The removal and degradation of pharmaceutical

compounds during membrane bioreactor treatment

H. Fr. Schrder, J. L. Tambosi, R. F. Sena, R. F. P. M. Moreira, H. J. Jos
and J. Pinnekamp
ABSTRACT
Pharmaceutical compounds such as non-steroidal anti-inammatory drugs (NSAIDs) and antibiotics
have been detected in sewage treatment plant (STP) efuents, surface and ground water and even in
drinking water all over the world, and therefore have developed as compounds of concern.
Membrane bioreactor (MBR) treatment has gained signicant popularity as an advanced wastewater
treatment technology and might be effective for an advanced removal of these pollutants. This paper
evaluates the treatment of wastewater containing three NSAIDs (acetaminophen, ketoprofen and
naproxen) and three antibiotics (roxithromycin, sulfamethoxazole and trimethoprim) performed in
two MBRs with sludge retention times (SRTs) of 15 (MBR-15) and 30 (MBR-30) days over a period of
four weeks. It was observed that NSAIDs were removed with higher efciencies than the antibiotics
for both MBRs, and the MBR-30 presented higher removal efciencies for all the compounds than
obtained by MBR-15. Removal rates ranged from 55% (sulfamethoxazole) up to 100%
(acetaminophen, ketoprofen). Besides mineralisation biological transformation products of
ketoprofen and naproxen produced by wastewater biocoenosis were identied in both MBR
permeates using liquid chromatography coupled with mass spectrometry (LC-MS). The results
indicated the importance of investigating the environmental fate of pharmaceuticals and their
transformation products reaching the environment.
H. Fr. Schrder (corresponding author)
J. L. Tambosi
R. F. Sena
J. Pinnekamp
Institute of Environmental Engineering,
RWTH Aachen University,
Aachen,
Germany
E-mail: hf.schroeder@post.rwth-aachen.de
J. L. Tambosi
R. F. Sena
R. F. P. M. Moreira
H. J. Jos
Department of Chemical Engineering and Food
Engineering,
Federal University of Santa Catarina,
Florianpolis,
Brazil
Key words | antibiotics, high resolution mass spectrometry (HRMS), membrane bioreactor (MBR),
non-steroidal anti-inammatory drugs (NSAID), transformation products, wastewater
treatment
INTRODUCTION
To reach the desired therapeutic effects of drugs normally
applied under therapeutic use, on the one hand pharma-
ceutical compounds are designed to be stable after
ingestion till the resorption in the digestive tract has taken
place. On the other hand, these drugs should be polar struc-
tured to facilitate renal excretion after their successful
absorption and after the desired therapeutic effects has
taken place. Both properties, persistence against biochemical
degradation and polar structure, however, may be respon-
sible for the incomplete removal during conventional
biological sewage treatment. With the rapid development
of analytical techniques, it has been reported that the aquatic
environment will become more and more polluted with
pharmaceutically active compounds (drugs) at low concen-
trations (Gebhardt & Schrder zoo;; Gbel et al. zoo;).
Different sources can be indicated to explain the appearance
of drugs in the aquatic environment. Nowadays, it is widely
accepted that the main source of pollution are sewage treat-
ment plant (STP) efuents (Andreozzi et al. zoo). The
occurrence of several drugs has been reported in STP efu-
ents as well as in surface and drinking water in Brazil
(Stumpf et al. I; Bieling et al. zoo;; Favier et al. zoo;),
Canada (Miao et al. zoo|), China (Xu et al. zoo;), Germany
(Kmmerer zooI), Italy (Andreozzi et al. zoo), Spain
(Carballa et al. zoo), Switzerland (Tauxe-Wuersch et al.
zoo) and the United States (Brown et al. zoo6).
Consumption of drugs, such as non-steroidal anti-inam-
matory drugs (NSAIDs) and antibiotics belonging to classes
of pharmaceuticals that are extensively used worldwide
and consumed predominantly in developed countries, is
833 IWA Publishing 2012 Water Science & Technology | 65.5 | 2012
doi: 10.2166/wst.2012.828
assumed to be higher than several hundreds of tons per year
(Daughton & Ternes I; Kmmerer zoo|). It is supposed
that in 1995 in Germany alone more than 100 t of these
drugs were prescribed by doctors to their patients. Recent
estimations indicate that in Europe, which holds about
26% of the international pharmaceutical market, more
than 2000 different pharmaceutical products are used. So
the annual consumption of antibiotic-type substances is
comparable in quantity with that of some pesticides applied
in agriculture (Stackelberg et al. zoo|; Molinari et al. zoo6).
Some of the adverse effects caused by drug pollution
include aquatic toxicity, resistance development in patho-
genic bacteria, genotoxicity, and endocrine disruption
(Le-Clech et al. zoo6). The presence of trace pharmaceutical
and other xenobiotic compounds in drinking water is of
public health concern, as little is known about potential
chronic health effects associated with long-term ingestion
of mixtures of these compounds with the drinking water
(Quintana et al. zoo).
As conventional water and wastewater treatment pro-
cesses are unable to act as a reliable barrier towards some
pharmaceuticals, it is necessary to introduce and apply
additional advanced treatment technologies. Membrane
bioreactor (MBR) technology combines the biological
degradation process using activated sludge with a direct
solidliquid separation by membrane ltration (Ternes
et al. zoo;). MBR treatment has gained signicant popularity
recently and can be useful for the above mentioned pur-
poses. Drug removal by MBRs has been reported in the
literature (Gebhardt & Schrder zoo;; Gbel et al. zoo;).
In this study, six pharmaceuticals of large consumption
worldwide, three NSAIDs (acetaminophen, ketoprofen and
naproxen) and three antibiotics (roxithromycin, sulfa-
methoxazole and trimethoprim) were selected to monitor
their fate during MBR pilot plant treatment, as well as
their total removal efciencies. The qualitative and quanti-
tative monitoring of the compounds along the MBR
treatment was performed using liquid chromatography
coupled with mass spectrometry (LC-MS).
METHODS
Materials
Ultra-pure water used during sample treatment or as LC
mobile phase component was prepared using a Milli-Q
system (Millipore, Milford, MA, USA). All solvents used as
mobile phases, for desorption of the pharmaceuticals and
their potential degradation products extracted by solid
phase extraction (SPE), were nanograde solvents purchased
from LGC Promochem (Wesel, Germany). All other chemi-
cals used were of analytical reagent or residue analysis
purity grade. Gases applied were products of Linde,
Germany, and were of 99.99% purity.
The pharmaceutical compounds used in this study
were purchased from Sigma-Aldrich. Relevant information
about these pharmaceuticals is given in Table 1. Concen-
trated stock solutions were used for the analytical
determination and for spiking purposes. To avoid degra-
dation during the test period these methanolic solutions
were kept at 18
W
C.
Membrane bioreactor (MBR) pilot plants
Wastewater used as feed for the MBR pilot treatment plant
was taken continuously from the efuent of the pre-settling
tank of the municipal STP of Aachen, Germany. MBR treat-
ment was performed over a period of four weeks. The sludge
retention time (SRT), sludge concentration (SC) and the
hydraulic retention time (HRT) of the pilot plants were
15 d, 12 g/L and 9 h for MBR-15, and 30 d, 12 g/L and
13 h for MBR-30, respectively. Both MBRs used in this
study were equipped with hollow-bre ultraltration (UF)
membranes (PURON, KMS Germany), 1.43 m
2
in dimen-
sion. The nominal pore size and material of the membrane
were 0.04 m and polyethersulfone (PES), respectively.
The steady-state in the MBR was reached over six months
before the nal monitoring tests started. The ideal mixing
in the MBRs was monitored and conrmed by using a con-
ductivity probe. This was accomplished by a sodium
chloride (NaCl) addition applied as tracer compound in par-
allel to the daily drug dosages.
Spiking and sampling
For spiking a mixture of a dened stock solution of the
target pharmaceuticals in combination with a NaCl solution
was spiked into the feed of each MBR to reach a mean
steady-state concentration of 50 g/L of the target pharma-
ceuticals and 0.8 g/L NaCl. Within the week, spiking was
performed by the addition of 2/3 (33.33 g/L) of the total
daily spiking quantity in the morning (10:00 a.m.) and 1/3
(16.67 g/L) in the afternoon (04:00 p.m.). Spiking during
the weekend was performed by the addition of the total
amount of 50 g/L at 04:00 p.m. in the afternoon. Every
day at 03:00 p.m. in the afternoon samples of 500 mL of
each MBR and its permeate were taken. In parallel, a
834 H. Fr. Schrder et al. | Removal and degradation of pharmaceutical compounds Water Science & Technology | 65.5 | 2012
sludge quantity of 16L (MBR-15) or 8L (MBR-30) of excess
sludge was discharged in order to keep the sludge concen-
tration (SC) constant in each MBR.
Sample preparation
The pharmaceuticals present in the MBR permeates were
concentratedusing commercially available solidphase extrac-
tion (SPE) cartridges (1 mL) lled with 100 mg of Isolute
ENVmaterial from IST (Mid Glamorgan, UK). Prior to
use SPE cartridges were handled as prescribed by the manu-
facturer. After the SPE procedure, the cartridges were
rinsed with three bed volumes of ultra-pure water to remove
salts prior to being dried in a gentle stream of nitrogen at
30
W
C. The pharmaceuticals adsorbed at the SPE material
were desorbed by the in-series addition of 6 1 mL of metha-
nol. STP eluates were brought to dryness in a gentle stream
of nitrogen at 60
W
C. The dry residues containing the pharma-
ceuticals were reconstituted in 1 mL of methanol/water (1:1)
and were used for injection during LC-MS analysis.
Table 1 | Name, sum formula, CAS N
W
, structure, pK
a
and log K
OW
of pharmaceuticals and transformation products under research (Kimura et al. 2005; Kim et al. 2007)
Name (Sum formula) CAS Structure Acidic, base or neutral pKa log Kow
Acetaminophen (C
8
H
9
O
2
N) 103-90-2 N 9.39 0.46
Ketoprofen (C
16
H
14
O
3
) 22071-15-4 A 4.45 3.12
Naproxen (C
14
H
14
O
3
) 22204-53-1 A 4.15 3.18
Roxithromycin (C
41
H
76
N
2
O
15
) 80214-83-1 B 8.89.2 2.75
Sulfamethoxazole (C
10
H
11
N
3
O
3
S) 723-46-6 A 1.85.7 0.89
Trimethoprim (C
14
H
18
N
4
O
3
) 738-70-5 B 6.67.2 0.91
Ketoprofen transformation product (C
11
H
12
O
5
) A
Naproxen transformation product (C
13
H
12
O
3
)
A

835 H. Fr. Schrder et al. | Removal and degradation of pharmaceutical compounds Water Science & Technology | 65.5 | 2012
Liquid chromatographic and MS data
LC-separations were carried out with a Hypersil GOLD aQ
column (RP5, 5 m, spherical; 150 2.1 mm I.D.) equipped
with a Hypersil GOLD aQ pre-column (10 2.1 mm I.D.),
also lled with 5 m spherical material (Thermo Electron,
USA). Gradient elution by means of (A) methanol/water
90:10 (v:v) in combination with (B) Milli-Q-puried water/
methanol 90:10 (v:v) was applied, both containing 2 mM
ammonium acetate. The gradient was programmed as fol-
lows. Starting with 20% A/80% B the concentration was
increased linearly to 90% A/10% B within 12 min. The com-
position was kept constant for 20 min. The overall ow rate
was 0.2 mL/min. Instrument control data acquisition and
data processing were performed using Xcalibur 2.0 software
(Thermo Electron). Identication and quantication of
spiked pharmaceuticals as well as recognition and identi-
cation of transformation products, respectively, in MBR
permeates were performed by means of a LTQ Orbitrap
mass spectrometer (Thermo Electron, Germany). Electro-
spray ionization (ESI) was applied in the positive (for
roxithromycin, sulfamethoxazole, trimethroprim and aceta-
minophen) or in the negative (for ketoprofen and
naproxen and their transformation products) ionization
mode as described by Gebhardt & Schrder (zoo;). To cal-
culate the efciency of drug removal from the spiked
wastewater, the concentrations of the precursor drugs in
the MBR inow were determined in parallel quantitatively
using LC-MS after SPE.
Recovery, determination and quantication of spiked
pharmaceuticals in feed and permeates were performed by
means of LC-MS applying ESI ionization in positive or
negative mode (Bieling et al. zoo;) under high resolution
mass spectrometric conditions (HRMS). The limits of detec-
tion (LODs) and the limits of quantication (LOQs) in
LC-MS mode were calculated by a signal-to-noise ratio of
3 (S/N 3:1).
RESULTS AND DISCUSSION
Removal of pharmaceutical compounds
The mean removal rates of target pharmaceuticals spiked
into two MBRs with different SRTs and treated over a
period of four weeks are shown in Figure 1. During the spik-
ing period we observed the behaviour of the compounds
differing one from another. This will be discussed below.
A complete removal of the hydrophilic compound acet-
aminophen (log K
ow
<1) in both MBRs was observed (cf.
Figure 1) due to its less complex chemical structure. Elimin-
ation could be cleared up by LC-MS monitoring as
biodegradation. These results are in agreement with the
results reported by Kim et al. (zoo;), who obtained a 99%
removal of acetaminophen during the treatment of munici-
pal wastewater in a MBR pilot plant.
Concerning the ketoprofen behaviour, an almost com-
plete removal of the precursor drug can also be observed
for this compound in both MBRs. The compound ketopro-
fen has a moderate hydrophobic nature (log K
ow
>3) and
acidic character. According to Quintana et al. (zoo), for
polar compounds like acidic pharmaceuticals, microbial
degradation obviously is the most important removal pro-
cess in activated sludge wastewater treatment while
Figure 1 | Mean elimination rates of pharmaceutical compounds during a four week MBR treatment period applying in parallel two different sludge ages. : 15 days (MBR-15) or

: 30
days (MBR-30).
836 H. Fr. Schrder et al. | Removal and degradation of pharmaceutical compounds Water Science & Technology | 65.5 | 2012
neither retention by adsorption at the sewage sludge nor
membrane material will take place. Kimura et al. (zoo)
compared the elimination of ketoprofen treating municipal
wastewater in parallel using either an MBR pilot plant or a
conventional activated sludge treatment (CAST) plant.
Wastewater treatment in a CAST plant led to a concen-
tration of 300 ng/L of ketoprofen in the efuent while in
the permeate after MBR treatment only about 10 ng/L was
found.
The compound naproxen has comparable physicochem-
ical properties as ketoprofen, however, naproxen removal
in both MBRs was lower than ketoprofen removal. This be-
haviour of naproxen can be partially explained by its more
steric complex chemical structure stabilized by an aromatic
naphthalene ring system. According to the study of Quintana
et al. (zoo) on microbial degradation of pharmaceuticals, the
degradation of naproxen was found to be low with an
approximately 60% transformation in 28 days. In parallel
only one transformation product could be detected.
The compound roxithromycin has a low hydrophobic
nature (log K
ow
2.75) and a basic character. Roxithromy-
cin equipped with the most complex chemical structure
compared to the target compounds acts as an antibacterial
agent. Similar results for roxithromycin removal for MBR
were reported by Gbel et al. (zoo;), where the elimination
varied between 39% for an SRT of 16 days and 60% for
higher SRTs (33 and 60 days).
The compound sulfamethoxazole is a hydrophilic com-
pound (log K
ow
<1) with two ionizable amine groups. At
pH values between the pK
a
values of the compound (pH
1.8 and 5.7), sulfamethoxazole is present predominantly as
a neutral species, while above the second pK
a
value of the
compound (pH 5.7), it becomes a negatively charged
species. These physicochemical properties give an indi-
cation that in the MBR system we studied, the sludge
adsorption mechanism at pH 7.2 played a negligible role,
due to electrostatic repulsion between the negatively
charged groups of the compound and the negatively charged
surfaces of the sludge. Therefore, biodegradation has to be
the main mechanism responsible for the removal, however,
will be diminished by its antibacterial property. Gbel et al.
(zoo;) who also studied the elimination of sulfamethoxazole
reported an elimination efciency of around 80%, indepen-
dent of adjusted SRTs.
For the compound trimethoprim the highest removal
efciency among the antibiotics examined could be
observed. This can be partially explained by its hydrophilic
nature (log K
ow
<1), the basic character and its reduced
antibacterial potency compared to sulfamethoxazole and
roxithromycin. As also observable for the other drugs the tri-
methoprim removal observed for MBR-30 was 10% higher
than with the shorter SRT in the MBR-15 treatment.
Gbel et al. (zoo;) also studied the elimination of trimetho-
prim by MBR, reporting comparable elimination rates for
SRT of 16 and 33 days (30%), while 87% of removal was
obtained for SRT of 6080 days.
Mechanisms inuencing the removal of pharmaceutical
compounds
The elimination of pharmaceutical compounds can occur
through various mechanisms during MBR treatment pro-
cess. Sorption onto sludge is one of the mechanisms and
therefore the absorption and adsorption factors have to be
taken into account. According to Carballa et al. (zoo),
absorption refers to the hydrophobic interactions of the ali-
phatic and aromatic groups of a compound with fats present
in the sludge or with the lipophilic cell membranes of the
microorganisms, depending on the target K
ow
value. Adsorp-
tion refers to the electrostatic interactions of positively
charged groups of dissolved chemicals with the negatively
charged surfaces of the microorganisms (characterized by
the dissociation constant pK
a
). Gbel et al. (zoo;) studied
the elimination of pharmaceuticals by MBRs as well as
CAST and concluded that the contribution of activated
sludge adsorption in the case of pharmaceutical compounds
was less than 6%.
The physical retention of the pharmaceutical targets we
have to take into account, was a result of adsorption by an
increased sludge concentration (MLSS) while no retardation
will happen by membrane separation. Membranes used in
the ultraltration MBR process have molecular weight
cut-offs (MWCO) of approx. 100,000 Da while target phar-
maceuticals had molecular weights below 1,000 Da. Target
compounds which are unpolar will adsorb onto the biomass
and therefore will be removed together with the excess
sludge, while polar drugs, with a low tendency to adsorb at
the lipophilic sludge surface, will neither be eliminated by
adsorption nor by biodegradation. The reason is that the
interaction with wastewater biocoenosis essential for the bio-
degradation process may be too short for a degradation.
Nevertheless, biochemical degradation is the most
important elimination mechanism for the target compounds
in wastewater. This degradation often has transformation
products which are more stable than their precursor drugs.
In our examinations part of the transformation products
observed by Quintana et al. (zoo) for ketoprofen and
naproxen were also observed, with their structure as
837 H. Fr. Schrder et al. | Removal and degradation of pharmaceutical compounds Water Science & Technology | 65.5 | 2012
shown in Table 1. Their recognition in the wastewater was
only possible by extraction of their mass traces from the
negatively generated TICs recorded in HRMS mode. There-
fore, the presence of the ketoprofen transformation product
3-(hydroxy-carboxymethyl)hydratropic acid as an intermedi-
ate compound and the naproxen transformation product
O-desmethyl-naproxen could easily be conrmed.
CONCLUSIONS
The performance of two MBR pilot plants with submerged
membranes was examined in this study. The results obtained
proved that the MBR-30 presented higher removal efcien-
cies for all the compounds than obtained by MBR-15. The
compounds acetaminophen and ketoprofen had the highest
removal efciencies, while roxithromycin and sulfamethox-
azole as bacteriostatics exhibited persistence to microbial
attack and were removed to a less extent in both MBRs.
Concerning the potential mechanisms responsible for the
removal of the target pharmaceuticals in MBRs (sludge sorp-
tion biodegradation membrane retention), it was not
possible to determine exactly to what extent each mechan-
ism contributed to the removal efciency because excess
sludge analysis was not performed in this examination.
Retention by membranes using microltration or ultraltra-
tion membranes with MWCO of 100,000 Da can be
neglected. Biodegradation, however, played an important
role, since higher removal efciencies was obtained for
higher SRTs. Nevertheless, the elimination by MBR treat-
ment using ultraltration was only partially successful and
therefore, persistent pharmaceuticals in small concen-
trations were discharged with the wastewater into the
environment. This discharge could be reduced with the
application of additional post treatment steps using
advanced treatment techniques, e.g., activated carbon
adsorption, ozone oxidation or advanced oxidation pro-
cesses (AOP). In conclusion, the results indicated the
importance of investigating the generation and environ-
mental fate of transformation products of pharmaceuticals,
especially their whereabouts during wastewater treatment
process. Thus, additional research is overdue to assess the
impact of these compounds, hitherto hardly known but
more polar than their precursors and therefore quite
mobile in the aquatic environment. Discharged with treat-
ment plant efuents into surface waters the compounds
will reach ground water predetermined to reach drinking
water treatment and nally drinking water (Stackelberg
et al. zoo|; Kim et al. zoo;).
ACKNOWLEDGEMENTS
The authors would like to thank the Coordenao de Aper-
feioamento de Pessoal de Nvel Superior (CAPES) and the
Deutscher Akademischer Austauschdienst (DAAD, German
Academic Exchange Service) for nancial support. Analyti-
cal support from the staff of the Environmental Analytical
Laboratory of the Institute of Environmental Engineering
of RWTH Aachen University is also kindly acknowledged.
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839 H. Fr. Schrder et al. | Removal and degradation of pharmaceutical compounds Water Science & Technology | 65.5 | 2012