Journal of Hazardous Materials 239–240 (2012) 64–69

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Journal of Hazardous Materials

journal homepage: www.elsevier.com/locate/jhazmat

Removal of emerging contaminants from municipal wastewater with an

integrated membrane system, MBR–RO
Davor Dolar a,b,∗ , Meritxell Gros b , Sara Rodriguez-Mozaz b , Jordi Moreno c , Joaquim Comas c ,
Ignasi Rodriguez-Roda b,c , Damià Barceló b,d
a
Faculty of Chemical Engineering and Technology, Department of Physical Chemistry, Marulićev trg 19, HR-10000 Zagreb, Croatia
b
Catalan Institute for Water Research (ICRA), Parc Científic I Tecnològic de la Universitat de Girona, E-17003, Girona, Spain
c
Laboratory of Chemical and Environmental Engineering (LEQUiA), University of Girona, Girona. E17071, Spain
d
Department of Environmental Chemistry, IDAEA-CSIC, C/Jordi Girona 18-26, 08034, Barcelona, Spain

a r t i c l e i n f o a b s t r a c t

Article history: The presence of emerging contaminants in the aquatic environment and their potential effects on living
Received 15 September 2011 organisms has become an issue of growing concern. Among emerging contaminants, pharmaceuticals
Received in revised form 1 February 2012 may enter the aquatic environment due to their high consumption and their incomplete removal in
Accepted 9 March 2012
conventional municipal wastewater treatment plants (WWTPs).
Available online 20 March 2012
The main goal of this study was the assessment of the removal efficiency of pharmaceuticals found
in municipal wastewater of a coastal WWTP (Castell-Platja d’Aro, Spain) using an integrated pilot scale
Keywords:
membrane system (MBR–RO).
Emerging contaminants
Pharmaceutical
Twenty multiple-class pharmaceuticals (including psychiatric drugs, macrolide antibiotics, ␤-blockers,
Membrane bioreactor sulfonamide and fluoroquinolone antibiotics, histamine H2 receptor antagonists, anti-inflammatories,
Reverse osmosis nitroimidazole, ␤-agonist and antiplatelet agent) were measured in real influent with the lowest average
Removal from municipal wastewater concentration for psychiatric drugs (0.017 ␮g L−1 ) to the highest for macrolide antibiotics (2.02 ␮g L−1 ).
Although some contaminants were in relatively high concentrations (even up to 2.90 ␮g L−1 in the case
of ofloxacin).
The combination of MBR and RO treatment showed excellent overall removal of target emerging
contaminants with removal rates above 99% for all of them. For some compounds (metronidazole,
hydrocodone, codein, ranitidine) MBR provided high removal efficiency (up to 95%). Additionally RO
membrane showed removal rates always higher than 99%.
© 2012 Elsevier B.V. All rights reserved.

1. Introduction their large usage. As many studies have reported, the elimination
of some pharmaceutical compounds during conventional wastew-
The growing use of micropollutants, worldwide, including phar- ater treatment processes is rather low [4,5] and as a result, they
maceutical compounds, has become a new environmental problem, are found in surface, ground and even drinking water [6,7]. Con-
which has awakened great concern among scientists in the last few sequently, there is a growing need to develop reliable wastewater
years. Even though pharmaceutical compounds are found in very treatment methods, which enable an efficient removal of emerging
low concentrations in the environment [1–3], there is still a lack contaminants at trace levels.
of knowledge about long-term risks that the presence of a large The combination of membrane bioreactor coupled to reverse
variety of drugs may pose to aquatic organisms and human health, osmosis (MBR–RO) for water treatment has been successfully
even at those low concentrations. applied for the treatment of raw sewage and secondary effluent to
One of the biggest contributors of pharmaceuticals in the produce reclaimed water [8] and also for the treatment of municipal
environment are wastewater treatment plants (WWTPs). Pharma- wastewater [9]. The latter authors showed that combination of MBR
ceuticals are continuously introduced into sewage waters due to and RO provided a superb quality effluent due to excellent removal
of suspended solids (SS), turbidity and chemical oxygen demand
(COD) for 99.99%, 99.72% and 97.3%, respectively. The levels found
for these parameters were below 1 mg L−1 for SS and 8–32 mg L−1
∗ Corresponding author at: Faculty of Chemical Engineering and Technology, for COD.
Department of Physical Chemistry, Marulićev trg 19, HR-10000 Zagreb, Croatia. According to the authors knowledge only few papers were
Tel.: +385 1 4597 232; fax: +385 1 4597 250.
E-mail address: [email protected] (D. Dolar).
investigating removal of emerging contaminants with MBR–RO

0304-3894/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.jhazmat.2012.03.029
 D. Dolar et al. / Journal of Hazardous Materials 239–240 (2012) 64–69 65

[10–12]. These studies were performed at lab-scale with either syn- cartridges (Waters Milford, MA, USA). Elution was performed with
thetic or real water spiked with target compounds. Sahar et al. 6 mL of methanol at 1 mL min−1 . The extracts were evaporated
[10] compared conventional activated sludge (CAS)-UF/RO with under a gentle nitrogen stream and reconstituted with 1 mL of
MBR–RO system for treating raw sewage of the Tel-Aviv WWTP methanol-water mixture (10:90, v/v). Finally 10 ␮L of a 1 ng mL−1
in a pilot plant scale and investigated removal of 11 selected standard mixture containing isotopically labeled standards were
compounds (six antibiotics, three pharmaceuticals, BPA and choles- added in the extract for internal standard calibration to compensate
terol). Authors showed high removal rates (>93%) after the RO for possible matrix effects, which are one of the main drawbacks of
stage. However, low antibiotics concentrations in permeate indi- liquid chromatography (LC) coupled to mass spectrometry analysis.
cated that although RO is an efficient removal treatment option, it Instrumental analysis was performed with an ultraperfor-
cannot serve as an absolute barrier to various organic micropollu- mance liquid chromatography (UPLC) (Waters Corp., Milford, MA,
tants [10,11]. Alturki et al. [12] used laboratory scale MBR treatment USA) coupled to a quadrupole-linear ion trap (QqLIT) 5500QTRAP
with NF and RO membrane filtration for the removal of 40 spiked mass spectrometer (Applied Biosystems-Sciex, Foster City, CA,
trace organic contaminants (pharmaceutically active compounds, USA). Quantitative analysis was performed using Selected Reaction
steroid hormones, industrial compounds and pesticides). They Monitoring mode (SRM), in positive and negative electrospray-
reported that NF/RO and MBR treatment can complement each ionization mode.
other very well to achieve an enhanced removal efficiency of a wide Regarding quality parameters, method LOQs were calculated on
range of trace organic contaminants. the basis of signal-to-noise ratio (S/N) of 10. Recoveries of target
Thus, the main goal of this work was to assess the removal effi- compounds ranged from 60% to 120% and are reported in detail by
ciency (after each step and overall) of selected pharmaceuticals Gros et al. [15].
from a real influent of a coastal municipal WWTP (Castell-Platja Considering that pharmaceuticals have rather different physico-
d’Aro, in Catalonia, NE of Spain) by using an integrated membrane chemical characteristics, their removal during treatment is
system (MBR–RO) in a pilot scale. expected to be diverse. In the literature, the removal efficiency is
generally computed as the percentage of reduction between the
dissolved aqueous phase concentration of the contaminant in the
2. Methods and materials
influent and the dissolved aqueous phase concentration of the con-
taminant in the effluent. Except for a few studies, pharmaceutical
2.1. MBR–RO pilot plant
concentrations in sludge or suspended solid are generally not con-
sidered nor measured, probably because of the difficulty to sample
This study was carried out in a MBR–RO pilot plant (Fig. 1)
and to analyze such complex matrices [16].
installed in the full-scale Castell-Platja d’Aro WWTP and treating
(4.3 m3 day−1 ) real raw municipal wastewater. The plant consists
3. Results and discussion
of a primary wastewater settler followed by a MBR with Univer-
sity of Cape Town (UCT) configuration (i.e. anaerobic, anoxic and
3.1. Occurrence of emerging contaminants in the influent
aerobic tanks) and membrane compartment for biological nutrient
removal as described in detail by Monclús et al. [13]. The membrane
Target pharmaceuticals found in the influent of wastewater
compartment holds 8 m2 of flat sheet membranes (Kubota, porous
treatment plant and their physicochemical properties are given in
size of 0.4 ␮m). The temperature inside the reactor was 16.1 ± 0.5 ◦ C
Table 1. Pharmaceuticals analyzed are representative of different
during the whole sampling campaign. Sludge from WWTP was
chemical families and have different physicochemical properties.
cultivated over a period of approximately 3 months to reach steady-
They were selected based on their very frequent usage and there-
state conditions before running the removal experiments in the
fore ubiquitous presence in wastewaters.
pilot plant. The MBR was operating with hydraulic retention time
In Table 2 range of levels observed in influent wastewaters
(HRT) of 12.5 h and solid retention time (SRT) was 45 days during
for each contaminant (with their mean values) are presented.
the sampling campaign. MBR provides feed water for the coupled
Levels of target compounds were in the ng L−1 range but concen-
RO system, composed of one pressure vessel housing, a double
trations of some of them exceed 1 ␮g L−1 range (clarithromycin,
element (Ropur membranes TR70-4021-HF) with an automatic
ofloxacin, metronidazole and atenolol). The WWTP Castell-Platja
cleaning system. The RO membrane is a high flow, crosslinked,
d’Aro (located at the area of Mid-Costa Brava) receives domestic
aromatic polyamide, negative charge spiral wound module [14].
(95%) and industrial (5%) wastewater, and thus high concentrations
Transmembrane pressure in RO module was 10 ± 1 bar while flow
of selected compounds were found.
of the reverse osmosis element was 179.35 ± 1.28 L h−1 .
Among the encountered emerging contaminants the
highest concentrations in influent were found for fluoro-
2.2. Sampling, sample preparation and instrumental analysis quinolone antibiotic ofloxacine (up to 2.90 ␮g L−1 ), macrolide
antibiotics clarithromycin (0.700–2.72 ␮g L−1 ), ␤-blocker
Samples were taken along a week in 5 occasions at three dif- atenolol (0.916–2.44 ␮g L−1 ), antibiotic metronidazole (up to
ferent points of the MBR–RO pilot plant taking into account the 1.14 ␮g L−1 ) and histamine H2 receptor antagonist ranitidine
HRT of the MBR. The sampling points were: (1) real fresh munici- (0.202–0.932 ␮g L−1 ). Other authors [17–19] presented simi-
pal wastewater-sewer (influent), (2) MBR effluent, i.e. feed for RO lar ranges (ng L−1 to ␮g L−1 ) for the pharmaceuticals found in
element, and (3) permeate of RO element. Wastewater samples the municipal wastewaters. Macrolide antibiotics are largely
were collected in 1 L amber glass bottles pre-rinsed with Milli- excreted into sewage in their unchanged forms at excretion
Q water. Samples were kept at 4 ◦ C during transportation (1 h) rates greater than 60% [17] and they are usually found in
and were immediately (after arrival at the laboratory) vacuum wastewaters at high concentrations. Very high concentrations of
filtered through 1 ␮m glass microfibre filter (Whatman, UK) fol- clarithromycin (0.700–2.72 ␮g L−1 ) were observed. Despite of its
lowed by 0.45 ␮m Nylon membrane filters (Millipore, Ireland). high consumption, erythromycin was found at much lower levels
The target compounds were preconcentrated from water phase (0.032–0.080 ␮g L−1 ) than clarithromycin. This might be caused
using the method described by Gros et al. [15]. An automated by the conversion of erythromicin to erythromycin-H20 in the
solid phase extraction system, GX-271 ASPECTM (Gilson, Middle- aquatic environment as it has been previously reported [20]. On the
ton, USA) was used for sample preconcentration using Oasis HLB other hand, ␤-blockers, used for various indications (heart attack,
66 D. Dolar et al. / Journal of Hazardous Materials 239–240 (2012) 64–69

Fig. 1. Schematic representation of the MBR–RO pilot plant showing the different compartments, flow directions, main instruments and equipment.

cardiac arrhythmias and hypertension), were present in relatively The most important removal pathways of organic com-
high concentration (up to 2.44 ␮g L−1 ) and is in an agreement pounds with MBR are biotransformation/biodegradation (biotic)
with concentrations presented by other authors [19,21]. One of and adsorption (abiotic) by the sludge (excess sludge removal). Abi-
the highest concentration was for ofloxacin but it was more than otic and biotic processes could not be distinguished in this study
10 times smaller than concentration obtained by Radjenović et al. and therefore removal percentage stands for the overall elimination
[19]. of the parent compound from water.
For the macrolide antibiotics MBR treatment showed mean
3.2. Removal of emerging contaminants with MBR removal from 75% to 87%. Under typical wastewater conditions,
many macrolides can be adsorbed into biomass, mainly attributed
Overall removal of the 20 detected pharmaceuticals with to hydrophobic interactions due to their high log DpH 6–8 partition-
MBR–RO system is presented in Fig. 2. When comparing pharma- ing coefficients (Table 1). Many macrolides are positively charged
ceutical concentrations in influent and MBR effluent or RO perme- whereas sludge surface is predominantly negatively charged,
ate, as we did in this work, lower levels in effluent or permeate which leads to adsorption of these compounds to biomass via cation
were interpreted as a removal of the compound in the MBR or RO. exchange processes [17].

Table 1
Physicochemical properties of detected pharmaceuticals.

Name CAS number Formula MW (g mol−1 ) log KOW log Da

Codeine 76-57-3 C18 H21 NO3 299.37 1.19 –

Hydrocodone 143-71-5 C18 H21 NO3 299.37 2.16 –
Carbamazepine 298-46-4 C15 H12 N2 O 236.28 2.45 2.67b
Diazepam 439-14-5 C16 H13 ClN2 O 284.75 2.82 –
Lorazepam 846-49-1 C15 H10 Cl2 N2 O2 321.17 2.39 –
Famotidine 76824-35-6 C8 H15 N7 O2 S3 337.45 −0.64 –
Ranitidine 66357-35-5 C13 H22 N4 O3 S 314.41 0.27 –
Azithromycin 83905-01-5 C38 H72 N2 O12 749.00 4.02 −0.65 to 2.3c
Clarithromycin 81103-11-9 C38 H69 NO13 747.97 3.16 1.1–2.8c
Erythromycin 114-07-8 C37 H67 NO13 733.95 3.06 0.72–2.4c
Sulfamethoxazole 723-46-6 C10 H11 N3 O3 S 253.28 0.89 0.49 to −0.9c
Ofloxacin 82419-36-1 C18 H20 FN3 O4 361.38 −0.39 –
Metronidazole 443-48-1 C6 H9 N3 O3 171.16 −0.02 −0.01c
Atenolol 29122-68-7 C14 H22 N2 O3 266.34 0.16 −1.09b
Metoprolol 37350-58-6 C15 H25 NO3 267.37 1.88 –
Nadolol 42200-33-9 C17 H27 NO4 309.41 0.81 –
Propranolol 525-66-6 C16 H19 NO2 257.34 3.48 –
Sotalol 3930-20-9 C12 H20 N2 O3 S 272.37 0.24 –
Salbutamol 18559-94-9 C13 H21 NO3 239.32 0.64 –
Clopidogrel 135046-48-9 C16 H16 ClNO2 S·H2 SO4 419.90 – –
a
Octanol-water distribution coefficient of a given pH.
b
[10] (pH 8).
c
[15] (pH 6–8); MW: molecular weight.
 D. Dolar et al. / Journal of Hazardous Materials 239–240 (2012) 64–69 67

Table 2
Concentration ranges and mean values (n = 5) of target contaminants in wastewater influent and LOQ with standard deviation (S.D.) in parentheses (n = 5).

Compounds LOQ Influent concentration (␮g L−1 )

−1
ng L Range Mean

Analgesics/anti-inflammatories
Codeine 6.35 (2.72) 0.055–0.338 0.152
Hydrocodone 1.73 (0.85) 0.014–0.110 0.046

Psychiatric drugs
Carbamazepine 3.13 (1.78) 0.064–0.099 0.083
Diazepam 13.82 (6.81) 0.013–0.019 0.017
Lorazepam 19.30 (5.69) 0.051–0.082 0.074

Histamine H2 receptor antagonists

Famotidine 23.01 (17.08) 0.115–0.132 0.128
Ranitidine 3.25 (1.66) 0.202–0.932 0.485

Macrolide antibiotics
Azithromycin 23.12 (4.98) 0.110–0.142 0.118
Clarithromycin 35.11 (15.88) 0.700–2.72 2.02
Erythromycin 43.40 (45.90) 0.032–0.080 0.049

Sulfonamide antibiotics
Sulfamethoxazole 6.83 (3.22) 0.020–0.268 0.102

Fluoroquinolone antibiotic
Ofloxacin 2.03 (4.25) n.d.–2.90 0.605

Nitroimidazole
Metronidazole 208.9 (102.5) n.d.–1.14 0.486

␤-blockers
Atenolol 6.89 (3.27) 0.916–2.44 1.82
Metoprolol 9.58 (4.58) 0.033–0.076 0.049
Nadolol 4.54 (2.75) 0.030–0.048 0.041
Propranolol 69.54 (29.79) 0.072–0.309 0.183
Sotalol 6.26 (1.59) 0.040–0.222 0.118

␤-agonist
Salbutamol 1.79 (1.38) 0.016–0.040 0.028

Antiplatelet agent
Clopidogrel 8.76 (4.56) 0.106–0.133 0.124

n.d.: not detectable (below the LOQ).

Sulfamethoxazole was partially removed (69%) with MBR prob- potential. Göbel et al. [23] described lower removal of sulfamethox-
ably due to a moderate sorption to sludge and to its limited azole (37–38%) with a MBR system and constant HRT (13 h) but
biodegradability. Chemicals with log D < 2.5, as it is the case of sul- variable SRT (16–80 days).
famethoxazole, are considered to have low hydrophobic sorption MBR ␤-blockers removal rates were 87.10% (atenolol), 71.16%
(metoprolol), 88.65% (nadolol), 67.01% (propranolol) and 70.88%
(sotalol). These removal rates are higher, except propranolol, than
RO MBR those observed by Radjenovic et al. [19]. Maurer et al., [22] found
100 that removal mechanism of ␤-blockers with MBR sludge is mainly
biodegradation whereas only in the case of propanolol, sorption
was a possible removal pathway.
80
According to Alexy et al. [24] metronidazole was not biodegrad-
able in laboratory-based batch experiment and is relatively
hydrophilic (Table 1). Due to these factors this compound was
not expected to be effectively removed during conventional
Removal (%)

60
wastewater treatment. But conversely, an excellent removal of
metronidazole (95%) was observed with MBR of Platja d’Aro. A
possible reason for the high removal of this compound could
40
be the rapid metabolization of the nitroimidazoles into 1-(2-
hydroxyethyl)-2-hydroxymethyl-5-nitroimidazole) [25].
Removal of psychiatric drugs was 48% (lorazepam), 51% (carba-
20
mazepine) and 67% (diazepam). Removal rates for carbamazepine
are much higher than removal rates observed by other researchers
[10,18,26]. Negligible or no removal in other investigations can
0 be explained by potential cleavage of hydroxylated human car-
az ne

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Ca dro eine

az e

ho in
M Oflo ole
lfa hro cin

ni in

ra l
S ol
lb lol

id l
l
Az anit ne

et lo

re
op lo

op o
Di epin

Cl utam
Lo epa

l
ith yc

ro c
et yc
am o

R tidi

ro
M eno

Pr do
no

og
Sa ota
Su ryt my

z
Fa zep

z
et xa
i id

bamezapine metabolites back to free forms during microbial

rb cod

da
xa
ar m

m m
Hy Cod

activity in wastewater treatment plants, as described by Miao et al.

[26].
MBR system showed no elimination for ofloxacin which does
Fig. 2. Overall removal efficiency of the detected emerging contaminants by
MBR–RO system. not match with the high removal (>90%) observed in other studies
68 D. Dolar et al. / Journal of Hazardous Materials 239–240 (2012) 64–69

[19]. Additionally codeine, hydrocodone, salbutamol, clopidogrel, to 2.90 ␮g L−1 ). Average concentrations of some pharmaceutical
famotidine and ranitidine were detected in influent wastewater groups ranged from 0.017 ␮g L−1 (psychiatric drugs) and 0.028 (␤-
and removal rates were equal to 88%, 93%, 79%, 69%, 84% and 89%, agonist) to 2.02 ␮g L−1 for macrolide antibiotics.
respectively. Only for hydrocodone and famotidine removal rates High removal rates (till levels below LOQ) were achieved with
were similar to the ones obtained by Snyder et al. [27] (<94%) and the combination of MBR–RO treatment for all pharmaceuticals
Radjenović et al. [19] (64.6 ± 24.5%), respectively. Further, removal determined in influent. Removal efficiency of MBR varied quite
rate for clopidogrel (69%) was higher than 25.6% obtained by Chon significantly (0–95%) depending on the compound due to diverse
et al. [28] and for ranitidine (89%) than 44.2 ± 29.6% by Radjenović physicochemical properties of the 20 target compounds. The RO
et al. [19]. To encompass the novelty of these findings in next sam- membrane showed excellent removal rates (>99%) for all com-
pling campaign removal mechanism of these compounds will be pounds. Size exclusion and electrostatic attraction or repulsion are
further investigated. supposed to be the main mechanisms involved in the removal of
target compounds with RO membranes.
3.3. Removal of emerging contaminants with RO
Acknowledgments
As it can be observed in Fig. 2 RO membranes can complement
MBR treatment very well since the majority of compounds stud- This research was financed by the Spanish Ministry of Economy
ied in the influent were completely removed or concentrations and Competitiveness (CTM2009-14742-C02-01, CTQ2010-21776-
were below LOQ after RO filtration. Overall removal rates were C02-02 (DEGRAPHARMAC), CONSOLIDER-CSD2007-00055), by The
greater than 99% which means that additional removal of selected Agency for Administration of University and Research Grants
emerging contaminants with RO membrane was higher than 99% (AGAUR, 2009 CTP 00034, MBRMed), by the National Foundation
and are in agreement with results obtained by other researchers for Science, Higher Education and Technological Development of
[12,29–31]. Joss et al. [11] obtained that most organic micropollu- the Republic of Croatia and by the Croatian Ministry of Science,
tants (atenolol, clarithromycin, erythromycin, metoprolol etc.) are Education and Sports Project: (125-1253008-3009). Prof. Barceló
degraded and/or retained to below the detection limit (≤10 ng L−1 ) acknowledges King Saud University for his visiting professorship.
–
by RO. Radenovi ć et al. [29] and Gur-Reznik et al. [30] showed
–
100% removal of carbamazepine. Also Radenovi ć et al. [29] showed References
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