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LEQUiA, Laboratory of Chemical and Environmental Engineering, University of Girona, Campus Montilivi, Girona, 17071, Spain
ICRA, Catalan Institute for Water Research, Carrer Emili Grahit, 101, Parc Cientc i Tecnolgic de la Universitat de Girona, 17003 Girona, Spain
Dept. Environmental Chemistry, Institute of Environmental Assessment and Water Research (IDAEA), CSIC, c/Jordi Girona 18-26, E-08034 Barcelona, Spain
a r t i c l e
i n f o
Article history:
Received 16 March 2012
Received in revised form 8 June 2012
Accepted 16 June 2012
Available online 15 July 2012
Keywords:
Ibuprofen
Kinetics
Biodegradation
Transformation products
a b s t r a c t
Pharmaceutically active compounds (PhACs) deserve attention because of their effect on ecosystems and
human health, as well as their continuous introduction into the aquatic environment. Classication schemes
are suggested to characterise their biological degradation, e.g., based on pseudo-rst-order kinetics, but these
schemes can vary signicantly, presumably due to pharmaceutical loads, sludge characteristics and experimental conditions. Degradation data for PhAC transformation products (TPs) are largely lacking.
The present work focuses not only on the biodegradation of the pharmaceutical compound ibuprofen but also
on its best-known TPs (i.e., carboxyl ibuprofen and both hydroxyl ibuprofen isomers). Ibuprofen is one of the
most commonly consumed PhACs and can be found in different environmental compartments.
The experiment performed consisted of a set of aerated batch tests with different suspended solid and ibuprofen concentrations to determine the inuence of these parameters on the calculated biodegradation constant (Kbiol). Sampling of the liquid phase at different scheduled times was assessed, removal efciencies
were calculated and pseudo-rst-order kinetics were adjusted to obtain experimental Kbiol values for the parent compound and its TPs.
The experimental data were successfully tted to ASM-based models, with Kbiol values for the target compounds ranging from almost 1 to 17 L gSST 1 d1, depending on the concentrations of the biomass and ibuprofen. This work provides innovative knowledge not only regarding the removal of TPs but also the
formation kinetics of these TPs.
2012 Elsevier B.V. All rights reserved.
1. Introduction
Residues of pharmaceutically active compounds (PhACs) have
raised concern because of their continuous introduction into the aquatic
environment (Barcel and Petrovic, 2007; Santos et al., 2009). PhACs
are administered in large quantities to humans and animals and have
been detected in all compartments of the aquatic environment
(Castiglioni et al., 2006; Bartelt-Hunt et al., 2009). The real effect of
PhACs on ecosystems and human health, directly via drinking water
and/or indirectly via the food chain, has not been completely elucidated.
Moreover, there is no legislation regarding the regulation of PhACs.
However, the impact of PhACs, considering both acute and chronic effects on non-target organisms, has been studied, with an emphasis on
Abbreviations: ASM, activated sludge model; IBU, ibuprofen; IBU-OH, hydroxyl
ibuprofen; IBU-1OH, 1-hydroxyl ibuprofen; IBU-2OH, 2-hydroxyl ibuprofen; IBU-CBX,
carboxyl ibuprofen; Kbiol, biodegradation reaction rate constant; KD, adsorption coefcient; PhACs, pharmaceutically active compounds; TP, transformation product; TSS,
total suspended solid; WWTP, wastewater treatment plant.
Corresponding author.
E-mail address: irodriguezroda@icra.cat (I. Rodriguez-Roda).
0048-9697/$ see front matter 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.scitotenv.2012.06.060
297
298
Fig. 1. Structures of: (a) ibuprofen; (b) carboxyl ibuprofen (IBU-CBX); (c) 1-hydroxyl-ibuprofen (IBU-1OH); (d) 2-hydroxyl-ibuprofen (IBU-2OH).
3. Results
3.1. Biodegradation studies on ibuprofen
Aerobic batch tests were run at different initial ibuprofen and solid
concentrations. The removal efciencies obtained are presented in
Fig. 2, illustrating variable degradation rates.
A nal signicant ibuprofen removal was achieved in most of the
tested combinations within three days. The proles shown in Fig. 2 demonstrate that the higher removal rates were obtained at higher concentrations of biomass, with faster and more complete ibuprofen removal.
In contrast, high loads of pharmaceutical compound with low biomass
concentration (50 mgTSS L1) lead to a partial ibuprofen biodegradation (b 10%, 44% and 60% accounting for 10, 100 and 1000 g L1 of
ibuprofen, respectively) and thus slower removal rates.
Therefore, the most important degradation mechanisms for ibuprofen are sorption into the sludge and biodegradation. The literature suggests that for most of the pharmaceutical compounds, removal in
activated sludge is typically described with pseudo-rst-order or mixed
second-order reaction kinetics (Joss et al., 2006; Schwarzenbach et al.,
2003). The transformation of the total (soluble plus sorbed) concentration of micropollutant is proportional to the concentrations of both
soluble micropollutant and suspended solids with a proportionality
rate constant Kbiol. If sorption equilibrium is assumed, the total concentration can be estimated as a function of the soluble concentration, a
sorption coefcient and the sludge concentration. Thus, the observed decrease in ibuprofen concentration in solution can be expressed as
rbiol
dSIBU Kbiol; IBU SIBU XTSS
1 1
L gSST d
dt
1KD;IBU XTSS
dSIBU
1 1
:
K biol; IBU SIBU X TSS L gSST d
dt
The experimental data at different biomass and ibuprofen concentrations from the previous section were tted to Eq. (1), and the ibuprofen biodegradation constants were calculated. Table 1 summarises
the corresponding set of Kbiol values obtained and the pertinent R 2
values (which were satisfactory (0.90), except for the batch test at
a low biomass content (50 mgTSS L 1) and high ibuprofen concentration (1000 g L 1)). A correspondence can be observed between
the highest Kbiol values (e.g., 1000 mgTSS L 1 with 10 gIBU L 1)
Table 1
Kbiol,IBU values with 95% condence interval and R2 values in parentheses.
[gTSS L1]
Fig. 2. Ibuprofen removal normalised to the spiked concentration (C0) at the initial time.
The continuous lines correspond to the lowest biomass concentration (50 mgTSS L1);
the discontinuous lines correspond to 100 mgTSS L1, and the dotted and discontinuous
lines correspond to 1000 mgTSS L1.
[gIBU L1]
10
100
1000
50
100
1000
6.12 (0.97)
3.97 (0.90)
0.72 (0.47)
15.70 (0.95)
6.92 (0.97)
2.02 (0.98)
17.44 (0.99)
8.57 (0.98)
4.76 (0.99)
and the more pronounced degradation proles obtained (Fig. 2), indicating a high biodegradability. The degradation proles were less pronounced for the lower reaction rate constants.
The Kbiol values obtained range from 0.72 to 17.44 L gTSS1 d1;
these values correspond well with the classication proposed by Joss
et al. (2006), indicating a partial biodegradation (2090%) for 0.1 b Kbiol b 10 and substantial removal for Kbiol values higher than
10 L gTSS 1d 1. Similar Kbiol values (935 L gTSS 1 d 1) were
observed in activated sludge systems (3 g L 1 ibuprofen and
0.51 gTSS L 1), depending on the applied technology (Joss et al.,
2006).
In contrast, lower values at higher biomass concentrations (3.8
6.2 gTSS L 1 at 1.333 L gTSS 1 d 1; Abegglen et al., 2009 and
0.209 L gTSS 1 d 1 at 2.5 gTSS L 1; Urase and Kikuta, 2005) were
obtained for low (0.52 gIBU L 1) and medium (100 gIBU L 1)
ibuprofen concentrations, respectively.
These values also depend on the sludge activity and operating
conditions. Our tests were only performed under aerobic conditions.
Values obtained at concentrations (of ibuprofen or biomass) that
are different by one or more orders of magnitude may not be representative. Thus, the correlation between the different combinations
of ibuprofen concentration, biomass concentration and Kbiol values
becomes essential (Fig. 3). The higher the ibuprofen concentration,
the lower the Kbiol value. A pattern of decreasing Kbiol values with a
decrease in the biomass concentration was also observed.
299
Ibup
rofen
[g L -1
]
TS
S
[m
gT
SS
L -1
]
Kbiol [L gTSS-1d-1]
dSIBUCBX
Kbiol;IBUCBX SIBUCBX XTSS yCBX Kbiol;IBU SIBU
dt
XTSS
4
Fig. 3. Kbiol,IBU variability among the different combinations of TSS and ibuprofen concentrations. The colour intensity of the graph changes according to the Kbiol value.
where the symbols, as presented for Eq. (2), pertain to 2-hydroxylibuprofen and carboxy-ibuprofen for Eqs. (3) and (4), respectively.
The model was applied successfully, and the experimental data
(TP formation and degradation included) were tted satisfactorily
to the simulated curve, as shown in Fig. 4, leading to the determination of Kbiol and the yield factors (Table 3). The values obtained
show a higher TP formation for IBU-2OH, while the other two TPs
maintain lower concentrations.
No references regarding yield factors for TPs are available in the
literature so far because most of the research published on the topic
investigates only their biodegradation (Quintana et al., 2005), not
their formation coordinated with the parent compound removal. As
a preliminary result, we can afrm that the yield factors obtained illustrate a higher value for IBU-2OH, indicating the predominance of
the formation of this compound compared to those of the other two
compounds. Regarding the Kbiol values, the increase in biodegradation
300
Table 2
Concentrations of ibuprofen and its TPs, together with their formation percentage ratio according to the initial parent compound concentration (100 mgTSS L1; 10 g L1
ibuprofen).
% TP/ibuprofen
t (h)
IBU
gL
0
1
18
24
42
48
66
72
10.89
8.89
4.24
3.61
1.29
0.81
0.09
0.06
IBU-1OH
IBU-2OH
mM
gL
5.29E05
4.32E05
2.06E05
1.75E05
6.26E06
3.93E06
4.37E07
2.91E07
0.18
0.31
0.21
0.72
0.43
0.48
0.34
0.33
mM
gL
7.92E07
1.42E06
9.57E07
3.23E06
1.93E06
2.17E06
1.52E06
1.47E06
0.00
1.04
1.64
2.29
1.44
0.93
0.00
0.00
IBU-CBX
1
mM
gL
0.00
4.66E06
7.37E06
1.03E05
6.50E06
4.19E06
0.00
0.00
0.00
0.98
1.21
0.80
0.59
0.58
0.65
0.00
IBU-1OH
IBU-2OH
IBU-CBX
mM
0.00
4.14E06
5.14E06
3.41E06
2.51E06
2.44E06
2.75E06
0.00
1.50
2.68
1.81
6.11
3.65
4.10
2.87
2.78
0.00
8.82
13.95
19.49
12.30
7.93
0.00
0.00
0.00
7.82
9.72
6.44
4.75
4.61
5.21
0.00
is in the following order: IBU-1OH b IBU-CBXb IBU-2OH. The most present yet most biodegradable TP was IBU-2OH, as shown by its higher
Kbiol value.
A model that separately encompasses both the formation and degradation of the three major ibuprofen TPs was suggested. A satisfactory t
was obtained, and the yield factor and Kbiol values were calculated.
4. Conclusions
Acknowledgements
IBU
IBU-CBX
IBU-2OH
8
6
4
2
0
IBU-1OH
12
10
simulated
experimental
simulated
experimental
2
1
0
3
simulated
experimental
2
1
0
3
simulated
experimental
2
1
0
0
10
20
30
40
50
60
70
80
Time (h)
Fig. 4. Experimental and simulated data, in g L1, for ibuprofen and its TPs (test at
100 mgTSS L1, 10 g L1 ibuprofen).
Table 3
Kbiol and yield values for the ibuprofen TPs (100 mgTSS L1; 10 g L1 ibuprofen).
IBU
IBU-1OH
IBU-2OH
IBU-CBX
15.7
6
0.1
12
0.4
9.6
0.2
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