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Abstract
Antibiotic formulation effluent is well known for its important contribution to environmental pollution due to its fluctuating and
recalcitrant nature. In the present study, the chemical treatability of penicillin formulation effluent (average filtered CODoZ830 mg/l;
average soluble CODoZ615 mg/l; pHoZ6.9) bearing the active substances penicillin Amoxicillin Trihydrate (C16H19N3O5S$3H2O) and the
b-lactamase inhibitor Potassium Clavulanate (C8H8KNO5) has been investigated. For this purpose, the penicillin formulation effluent was
subjected to ozonation (applied ozone doseZ2500 mg/(l!h)) at varying pH (2.5–12.0) and O3CH2O2 (perozonation) at different initial
H2O2 concentrations (Z2–40 mM) and pH 10.5. According to the experimental results, the overall Chemical Oxygen Demand (COD)
removal efficiency varied between 10 and 56% for ozonation and 30% (no H2O2) and 83% (20 mM H2O2) for the O3CH2O2 process. The
addition of H2O2 improved the COD removal rates considerably even at the lowest studied H2O2 concentration. An optimum H2O2
concentration of 20 mM existed at which the highest COD removal efficiency and abatement kinetics were obtained. The ozone absorption
rate ranged between 53% (ozonation) and 68% (perozonation). An ozone input of 800 mg/l in 20 min was sufficient to achieve the highest
BOD5/COD (biodegradability) ratio (Z0.45) and BOD5 value (109 mg/l) for the pre-treated penicillin formulation effluent. After the
establishment of optimum ozonation and perozonation conditions, mixtures of synthetic domestic wastewaterCraw, ozonated and
perozonated penicillin formulation effluent were subjected to biological activated sludge treatment at a food-to-microorganisms (F/M) ratio
of 0.23 mg COD/(mg MLSS!d), using a consortium of acclimated microorganisms. COD removal efficiencies of the activated sludge
process were 71, 81 and 72% for pharmaceutical wastewater containing synthetic domestic wastewater mixed with either raw, ozonated or
perozonated formulation effluent, respectively. The ultimate COD value obtained after 24-h biotreatment of the synthetic domestic
wastewaterCpre-ozonated formulation effluent mixture was around 100 mg/l instead of 180 mg/l which was the final COD obtained for the
wastewater mixture containing raw formulation effluent, indicating that pre-ozonation at least partially removed the non-biodegradable COD
fraction of the formulation effluent.
q 2004 Elsevier Ltd. All rights reserved.
Keywords: Advanced oxidation processes; Biodegradability improvement; Combined chemicalCbiological treatment; Pharmaceutical wastewater;
Ozonation; O3CH2O2 process; Penicillin formulation effluent
k2
2 C O3
HOK / HO$2 C O$K
3 k2 Z 2:8 !106 l=ðmole !sÞ
(6)
HO$2 % O$K
2 CH
C
pKa Z 4:8 (7)
k3
2 C O3
O$K / O$K
3 C O2 k3 Z 1:6 !109 l=ðmole !sÞ
(8)
k4
HC C O$K
3 % HO3
$
k4 Z 5:0 !1010 l=ðmole !sÞ (9)
k5
HO$3
/ OH$ C O2 k5 Z 1:4 !105 l=ðmole !sÞ (10)
k6
2
HO$2 C O$K / HOK
2 C O2 k6 Z 8:7 !107 l=ðmole !sÞ
(11)
The reaction rate dependence on H2O2 concentration
Fig. 2. COD abatement rates at varying initial pH values. Experimental suggests that H2O2 is acting as a free radical scavenger
conditions: ozonation timeZ1 h; soluble CODoZ637 mg/l, filtered at concentrations above the theoretical, optimum require-
CODoZ838 mg/l; applied ozone doseZ2500 mg/l h. ment, i.e. at excess H2O2 concentrations. In this case,
I.A. Alaton et al. / Journal of Environmental Management 73 (2004) 155–163 159
the following radical scavenging reactions may become 30 mM, COD removal rates began to decrease revealing
important (Buxton et al., 1988): that in accordance with reactions (12) and (13), inhibition of
k7
COD removal was observed when H2O2 was applied in
H2 O2 C OH$
/ HO$2 C H2 O C O2 excess and started to consume OH%. The presence of an
(12)
k7 Z 2:7 !107 l=ðmole !sÞ optimum, critical H2O2 concentration or concentration
range for the O3/H2O2 process that usually coincided with
k8
the theoretical, stoichiometric requirement given in Eq. (4),
2 C OH
HOK OHK C HO$2
$
/ has already been evidenced in previous work (Beltran et al.,
(13)
k8 Z 7:5 !109 l=ðmole !sÞ 1998; Mitani et al., 2002). In Fig. 3, it is evident that the
inhibition of COD removal at [H2O2]oZ40 mM was only
Instead of OH%-initiated oxidative chain reactions with observed in the later stages of perozonation, i.e. at
organic pollutants symbolized as R: tR30 min. The ‘delayed’ inhibition of COD removal is
k7 speculatively attributable to the formation and accumulation
OH$ C R
/ ROH$ $2
/RO
// of more selective HO%2 oxidation products in accordance
(14)
k9 Z 108 –1011 l=ðmole !sÞ with reaction (12).
Table 4 summarizes kCOD values and percent overall
H2O2/O3 experiments were conducted at six different COD removal efficiencies obtained at different initial H2O2
initial H2O2 concentrations in the range of 2–40 mM and concentrations. For perozonation in the presence of 40 mM
pHoZ10.5. This range was selected considering typical H2O2, only the first 30 min were considered for kinetic
concentrations that have been investigated in previous evaluation of COD abatement rates.
experimental studies (Gulyas et al., 1995; Arslan-Alaton From Table 4, it can be inferred that although the best
and Akmehmet Balcioglu, 2002) and the fact that the ozone results were obtained in the presence of 20 mM H2O2, it
feed rate selected for the present work made up a total ozone would be more feasible to select 2 mM for pre-treatment
dose of 52 mM (Z2500 mg/l) after 1 h ozonation. Again, process economy. Perozonation treatment with 2 mM H2O2
the reaction pH was not controlled throughout the process resulted in comparably good COD abatement kinetics and
because it decreased to pH z8 at the end of the reaction removal efficiencies. On the other hand, it should be kept in
period which is a pH range required for the succeeding mind that because of the fact that a second, biological
biotreatment step. treatment step would follow the perozonation process, COD
Fig. 3 depicts changes in normalized COD values during ‘over-oxidation’ should be minimized. Consequently, 2 mM
perozonation at different initial H2O2 concentrations. Final H2O2 was selected as the optimum for the perozonation
COD/CODo values were obtained as 0.70, 0.24, 0.29, 0.35, process at pH 10.5.
0.17,0.30 and to 0.63 for initial concentrations of 0, 2, 5, 10, Table 5 shows O3A values and specific COD removal
20, 30 and 40 mM H2O2, respectively. From Fig. 3, it can be rates for ozonation at pH 10.5 and varying H 2O 2
stated that even at the lowest studied H2O2 concentration, concentrations. From Table 5, it is obvious that the specific
COD removal kinetics were significantly enhanced and the COD removal was highest for perozonation at 2 mM H2O2,
OH%-initiated chain reaction mechanism was favored for the speaking for the most efficient use of ozone at this H2O2
chemical, oxidative pre-treatment of the formulation concentration. Ozone absorption rates on the other hand
effluent. However, at H2O2 concentrations exceeding increased gradually with increasing H2O2, indicating that an
increase in ozone absorption rate does not necessarily result
in a higher COD removal efficiency. 51% of the applied
ozone (Z1272 mg) was absorbed during perozonation in
Table 4
First order COD removal rate constants and percent COD removal
efficiencies at varying initial H2O2 concentrations
Table 5
Ozone absorption (O3A) and specific COD removal rates at varying initial
H2O2 concentrations
Table 6b
Treatment performance of stand-alone biological treatment of simulated pharmaceutical effluent mixture, ozonation of penicillin formulation effluentC
activated sludge treatment of whole pharmaceutical effluent as well as perozonation of penicillin formulation effluentCactivated sludge treatment of whole
pharmaceutical effluent
decomposition to free radicals at elevated pH values. The in the final, treated effluent. Overall COD removal
COD abatement mechanism of ozonation seemed to efficiencies of 84 (O3) and 79% (O3/H2O2) were obtained
change and was more efficient at high pH values, for chemical oxidation of segregated penicillin formu-
especially when exceeding pH 10.5. The highest COD lation effluent combined with biological oxidation of the
removal efficiency (Z56%) was achieved at the highest whole pharmaceutical effluent.
pH tried (12.0).
† Even the lowest studied H2O2 concentration resulted in From the results obtained via combined chemical and
an appreciable enhancement in COD removal rates. COD biological oxidation of penicillin formulation effluent, it can
removal efficiency increased from 30% without H2O2 be stated that advanced oxidation has proven to be
addition to 76% in the presence of 2 mM H2O2 at pH reasonably suited and quite feasible for application as a
10.5 and an ozone dose of 2500 mg/(l!h). The highest pre-treatment method. However, a non-degradable fraction
COD removal efficiency obtained was 83% for perozo- remained in the chemically pre-treated effluent that may
nation at a H2O2 concentration of 20 mM. The COD inhibit or at least retard a succeeding biological treatment
removal rate obtained by perozonation with 20 mM system. This led us to the conclusion that factories may
H2O2 was about 50 times faster than ozonation alone at consider applying advanced oxidation as a stand-alone
pH 10.5. When the H2O2 concentration exceeded option whenever stream segregation into biodegradable and
20 mM, COD removal was inhibited seriously, revealing non-biodegradable fractions is possible so that effluent
the presence of an optimum, critical H2O2 concentration. volume and hence treatment costs can be reduced
† Preliminary experiments that were conducted to select an considerably.
optimum ozone dose to obtain the highest possible
biological treatment efficiency were simply based on Acknowledgements
BOD5 measurements. The BOD5/COD (biodegradabil-
ity) ratio increased by a factor of 6 and 23 for ozonation The authors wish to thank TUBITAK (Turkish National
at pH 12.0 and perozonation with 2 mM H2O2 at pH 10.5, Scientific and Technology Research Council) for the
respectively, at an ozone input of 800 mg/l (20 min financial support under project: ‘ICTAG—C-042’.
ozonation).
† Pharmaceutical wastewater containing raw, ozonated or
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