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Treatment of pharmaceutical wastewater containing

antibiotics by O3 and O3/H2O2 processes

Isl Akmehmet Balcogglu *, Merih OOtker

Institute of Environmental Sciences, Boggazici University, Bebek-Istanbul 80815, Turkey

Received 19 November 2001; received in revised form 29 August 2002; accepted 29 August 2002

Abstract

Ozonation of three different synthetic pharmaceutical formulation wastewater containing two human antibiotics and

a veterinary antibiotic has been studied to enhance the their biodegradability. The effects 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 different antibiotics confirmed that the variation of biodegradability was associated with the target com-

pound. 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

effluents (Richardson and Brown, 1985; Halling-Sren-

sen et al., 1998; Kuummerer et al., 2000). These resultsinferred that antibiotics cannot be completely eliminated

during biological treatment and they are emitted into

receiving water systems. In an environmental aspect, the

most prominent effect of antibiotics is the exerting toxic

effects to aquatic organisms that would upset the

ecological balance (Lansky and Halling-Srensen, 1997;

Migliore et al., 1997). Moreover, the presence of anti-

biotics in natural systems leads to the development of

multi-resistant strains of bacteria. Hence, it is necessary

to treat the effluents 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 andanimals. High amount of antibiotics have also been used

as growth promoters in intensive farming. After ad-

ministration to human and animals up to 90% of anti-

biotics may be excreted through urine and feces into

sewage. Therefore significant 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 (Halling-

Srensen et al., 1998).

Activities in pharmaceutical industry may also be re-

sponsible for the presence of antibiotics in natural water

Chemosphere 50 (2003) 8595

www.elsevier.com/locate/chemosphere

*Corresponding author. Tel.: +90-212-385-15-40; fax: +90-

212-257-50-33.

E-mail address: [email protected] (I. Akmehmet

Balco

gglu).

0045-6535/03/$ - see front matter 2002 Elsevier Science Ltd. All rights reserved.

PII: S0 0 4 5 -6 5 3 5 (0 2 )0 0 5 3 4 -9
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systems. Pharmaceutical industry, which includes four

different 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 different operations in thisindustry, formulation effluent that rises from washing of

equipment is characterized by small effluent flow and low

pollution load. However the effluents originated from the

formulation of antibiotics have low biodegradability

since they contain almost only active substance. Hence a

chemical pretreatment is necessary for pharmaceutical

effluents, like antibiotic formulation, containing high

concentrations of bioinhibitory compounds.

During the last two decades, in order to augment

the biodegradability and also increase the efficacy of

subsequent treatment, advanced oxidation processes

(AOPs) have been applied to refractory organic pollu-tants and xenobiotics found in groundwater, surface

water and industrial wastewater (Takahashi et al., 1994;

Scott and Ollis, 1995; Alvares et al., 2001). These pro-

cesses involve the generation of highly free radicals,

mainly hydroxyl radical (HO) via chemical (O3/OH,

O3/H2O2, Fe2/H2O2), photochemical (UV-C/H2O2,

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 com-

pounds by different AOPs. However, few studies re-

ported in the literature dealt with pharmaceuticals (Rey

et al., 1999; Zwiener and Frimmel, 2000) and pharma-

ceutical effluents (Gulyas et al., 1995; Hoofl et al., 1997).

Considering the above mentioned facts, the present

investigation was aimed to study the pretreatment of

effluents originated from three different antibiotic for-

mulation process by O3 and O3/H2O2 AOPs for the

improvement of biodegradability. Cephalosporine,

penicillin, and quinolone group antibiotics were chosen

due to their high consumption rates in Turkey. The ef-

fect of initial pollution load of wastewater, pH, and

H2O2 concentration on the performance of ozonation

was evaluated in terms of conventional wastewatermeasures such as chemical oxygen demand (COD) and

biochemical oxygen demand (BOD)5. Moreover spec-

trophotometric measurements were performed for the

evaluation of aromaticity removal.

2. Materials and methods

2.1. Synthetic antibiotic formulation wastewater

Synthetic wastewaters were used throughout the

study since the formulation wastewater contains only the

finished 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 (enrofloxacin, quinolone

group; Bayer) includes 10% active substance and inor-ganic additives. Depending upon the studies carried out

on actual antibiotic formulation wastewaters initial

COD values of synthetic wastewaters were chosen be-

tween 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 ozonationsignificant changes were observed in pH value of waste-

water, buffer solutions were used in order to obtain pH

control.

The ozonation of synthetic wastewaters was per-

formed at three different pH values, which were adjusted

by phosphate buffer solutions (KH2PO4, H3PO4 for

pH 3; KH2PO4, Na2HPO4 for pH 7; Na2HPO4,

Na3PO4 for pH 10:6) (Christian, 1994).

2.2. The ozone reactor

Ozonation experiments were performed in a 1500 mlcapacity ozone bubble column for 1 h at semi-batch

mode with counter current recirculation of the liquid to

the gas flow (Arslan and Akmehmet Balcogglu, 2000).

Fisher OZ 500 model ozone generator was used for the

production of ozone from dry and pure oxygen. The

oxygen flow rate to the generator was maintained at 100

l/h and monitored with a rotameter incorporated into

the ozone generator. The diffusion rate of the ozone

oxygen mixture, introduced from the bottom of the re-

actor through a sintered glass diffusing plate, was 2.96 g/

l h. Excess ozone was passed into gas absorption bottle

containing 2% KI solution. All tubes from the ozonegenerator to the reactor and the gas absorption bottles

were made of Neoprene and the fittings from Teflon.

In experiments conducted by O3/H2O2 process, hydro-

gen peroxide addition was carried out just before

the ozone containing gas entered the reactor. All ex-

periments 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

86 I. Akmehmet Balcogglu, M. OOtker / Chemosphere 50 (2003) 8595

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absorbance at different wavelengths. Any residual H2O2was destroyed by the enzyme catalase from bovine liver

(176 000 A.U.; 1 A.U. destroys 1 lmol of H2O2/min at

pH 7 at 25 C) whenever residual H2O2 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 spectropho-

tometric 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 occurredafter 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 Hoignee, 1981), respectively. The amount of

ozone consumed within the reactor was determined from

the difference between the inlet and outlet concentra-

tions. The remaining H2O2 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 different 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 buffered solution at pH 7.

Fig. 2 shows the normalized COD, TOC and aroma-

ticity values of three different 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 ef-fective for human antibiotic I and veterinary antibiotic

wastewater and only a specific ozone dosage (O3 g/TOCig) of 1.4 g/g is needed to obtain an aromaticity removal

of 44%. Although COD and TOC values steadily de-

creased throughout the ozonation process, the absor-

bance 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

Fig. 1. Chemical structure of active substances.

I. Akmehmet Balcogglu, M. OOtker / Chemosphere 50 (2003) 8595 87

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and Huang, 1995). For human antibiotic I wastewater50% 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. Effect of pH

To elucidate the effect of pH on ozonation process,

synthetic wastewaters were subjected to ozonation in

buffered solutions at pH 3, 7 and 11 for 1 h. Table 1

displays overall COD and UV254 removals of wastewa-ters at three different 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 different 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

0

0.2

0.4

0.6

0.8

1

1.2

0 10 20 30 40 50 60 70

NormalizedTOC,

COD,

and

UV254

TOC UV254 CODHuman antibiotic I

CODi = 450 mg/l

TOCi = 167 mg/l

UV254i = 19.425

0

0.2

0.4

0.60.8

1

1.2

1.4

1.6

0 10 20 30 40 50 60 70

Normalized

TOC,

COD,

andUV254

Human antibiotic II

CODi = 450 mg/l

TOCi = 162 mg/l

UV254i= 0.456

0

0.2

0.4

0.6

0.8

1

1.2

0 10 20 30 40 50 60 70

Ozonation time (min)

NormalizedT

OC,

COD,

andU

V254

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 (buffered

solution at pH 7).


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decomposition (Langlais et al., 1991). Since the oxida-

tion 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 effect of ozonation pH on the overall

COD and aromaticity removal values exhibited a dif-

ferent 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

effect of pH on the overall COD removal of other

wastewaters was less pronounced. For veterinary anti-

biotic 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 anti-

biotic formulation contained inorganic additives, which

may act as radical scavengers at pH 11. These obser-

vations indicated that COD removal could be simply

achieved via both reaction pathways of ozone whereas

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


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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 athigher pH values.

In order to indicate importance of pH control during

ozonation process, separate ozonation experiments were

carried out by using nonbuffered solution of human

antibiotic I wastewater. At pH 7 by the application of

ozone to nonbuffered 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 electro-

philic attack that led to 16% lower overall COD removal

than that obtained in buffered solution. Reaction prod-ucts formed at acidic pH were resistant to oxidation by

ozone whereas in case of ozonation in buffered solution

at pH 7 both OH radicals and ozone are the oxidizing

agents hence a significant portion of COD was removed

by ozonation process. Additionally, in buffered 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 increas-

ingly important scavengers of hydroxyl radicals (Beltran

et al., 1999).

3.2. Effect of initial COD

Due to the fluctuation in the wastewater quality it is

of practical interest to examine how the initial waste-

water COD value affects the ozonation treatment. In

Fig. 4 overall COD and aromaticity removals obtained

in 1 h are summarized for various initial COD concen-

trations at pH 7, which is about natural pH of formu-

lation wastewaters.

In terms of COD elimination, the treatment efficiency

of synthetic wastewaters is seen to decrease with an in-

crease in the initial COD value (Fig. 4). From the ob-

tained 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. Con-

sequently, 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; BalcoggluAkmehmet 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 UV254absorbance values in initial stages of ozonation were

observed by increasing the initial COD value of waste-

water it was expected that reaction products of human

antibiotic II wastewater exerted higher ozone demand.

The contradiction between the obtained results for hu-

man 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 chemicalsexerting COD was low in antibiotic II wastewater.

3.3. Effect 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 re-

fractory organics removal from aqueous solutions

(Glaze et al., 1987; Masten and Davies, 1993). It was

shown that the conjugate base of H2O2 at milimolar

concentrations could initiate the decomposition of

ozone much more rapidly into hydroxyl radicals than

with the hydroxide ion (Staehelin and Hoignee, 1982).

With the above mentioned facts in mind, ozonation of

synthetic wastewater was performed in the presence of

H2O2 up to 100 mM. A lower limit for the effectiveness

of the H2O2/O3 AOP is in a pH range of 5 to 7 based on

results by Staehelin and Hoignee (1982), therefore H2O2/

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 H2O2 concentration. Additionally,

wastewaters were treated with mere hydrogen peroxide

at same concentrations for 1 h and during the experi-

ment no changes of parameters (COD and UV254 ab-sorbance) were observed since the hydrogen peroxide

alone is not a strong oxygen transfer agent (data not

shown).

The results obtained by H2O2/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 re-

activity 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

Table 1

Effect of pH on the overall COD and aromaticity removal rates

of wastewaters (CODi 450 mg/l) in 1 h ozonation process

Human

antibiotic I

Human

antibiotic II

Veterinary

antibiotic

COD removal (%)

pH 3 53 24 65

pH 7 74 69 88

pH 11 82 71 79

UV254 removal (%)

pH 3 75 70 82

pH 7 93 29 96

pH 11 90 25 95


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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 confirmed 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 isabove the optimum value at which H2O2 tended to ac-

cumulate 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 influence to properties of organic sub-

stances 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 (Hoignee, 1988; Heinzle

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 (Balcogglu Akmehmet and Arslan, 1998;

Balcogglu Akmehmet and Cecen, 1999; Beltran et al.,

1999). In this study in order to assess the effect of

ozonation on the biodegradability of the wastewater,

BOD5 measurements were conducted and biodegrada-

bility 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 wastewa-

ters were determined as nonbiodegradable. Initially, the

Fig. 4. Effect of initial COD on the ozonation of synthetic human antibiotic I, human antibiotic II and veterinary antibiotic for-

mulation wastewater. Experimental conditions: buffered solution at pH 7; treatment time 1 h.


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BOD5/COD ratio for all synthetic wastewater was no-

ticeably 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 first produces more biodegradable

intermediates, and that upon extension of the ozona-tion period biodegradability levels off (Balcogglu Ak-

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 specific pol-

lutant type in question. In this study, while the bio-

degradability of human antibiotic I levelled off, that of

human antibiotic II and veterinary antibiotic indicated

further increase with an increasing contact time. Al-

though significant 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. Correspond-

ingly only for this wastewater BOD5 was comparably

low.

Specific ozone consumption represented as a function

of time (Fig. 7) indicated that this value increased de-

pending upon the initial reactivity of substances found

in wastewater to ozonation. Although higher amount ofCOD removal was achieved for human antibiotic I

wastewater than that of human antibiotic II wastewater,

the biodegradability of reaction products was signifi-

cantly low.

4. Conclusions

The results of the present study have clearly delin-

eated that ozonation at natural pH values provides a

promising technique for the treatment of antibiotic

formulation wastewater. Results revealed that pH

Fig. 5. Effect of initial H2O2 concentration on the ozonation of synthetic human antibiotic I, human antibiotic II and veterinary

antibiotic formulation wastewater. Experimental conditions: buffered solution at pH 7; CODi 450 mg/l; treatment time

1 h.


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control was essential to obtain efficient COD and UV 254removal. Although the O3/H2O2 combination had no

advantage for COD removal kinetics over the direct O3application at pH 7 the higher total removal rates of

COD and UV254 were achieved by O3/H2O2 process once

adjusted for optimum H2O2 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

Fig. 7. Specific 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.

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.


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BOD5/COD was observed to increase for all synthetic

wastewaters. While the increase in the ratio for human

antibiotic I was leveled off after 1 h ozonation at the

value 0.1, further increase with a contact time was ob-

served 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 humanantibiotic 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 financial support of this study by the Research

Fund of Bogazici University (Project no 00Y-102) and

TUBITAK (grant no YDABCAG- 199Y017) aregratefully acknowledged. The authors also wish to thank

Aventis, Bayer, and Roche for supplying the antibiotics.

References

Alvares, A.B.C., Diaper, C., Parsons, S., 2001. Partial oxida-

tion by ozone to remove recalcitrance from wastewatersA

Review. Environ. Technol. 22, 409427.

APHA, 1989. Standard Methods for the Examination of Water

and Wastewater, 17th edition. American Public Health

Association, Washington, DC.

Arslan, I., Akmehmet Balcogglu, I., 2000. Effect of common

reactive dye auxiliaries on the ozonation of dyehouse

effluents containing vinylsulphone and aminochlorotriazine

dyes. Desalination 130, 6171.

Arslan, I., Akmehmet Balcogglu, I., Tuhkanen, T., 1999.

Oxidative treatment of simulated dyehouse effluent by UV

and near-UV light assisted Fentons reagent. Chemosphere

39, 27672783.

Bader, J., Hoignee, H., 1981. Determination of ozone in water

by the indigo method. Water Res. 15, 449456.

Balcogglu Akmehmet, I., Arslan, I., 1998. Application of

photocatalytic treatment to pretreated and raw effluents

from the Kraft bleaching process and textile industry.

Environ. Pollut. 103, 261268.

Balcogglu Akmehmet, I., Arslan, I., 2001. Partial oxidation of

reactive dyestuffs and a synthetic textile dye-bath by O3 and

O3/H2O2 processes. Water Sci. Technol. 43, 221228.

Balcogglu Akmehmet, I., Cecen, F., 1999. Treatability of Kraft

pulp bleaching wastewater by biochemical and photocata-

lytic oxidation. Water Sci. Technol. 40, 281288.

Beltran, F.J., Garcia-Araya, J.F., Alvarez, P., 1999. Integration

of continuous biological and chemical (ozone) treatment of

domestic wastewater: 1. Biodegradation and post ozona-

tion. J. Chem. Technol. Biotechnol. 74, 877883.

Benitez, F.J., Acero, J.L., Gonzalez, T., Garcia, J., 2001.

Ozonation and biodegradation processes in batch reactors

treating black table olives washing wastewaters. Ind. Eng.

Chem. Res. 40, 31443151.

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 treat-

ments. 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 Pharmaceu-tical Industry. US Environmental Protection Agency, Cin-

cinnati, 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 perox-

ide and ultraviolet radiation. Ozone Sci. Eng. 9, 335351.

Gulyas, H., von Bismarck, R., Hemmerling, L., 1995. Treat-

ment of industrial wastewaters with ozone/hydrogen perox-

ide. Water Sci. Technol. 32, 127134.

Halling-Srensen, B., Nors Nielsen, S., Lankzky, P.F., Ingers-

lev, F., Holten Luutzhft, H.C., Jrgensen, S.E., 1998.

Occurrence, fate and effects of pharmaceutical substancesin the environmentA review. Chemosphere 36, 357393.

Heinzle, E., Stockinger, H., Stern, M., Fahmy, M., Kut, O.M.,

1995. Biological and combined ozonation biological treat-

ment of chlorinated guajacols. J. Chem. Technol. Biotech-

nol. 62, 241252.

Hoofl, C., Sigl, G., Specht, O., Wurdack, I., Wabner, D., 1997.

Oxidative degradation of AOX and COD by different

advanced oxidation processes: a comparative study with

two samples of a pharmaceutical wastewater. Water Sci.

Technol. 35, 257264.

Hoignee, J., 1988. The Chemistry of Ozone in Water. In: Stucki,

S. (Ed.), Process Technologies for Water Treatment.

Plenum, New York, pp. 121143.

Imai, A., Onuma, K., Inamori, Y., Sudo, R., 1998. Effects of

pre-ozonation in refractory leachate treatment by the

biological activated carbon fluidized 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 effects

during the combined oxidative and biological treatment of

separated streams of tannery wastewater. Water Sci. Tech-

nol. 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, 209216.

Kuo, C.H., Huang, C.H., 1995. Aqueous phase ozonation of

chlorophenols. J. Haz. Mat. 41, 3145.

Kuummerer, K., Al-Ahmad, A., Mersch-Sundermann, V., 2000.

Biodegradability of some antibiotics, elimination of the

genotoxicity and affection 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 effect of the

antibiotic mentronidazol on aquatic organisms. Chemo-

sphere 35, 25532561.


7/29/2019 1264203.pdf

11/11

Masten, S.J., Davies, H.R., 1993. The use of ozone and other

strong oxidants for hazardous waste management. In:

Nriagen, J.O., Simmons, M.S. (Eds.), Environmental Oxi-

dants. John Wiley and Sons, New York, pp. 121.

Meyer, M.T., Bumgarner, J.E.,Thurman, E.M., Hostetler, K.A.,

Daughtridge, J.V., 1999. Occurrence of antibiotics in liquid

waste at confined animal feeding operations in surface andgroundwater. Proc. 20th Meeting of the Society of Environ-

mental Toxicology and Chemistry, Pensocola, Fla., 111.

Migliore, L., Civitareale, C., Brambilla, G., Delupis, G.D.,

1997. Toxicity of several important agricultural antibiotics

to artemia. Water Res. 31, 18011806.

Nemerow, N.L., 1978. Industrial Water Pollution: Origins,

Characters and Treatment. Addison-Wesley Publishing

Company, New York.

Ravikumar, J.X., Gurol, M.D., 1994. Chemical oxidation of

chlorinated organics by hydrogen peroxide in the presence

of sand. Environ. Sci. Technol. 28, 394400.

Rey, R.P., Padron, A.S., Leon, L.G., Pozo, M.M., Baluja, C.,

1999. Ozonation of cytostatics in water medium. Nitrogen

bases. Ozone Sci. Eng. 21, 6977.Richardson, M.L., Brown, J.M., 1985. The fate of pharmaceu-

tical chemicals in the aquatic environment. J. Pharm.

Pharmacol. 37, 112.

Scott, J.P., Ollis, D., 1995. Integration of chemical and

biological oxidation processes for water treatment: review

and recommendations. Environ. Prog. 14, 88103.

Staehelin, J., Hoignee, J., 1982. Decomposition of ozone in

water: rate of initiation by hydroxide ions and hydrogen

peroxide. Environ. Sci. Technol. 16, 676681.

Stan, H.-J., Heberer, T., Linkerh

aagner, M., 1994. Vorkommenvon Clofibrinsaaure im Gewaassersystem-ist der human-med-

izinische gebrauch Urasche fuur die kontamination von

Oberflaachen- grund und trinkwasser. Vom wasser. 83, 57

68.

Stockinger, H., Kut, O.M., Bourne, J.R., Heinzle, E., 1995.

Removal of chloro and nitro aromatic wastewater pollu-

tants by ozonation and biotreatment. Environ. Sci. Technol.

29, 20162022.

Takahashi, N., Nakal, T., Satoh, Y., Katoh, Y., 1994.

Variation of biodegradability of nitrogenous organic com-

pounds by ozonation. Water Res. 28, 15631570.

Wu, J., Eiteman, M.A., Law, S.E., 1998. Evaluation of

membrane filtration and ozonation processes for treat-

ment of reactive-dye wastewater. J. Environ. Eng. 124,272277.

Zwiener, C., Frimmel, F.H., 2000. Oxidative treatment of

pharmaceuticals in water. Water Res. 34, 18811885.


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