Publishers, USA. Lansky, P., Halling-Srensen, B., 1997. The toxic eect of the antibiotic mentronidazol on aquatic organisms. Chemosphere 35, 25532561.

BOD5 /COD was observed to increase for all synthetic wastewaters. While the increase in the ratio for human antibiotic I was leveled o after 1 h ozonation at the value 0.1, further increase with a contact time was observed in the ratio for human antibiotic II and veterinary antibiotic which reached to 0.27 and 0.38 respectively. Comparably a high value of UV254 /COD ratio of human antibiotic I wastewater might be an explanation leading to this observation. In the view of these experimental results it can be concluded that ozonation could be successfully used as a pretreatment step to improve the biodegradability of wastewater containing antibiotics.

Acknowledgements The nancial support of this study by the Research Fund of Bogazici University (Project no 00Y-102) and TUBITAK (grant no YDABCAG- 199Y017) are gratefully acknowledged. The authors also wish to thank Aventis, Bayer, and Roche for supplying the antibiotics.

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