Chemosphere 50 (2003) 85–95

www.elsevier.com/locate/chemosphere

Treatment of pharmaceutical wastewater containing

antibiotics by O3 and O3/H2O2 processes
€ tker
glu *, Merih O
Isßıl Akmehmet Balcıo

Institute of Environmental Sciences, Bo

gazicßi 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.
Ó 2002 Elsevier Science Ltd. All rights reserved.

Keywords: Antibiotic formulation wastewater; Advanced oxidation processes; Biodegradability enhancement; Ozonation

1. Introduction biotics in natural systems leads to the development of

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-Søren-
sen et al., 1998; K€ummerer et al., 2000). These results
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 effect of antibiotics is the exerting toxic
effects to aquatic organisms that would upset the
ecological balance (Lansky and Halling-Sørensen, 1997;
Migliore et al., 1997). Moreover, the presence of anti-
*
Corresponding author. Tel.: +90-212-385-15-40; fax: +90-
212-257-50-33.
E-mail address: balciogl@boun.edu.tr (I. Akmehmet
Balcıo

glu).
0045-6535/03/$ - see front matter Ó 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 4 5 - 6 5 3 5 ( 0 2 ) 0 0 5 3 4 - 9
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 and
animals. 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-
Sørensen et al., 1998).
Activities in pharmaceutical industry may also be re-
sponsible for the presence of antibiotics in natural water
86 I. Akmehmet Balcıo

glu, M. O
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 this
industry, 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 /H2 O2 , Fe2þ /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 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; H€ofl 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 /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 ef-
fect 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 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
€ tker / Chemosphere 50 (2003) 85–95
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 ozonation
significant 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 (KH2 PO4 , H3 PO4 for
pH ¼ 3; KH2 PO4 , Na2 HPO4 for pH ¼ 7; Na2 HPO4 ,
Na3 PO4 for pH ¼ 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 flow (Arslan and Akmehmet Balcıo
glu, 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 ozone
generator to the reactor and the gas absorption bottles
were made of Neopreneâ and the fittings from Teflon.
In experiments conducted by O3 /H2 O2 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
 I. Akmehmet Balcıo
€ tker / Chemosphere 50 (2003) 85–95
glu, M. O
Fig. 1. Chemical structure of active substances.
absorbance at different 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 ¼ 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 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 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 Hoigne, 1981), respectively. The amount of
ozone consumed within the reactor was determined from
the difference between the inlet and outlet concentra-
tions. 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).
87
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/TOCi
g) 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
88 I. Akmehmet Balcıo
€ tker / Chemosphere 50 (2003) 85–95
glu, M. O

1.2

Normalized TOC, COD,

TOC UV254 COD Human antibiotic I
1
CODi = 450 mg/l

and UV254
0.8 TOCi = 167 mg/l
0.6 UV254i = 19.425

0.4
0.2
0
0 10 20 30 40 50 60 70

1.6
Normalized TOC, COD,

1.4 Human antibiotic II

CODi = 450 mg/l
1.2
and UV254

TOCi = 162 mg/l

1
UV254i= 0.456
0.8
0.6
0.4
0.2
0
0 10 20 30 40 50 60 70

1.2
Normalized TOC, COD,

Veterinary antibiotic
1 CODi = 450 mg/l
and UV254

0.8 TOCi =165 mg/l

0.6 UV254i = 11.025

0.4
0.2
0
0 10 20 30 40 50 60 70
Ozonation time (min)
Fig. 2. Variations in normalized TOC, COD, and UV254 values of synthetic wastewaters as a function of ozonation time (buffered
solution at pH ¼ 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 ¼ 1:325) compare to
other wastewaters (UV254 ¼ 0:327 for human antibiotic
II wastewater; UV254 ¼ 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
 I. Akmehmet Balcıo
€ tker / Chemosphere 50 (2003) 85–95
glu, M. O 89

Fig. 3. Absorbance behavior of wastewaters during ozonation (buffered solution at pH ¼ 7; CODi ¼ 450 mg/l).

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
90 I. Akmehmet Balcıo
€ tker / Chemosphere 50 (2003) 85–95
glu, M. O

Table 1 COD is high, more intermediates are generated during

Effect of pH on the overall COD and aromaticity removal rates the initial period of ozonation. Hence they consume
of wastewaters (CODi ¼ 450 mg/l) in 1 h ozonation process more ozone either by decomposition or reaction. Con-
Human Human Veterinary sequently, the lower ozone concentration in liquid phase
antibiotic I antibiotic II antibiotic leads to reduction in overall COD and UV254 with similar
COD removal (%) results observed in previous studies conducted with
pH ¼ 3 53 24 65 textile industry wastewater (Wu et al., 1998; Balcıo
glu
pH ¼ 7 74 69 88 Akmehmet and Arslan, 2001). However the total COD
pH ¼ 11 82 71 79 removal of human II antibiotic wastewater decreased
UV254 removal (%) while overall UV254 elimination exhibited an increasing
pH ¼ 3 75 70 82 trend by increasing CODi (Fig. 4). Since higher UV254
pH ¼ 7 93 29 96 absorbance values in initial stages of ozonation were
pH ¼ 11 90 25 95 observed by increasing the initial COD value of waste-
water it was expected that reaction products of human
the reaction pH had to be at least 7 to enhance ozone antibiotic II wastewater exerted higher ozone demand.
decomposition for higher COD reduction. The overall The contradiction between the obtained results for hu-
aromaticity removal of human antibiotic II wastewater man II antibiotic wastewater and other wastes can be
decreased by increasing pH value from 3 to 11 since the explained by the fact that the ratio of chemicals having
increase in UV254 absorbance was more pronounced at absorbance values at UV254 to the organic chemicals
higher pH values. exerting COD was low in antibiotic II wastewater.
In order to indicate importance of pH control during
ozonation process, separate ozonation experiments were 3.3. Effect of hydrogen peroxide
carried out by using nonbuffered solution of human
antibiotic I wastewater. At pH 7 by the application of Combining ozone with hydrogen peroxide to enhance
ozone to nonbuffered solution of human antibiotic I, pH oxidizing ability has been extensively researched recently
rapidly dropped to 2.8 (data not shown) indicating the and is considered to be a promising alternative for re-
formation of acidic reaction intermediates. Low pH is fractory organics removal from aqueous solutions
known to suppress the formation of hydroxyl radicals (Glaze et al., 1987; Masten and Davies, 1993). It was
from ozone and ozone is reacting directly by an electro- shown that the conjugate base of H2 O2 at milimolar
philic attack that led to 16% lower overall COD removal concentrations could initiate the decomposition of
than that obtained in buffered solution. Reaction prod- ozone much more rapidly into hydroxyl radicals than
ucts formed at acidic pH were resistant to oxidation by with the hydroxide ion (Staehelin and Hoigne, 1982).
ozone whereas in case of ozonation in buffered solution With the above mentioned facts in mind, ozonation of
at pH 7 both OH radicals and ozone are the oxidizing synthetic wastewater was performed in the presence of
agents hence a significant portion of COD was removed H2 O2 up to 100 mM. A lower limit for the effectiveness
by ozonation process. Additionally, in buffered solutions of the H2 O2 /O3 AOP is in a pH range of 5 to 7 based on
even at high pH reaction rates slowed down by the results by Staehelin and Hoigne (1982), therefore H2 O2 /
progress of ozonation. This result may suggest that the O3 process was applied to synthetic wastewaters at pH 7.
generated intermediates and the acids become increas- The total COD and UV254 removal percentages obtained
ingly important scavengers of hydroxyl radicals (Beltran with an applied dose of 2.96 g/l h are represented in Fig.
et al., 1999). 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 experi-
3.2. Effect of initial COD ment no changes of parameters (COD and UV254 ab-
sorbance) were observed since the hydrogen peroxide
Due to the fluctuation in the wastewater quality it is alone is not a strong oxygen transfer agent (data not
of practical interest to examine how the initial waste- shown).
water COD value affects the ozonation treatment. In The results obtained by H2 O2 /O3 process for human
Fig. 4 overall COD and aromaticity removals obtained I and veterinary antibiotic wastewaters indicated that
in 1 h are summarized for various initial COD concen- during the 1 h reaction period the COD and absorbance
trations at pH 7, which is about natural pH of formu- results paralleled those without the added hydrogen
lation wastewaters. peroxide. These similarities may be due to the high re-
In terms of COD elimination, the treatment efficiency activity of compounds to ozonation and the presence
of synthetic wastewaters is seen to decrease with an in- of high ozone concentration. Consequently, increasing
crease in the initial COD value (Fig. 4). From the ob- hydrogen peroxide concentration up to an optimum
tained results it can be speculated that when the initial concentration slightly enhanced the oxidation rate in the
 I. Akmehmet Balcıo
€ tker / Chemosphere 50 (2003) 85–95
glu, M. O 91

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 ¼ 7; treatment time ¼ 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 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 is
above the optimum value at which H2 O2 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 (Hoigne, 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 (Balcıo
glu Akmehmet and Arslan, 1998;
Balcıo
glu 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 ¼ 900 mg/l) was 70 mg/l whereas
untreated human I and human II antibiotic wastewa-
ters were determined as nonbiodegradable. Initially, the
92 I. Akmehmet Balcıo
€ tker / Chemosphere 50 (2003) 85–95
glu, M. O

Fig. 5. Effect of initial H2 O2 concentration on the ozonation of synthetic human antibiotic I, human antibiotic II and veterinary
antibiotic formulation wastewater. Experimental conditions: buffered solution at pH ¼ 7; CODi ¼ 450 mg/l; treatment time ¼
1 h.

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 (Balcıo
glu 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 of
COD 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
 I. Akmehmet Balcıo
€ tker / Chemosphere 50 (2003) 85–95
glu, M. O 93

Fig. 6. Variations in BOD5 /COD, UV254 /COD ratios and BOD5 value of ceftriaxon sodium (CODi ¼ 1400 mg/l), human antibiotic II
(CODi ¼ 1400 mg/l) and veterinary antibiotic (CODi ¼ 900 mg/l) formulation wastewater as a function of treatment time.

Fig. 7. Specific ozone consumption of ceftriaxon sodium (CODi ¼ 1400 mg/l), human antibiotic II (CODi ¼ 1400 mg/l) and veterinary
antibiotic (CODi ¼ 900 mg/l) formulation wastewater.

control was essential to obtain efficient COD and UV254
removal. Although the O3 /H2 O2 combination had no
advantage for COD removal kinetics over the direct O3
application at pH ¼ 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 ¼
450 mg/l). Biodegradability represented in terms of
94 I. Akmehmet Balcıo
€ tker / Chemosphere 50 (2003) 85–95
glu, M. O
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 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 financial 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.
References
Alvares, A.B.C., Diaper, C., Parsons, S., 2001. Partial oxida-
tion by ozone to remove recalcitrance from wastewaters––A
Review. Environ. Technol. 22, 409–427.
APHA, 1989. Standard Methods for the Examination of Water
and Wastewater, 17th edition. American Public Health
Association, Washington, DC.
Arslan, I., Akmehmet Balcıo
glu, I., 2000. Effect of common
reactive dye auxiliaries on the ozonation of dyehouse
effluents containing vinylsulphone and aminochlorotriazine
dyes. Desalination 130, 61–71.
Arslan, I., Akmehmet Balcıo
glu, I., Tuhkanen, T., 1999.
Oxidative treatment of simulated dyehouse effluent by UV
and near-UV light assisted FentonÕs reagent. Chemosphere
39, 2767–2783.
Bader, J., Hoigne, H., 1981. Determination of ozone in water
by the indigo method. Water Res. 15, 449–456.
Balcıo

glu 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, 261–268.
Balcıo

glu Akmehmet, I., Arslan, I., 2001. Partial oxidation of
reactive dyestuffs and a synthetic textile dye-bath by O3 and
O3 /H2 O2 processes. Water Sci. Technol. 43, 221–228.
Balcıo

glu Akmehmet, I., Cecen, F., 1999. Treatability of Kraft
pulp bleaching wastewater by biochemical and photocata-
lytic oxidation. Water Sci. Technol. 40, 281–288.
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, 877–883.
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, 3144–3151.
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, 639–646.
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, 5–9.
Gilbert, E., 1987. Biodegradation of ozonation products as a
function of COD and DOC elimination by example of
substituted aromatic substances. Water Res. 21, 1273–1278.
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, 335–351.
Gulyas, H., von Bismarck, R., Hemmerling, L., 1995. Treat-
ment of industrial wastewaters with ozone/hydrogen perox-
ide. Water Sci. Technol. 32, 127–134.
Halling-Sørensen, B., Nors Nielsen, S., Lankzky, P.F., Ingers-
lev, F., Holten L€ utzhøft, H.C., Jørgensen, S.E., 1998.
Occurrence, fate and effects of pharmaceutical substances
in the environment––A review. Chemosphere 36, 357–393.
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, 241–252.
H€ofl, 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, 257–264.
Hoigne, J., 1988. The Chemistry of Ozone in Water. In: Stucki,
S. (Ed.), Process Technologies for Water Treatment.
Plenum, New York, pp. 121–143.
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, 213–221.
IOA Standardization Committee––Europe, 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, 337–345.
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, 31–45.
K€ummerer, 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, 701–710.
Langlais, B., Reckhow, D.A., Brink, D.R., 1991. Ozone in
Water Treatment: Application and Engineering. Lewis
Publishers, USA.
Lansky, P., Halling-Sørensen, B., 1997. The toxic effect of the
antibiotic mentronidazol on aquatic organisms. Chemo-
sphere 35, 2553–2561.
 I. Akmehmet Balcıo
€ tker / Chemosphere 50 (2003) 85–95
glu, M. O
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. 1–21.
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 and
groundwater. 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, 1801–1806.
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, 394–400.
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, 69–77.
Richardson, M.L., Brown, J.M., 1985. The fate of pharmaceu-
tical chemicals in the aquatic environment. J. Pharm.
Pharmacol. 37, 1–12.
95
Scott, J.P., Ollis, D., 1995. Integration of chemical and
biological oxidation processes for water treatment: review
and recommendations. Environ. Prog. 14, 88–103.
Staehelin, J., Hoigne, J., 1982. Decomposition of ozone in
water: rate of initiation by hydroxide ions and hydrogen
peroxide. Environ. Sci. Technol. 16, 676–681.
Stan, H.-J., Heberer, T., Linkerh€agner, M., 1994. Vorkommen
von Clofibrins€aure im Gew€assersystem-ist der human-med-
izinische gebrauch Urasche f€ ur die kontamination von
Oberfl€achen- 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, 2016–2022.
Takahashi, N., Nakal, T., Satoh, Y., Katoh, Y., 1994.
Variation of biodegradability of nitrogenous organic com-
pounds by ozonation. Water Res. 28, 1563–1570.
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,
272–277.
Zwiener, C., Frimmel, F.H., 2000. Oxidative treatment of
pharmaceuticals in water. Water Res. 34, 1881–1885.