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: 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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First received 23 May 2011; accepted in revised form 18 August 2011
839 H. Fr. Schrder et al. | Removal and degradation of pharmaceutical compounds Water Science & Technology | 65.5 | 2012