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Environmental
Monitoring
Cite this: DOI: 10.1039/c2em00007e
www.rsc.org/jem PAPER
Effectiveness of three configurations of membrane bioreactors on the removal
of priority and emergent organic compounds from wastewater: comparison
with conventional wastewater treatments
D. Camacho-Mu~ noz,a J. Martın,a J. L. Santos,*a E. Alonso,a I. Aparicio,a T. De la Torre,b C. Rodriguezb
and J. J. Malfeitob
Published on 04 April 2012 on http://pubs.rsc.org | doi:10.1039/C2EM00007E

Received 3rd January 2012, Accepted 16th February 2012

DOI: 10.1039/c2em00007e
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In this work the effectiveness of membrane bioreactors as advanced treatment on the removal of
emergent and priority organic compounds in wastewater treatment plants has been evaluated during
a one-year monitoring study. The studied wastewater treatment plant operates with flat sheet and
hollow fibre membranes in two parallel lines. Moreover, a reverse osmosis module connected in series
after the hollow fibre membrane was evaluated for one month. Comparison of membrane bioreactor
and conventional activated sludge treatment was also investigated, as well as the influence of the
physicochemical properties of the compounds on the removal rates achieved. Sixteen pharmaceutical
compounds belonging to seven therapeutic groups and eight priority organic pollutants, including
linear alkylbenzene sulfonates, nonylphenol and its ethoxylates and phthalate, were monitored. The
highest mean concentrations corresponded to priority organic pollutants (309 mg L
1 of linear
alkylbenzene sulfonate C12) followed by pharmaceutical compounds (24.5 mg L
1 of ibuprofen). No
significant difference of effectiveness was found among flat sheet and hollow fibre membranes.
However, an improvement was obtained with the addition of a reverse osmosis module for most of the
compounds. Biodegradation has been shown as the main route involved in the removal of organic
compounds during both technologies.

1. Introduction not regulated, there is a growing consensus among the scientific

The reuse of urban wastewater is a widespread practice in many
arid or semiarid countries where reclaimed wastewater has
become a part of the hydrological cycle. However, one essential
issue of wastewater reuse is the presence of organic pollutants in
the effluent. Although nowadays most of these contaminants are
a
Department of Analytical Chemistry, High Polytechnic School, Escuela
Polit 
ecnica Superior, University of Seville, C/Virgen de Africa
E-41011 Seville, Spain. E-mail: JLSantos@us.es; Fax: +34-9-5428-2777;
Tel: +34-9-5455-6250
b
Acciona Agua, Avenida de les Garrigues 22, 2a Planta, 08820 El Prat del
Llobregat, Barcelona, Spain
community and water authorities that their optimized removal in
wastewater treatment plants is a justifiably prudent approach to
environmental protection.1 Compounds found in wastewater
effluent belong not only to classical persistent organic
compounds, but also to emerging pollutants such as pharma-
ceutical compounds2 or flame retardants,3 and priority organic
pollutants, such as nonylphenol and its ethoxylates (NPE),4
phthalates,5 polycyclic aromatic hydrocarbons6 or pesticides.7
7, Wastewater treatments, based on conventional activated
sludge processes (CAS), are not specifically designed to remove
these organic pollutants and, in spite of the efforts to improve the
removal rates of these compounds through the optimization of

Environmental impact
Several studies have been carried out on the removal of emerging and priority organic pollutants in membrane bioreactor tech-
nologies; most of them have been development using laboratory-scale pilot plant bioreactors in which accurate controlled operating
parameters are applied. Only a few studies have shown the removal of organic pollutants in full-scale MBR plants. In this work, the
efficiency of three configurations of MBR for the removal of emerging and priority organic pollutants has been evaluated during
a one year period and compared with those achieved in conventional WWTP. Moreover, the influence of the physicochemical
properties of the organic compounds on their removal has been evaluated.

This journal is ª The Royal Society of Chemistry 2012 J. Environ. Monit.

 View Online

operational parameters such as solid retention time or hydraulic
retention time,8,9 organic pollutants are still present in waste-
water effluents10 at relevant concentrations.
Nowadays, the water scarcity and the progressive stringent
wastewater quality discharge regulations have shown the need to
search for advanced wastewater treatments that allow the
improvement of the removal of these compounds. Among them,
membrane bioreactor technologies (MBR) alone or as an addi-
tional step for CAS treatment seem to be a useful option for the
removal of these compounds. This is due to their several
advantages: (a) solids-free effluent, because it allows a complete
retention of the biomass in MBR systems,11 (b) the low sludge
load that can be expected to force bacteria also to mineralize
Published on 04 April 2012 on http://pubs.rsc.org | doi:10.1039/C2EM00007E
osmosis (RO) system feeding by UF permeate was operating for
one month.
2. Materials and methods
2.1 Chemicals and reagents
HPLC-grade acetonitrile, methanol and water were supplied by
Romil Ltd. (Barcelona, Spain). HPLC-grade acetone and hexane
and analytical grade sulfuric acid were obtained from Panreac
(Barcelona, Spain). Potassium dihydrogen phosphate of analyt-
ical grade was obtained from Scharlau (Barcelona, Spain). Car-
bamazepine, clofibric acid, diclofenac, ketoprofen, naproxen and
salicylic acid (>97%) were purchased from Sigma-Aldrich

poorly degradable organic compounds and (c) the high solid
retention time achieved in the membrane process.12,13
Several studies have shown an improvement of removal
efficiencies using MBR technologies for several organic pollutant
families8,11,14 including pharmaceutical compounds,15 surfac-
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(Steinheim, Germany). 17a-Ethinylestradiol, 17b-estradiol,
estriol, estrone, gemfibrozil, ibuprofen, propranolol hydrochlo-
ride, sulfamethoxazole and trimethoprim (>98.5%) were
purchased from Dr Ehrenstorfer (Augsburg, Germany). Caffeine

was obtained from Merck (Darmstadt, Germany).

tants4 or pesticides.12 Sipma et al. (2010)15 described that, A commercial LAS mixture containing C10 (12.3%), C11
although some pharmaceutical compounds such as acetamino- (32.1%), C12 (30.8%) and C13 (23.4%) LAS was supplied by
phen or ibuprofen are equally well removed in both CAS and Petroquımica Espa~ nola (PETRESA, Spain). DEHP and NP
MBR processes, in most cases the removal efficiency of moder- Pestanal technical grade were obtained from Riedel-de Ha€en
ately and slightly removed pharmaceuticals in CAS is better in (Seelze, Germany). Nonylphenol monoethoxylate (NP1EO) and
MBR. Similar conclusions were reported by Gonzalez et al. nonylphenol diethoxylate (NP2EO) Igepal CO-210 technical
(2008)16 for the case of surfactants: compounds such as linear mixture was obtained from Aldrich (Milwaukee, WI, USA).
alkylbenzene sulfonates (LAS) were removed in the same Stock standard solutions of 1000 mg mL
1 in each of the
proportion in CAS and MBR processes while other surfactants organic compounds were prepared in methanol and stored at
such as NPE showed higher removal rates in MBR systems. 4  C. A mixture of all pharmaceuticals at different concentration
The efficiency of MBR technologies on the removal of organic levels was freshly prepared by appropriate dilution of the stock
compounds from wastewater depends not only on the physico- standard solutions with methanol while the mixture of LAS, NP,
chemical properties of the trace organic pollutants17 but also on NPE and DEHP was prepared by diluting the stock standard
the configuration of the MBR system and the operational solutions in a methanol–water mixture (1 : 1, v/v).
parameters applied during the MBR process. Three-millilitre solid phase extraction (SPE) cartridges packed
So far, most studies have been carried out using laboratory- with 60 mg of OASIS HLB were purchased from Waters
scale plant bioreactors8,11,12,14,16,18 in which accurate controlled (Milford, MA, USA).
operating parameters are applied. In these studies removal rates
up to 95% have been achieved for several families of organic 2.2 The MBR system and sampling
pollutants such as pharmaceutical compounds, surfactants or
pesticides. However, a few studies have shown removal rates of Table 1 shows the operational parameters applied during the
organic pollutants in real full-scale plants based on MBR tech- study. The MBR system consists of two lines with an average
nology14,19,20 in which some uncontrolled parameters, such as
influent wastewater quality or climatic conditions, could affect Table 1 Operating conditions of the planta
the occurrence of these compounds.
HF-MBR FS-MBR
In this work, the monitoring of emerging and priority organic
pollutants in three membrane bioreactor configurations has been Area (m2) 250 160
carried out and the occurrence of these pollutants has been Pore size (mm) 0.05 0.4
evaluated. The studied compounds were sixteen pharmaceutical Flux (L mh
1) 10 15
SADm (m3 m
2 h
1) 0.4 0.6
compounds belonging to different therapeutic classes including Volume (m3) 29 37
five non-steroidal antiinflammatory drugs (diclofenac, SRT (d) 20 20
ibuprofen, ketoprofen, naproxen and salicylic acid), two antibi- TSS (g L
1) 6–9 4–7
otics (sulfamethoxazole and trimethoprim), a b-blocker HF/RO-MBR
(propranolol), two lipid regulators (clofibric acid and gemfi-
brozil), an antiepileptic drug (carbamazepine), four estrogens Permeability (L m
2 d
1 bar
1) 40
(17a-ethinylestradiol, 17b-estradiol, estriol and estrone) and Area (m2) 165.9
T ( C) 18–20
a nervous stimulant (caffeine) and eight priority pollutants No. of elements/tube 7
including NPE, LAS and a di(2-ethylhexyl)phthalate (DEHP). Recovery (%) 68
The study was carried out during a one-year period in a full-scale a
SADm: Specific Air Demand for unit of membrane area; SRT: Solid
MBR plant which comprises two parallel lines: an ultrafiltration Retention Time; and TSS: Total Suspended Solids.
line (UF) and a microfiltration line (MF). Additionally, a reverse

J. Environ. Monit. This journal is ª The Royal Society of Chemistry 2012


treatment capacity of 5 m3 h
1 operating in parallel. Each line treats
2.3 m3 h
1 of raw wastewater previously sieved (0.40 mm) and is
constituted by an anoxic reactor (10 m3) and two aerobic tanks
(15 m3). After the aerobic tanks were sited the two membrane units:
the UF unit (indicated as HF-MBR), constituted by a hollow fiber
membrane bioreactor (Koch Membranes, Germany) and the MF
unit (indicated as FS-MBR), composed of a flat sheet membrane
bioreactor (Kubota, Japan). Additionally, a RO (TriSep 4040-
X201-TSA, CA) system (indicated as HF/RO-MBR), feeding by
HF-MBR permeate, was operating for one month. A schematic
diagram of the studied MBR system and sampling points is shown
in Fig. 1. Influent wastewater was taken in sampling point S1 which
was located after the grit and grease traps from the CAS plant sited
necar (Granada, South of Spain), where the MBR plant is
Published on 04 April 2012 on http://pubs.rsc.org | doi:10.1039/C2EM00007E
in Almu~
located. Sampling points S2, S3 and S4 correspond to FS-MBR,
HF-MBR and HF/RO-MBR permeates, respectively. One
hundred wastewater samples were collected from each sampling
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point from July 2009 to June 2010. Except HF/RO-MBR, from
which six effluent samples were collected from March to April
2010, daily composite wastewater samples were obtained by mix-
ing aliquots collected every four hours by an automatic device
operating for 24 h. In addition, ten daily composite influent and
effluent wastewater samples were collected in September 2009
from the CAS plant of Almu~ necar. Samples were transferred to
amber bottles and kept at 4  C until analysis.
2.3 Analysis of wastewater samples
Sixteen pharmaceutical compounds and eight priority organic
pollutants were analyzed in wastewater samples. A summary of
Fig. 1 Scheme of the MBR plant and sampling points.
This journal is ª The Royal Society of Chemistry 2012
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the studied compounds and their physicochemical properties is
shown in Table 2.
2.3.1 Analysis of pharmaceutical compounds. Pharmaceutical
compounds were simultaneously extracted by SPE using Oasis
HLB cartridge according to a previously reported and validated
method.2 Determination was carried out by high performance
liquid chromatography with diode array and fluorescence detec-
tors sited on line. Separation of pharmaceutical compounds was
carried out using a Zorbax Eclipse XDB-C18 (150 mm  4.6 mm,
particle size 5 mm) cartridge column (Agilent, USA) protected by
a XDB-C18 (4 mm  4 mm i.d., 5 mm) guard column (Agilent,
USA). Limits of detection (LODs), limits of quantification
(LOQs) and recoveries of the method are shown in Table 3.
2.3.2 Analysis of LAS, NPE and DEHP. LAS, NPE and
DEHP were simultaneously extracted by SPE. Prior to extrac-
tion, 500 mL of wastewater samples were filtered through
a 1.2 mm glass fibre membrane filter (Whatman, Mainstone, UK)
and acidified to pH 2 with sulfuric acid. The Oasis HLB SPE
cartridges were conditioned with 3 mL of methanol and 3 mL of
deionized water acidified to pH 2 with sulfuric acid at a flow rate
of about 3 mL min
1. Samples were percolated through the
cartridges at a flow rate of about 10 mL min
1 using a vacuum
manifold system (Waters, USA) connected to a vacuum pump.
The elution was performed with three aliquots of 1 mL of
methanol at a flow rate of about 1 mL min
1. The combined
aliquots were evaporated to dryness by a gentle nitrogen stream.
The residues were dissolved in 0.2 mL of methanol and filtered
through a 0.45 mm nylon filter.
J. Environ. Monit.
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Table 2 Physicochemical properties of the selected organic pollutantsh

Therapeutic group Compound Mw (g mol
1) Solubility (mg L
1) pKa log KOW log DOW (pH 7)

Pharmaceutical compound
Antiinflammatory drugs Diclofenac 296.2 2.4 4.18a 4.06a 1.24
Ibuprofen 206.3 1200 4.41a 3.72a 1.13
Ketoprofen 254.3 300 4.23a 2.81a 0.04
Naproxen 230.3 16 4.84a 3.00a 0.84
Salicylic acid 138.1 2000 2.94b 2.26b
1.80
Antibiotics Sulfamethoxazole 253.3 610 5.81a 0.89a
0.74
Trimethoprim 290.3 171 7.20a 0.79a 0.32
Antiepileptic Carbamazepine 236.3 17.7 13.94a 2.67a 2.67
b-Blocker Propranolol 259.3 3009 9.14c 3.1c 0.96
Nervous stimulant Caffeine 194.2 21 600 10.4d
0.07d 0.16
Estrogens 17a-Ethinylestradiol 296.4 11.3 10.24a 4.52a 4.52
17b-Estradiol 272.4 3.6 10.27a 4.13a 4.13
Published on 04 April 2012 on http://pubs.rsc.org | doi:10.1039/C2EM00007E

Estriol 288.4 441 10.25a 2.94a 2.94

Estrone 270.4 30 10.25a 3.68a 3.68
Lipid regulators Clofibric acid 582.5 582 3.18c 2.84c
0.98
Gemfibrozil 250.3 10.9 4.75a 4.39a 2.14
Priority organic pollutant
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LAS C10 298 250 000 <1 2.15e 2.15

C11 312 250 000 <1 2.60e 2.60
C12 326 250 000 <1 3.17e 3.17
C13 340 250 000 <1 3.62e 3.62
NPE NP1EO 264.0 1.10 n.a. 4.17f 4.17
NP2EO 308.0 1.05 n.a. 4.20f 4.20
NP 220.4 6.00 10.14a 6.19a 6.19
Phthalate DEHP 390.6 0.285 n.a. 7.60g 7.60
a
Altuki et al., 2010 (ref. 1). b Kimura et al., 2003 (ref. 34). c Sipma et al., 2010 (ref. 15). d United State National Institute of Medicine (http://
chem.sis.nlm.nih.gov/chemidplus/). e Mauffret et al., 2010 (ref. 35). f Ahel and Giger, 1993 (ref. 36). g Koniecki et al. (2011) (ref. 37) n.a.: no
available. h log D calculated as it is described by Lin et al. 2010 (ref. 38).

Compounds were simultaneously determined by high perfor- 4.6 mm, particle size 5 mm) column (GL Sciences, Tokyo Japan)
mance liquid chromatography as was previously reported.21 protected by an Inertsil Ph-3 (4 mm  10 mm, 5 mm) guard
Separation was carried out using an Inertsil Ph-3 (150 mm  column (GL Sciences, Tokyo, Japan). Gradient elution with an

Table 3 Recoveries, limit of detection (LOD) and limit of quantification (LOQ) of emergent and priority organic pollutants in wastewater samples

Influent wastewater (n ¼ 3) Effluent wastewater (n ¼ 3)

1
1
Compound Recovery (%) LOD/mg L LOQ/mg L Recovery (%) LOD/mg L
1 LOQ/mg L
1

Pharmaceutical compound
Pharmaceutical compound Diclofenac 87 0.030 0.099 101 0.015 0.049
Ibuprofen 79 0.137 0.455 100 0.068 0.228
Ketoprofen 82 0.074 0.247 82 0.037 0.124
Naproxen 97 0.002 0.007 95 0.001 0.003
Salicylic acid 95 0.016 0.054 96 0.008 0.027
Sulfamethoxazole 63 0.017 0.056 75 0.008 0.028
Trimethoprim 61 0.012 0.040 71 0.006 0.020
Carbamazepine 70 0.016 0.054 72 0.008 0.027
Propranolol 77 0.001 0.003 73 0.001 0.002
Caffeine 75 0.029 0.096 107 0.014 0.048
17a-Ethinylestradiol 123 0.020 0.067 106 0.010 0.033
17b-Estradiol 82 0.045 0.150 88 0.023 0.075
Estriol 110 0.005 0.018 64 0.003 0.009
Estrone 82 0.323 1.078 88 0.162 0.539
Clofibric acid 81 0.001 0.004 78 0.001 0.002
Gemfibrozil 73 0.015 0.051 86 0.008 0.026
Priority organic pollutant
LAS C10 80 0.10 0.40 83 0.10 0.39
C11 75 0.16 0.53 80 0.15 0.50
C12 73 0.11 0.44 73 0.11 0.44
C13 70 0.06 0.17 77 0.05 0.16
NPE NP1EO 82 0.20 0.59 80 0.20 0.60
NP2EO 79 0.05 0.10 91 0.04 0.09
NP 80 0.05 0.25 79 0.05 0.25
Phthalate DEHP 72 0.17 0.56 75 0.16 0.53

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acetonitrile–methanol (6 : 4, v/v) mixture and water at a flow rate
of 1 mL min
1 was used. LODs, LOQs and recoveries of the
method are shown in Table 3.
3. Results and discussion
3.1 Concentrations of organic compounds in MBR and CAS
processes
3.1.1 Pharmaceutical compounds. Tables 4 and 5 show mean
and maximum concentrations quantified of the selected phar-
maceutical compounds in influent and effluent wastewaters from
MBR technologies and CAS treatment, respectively.
Published on 04 April 2012 on http://pubs.rsc.org | doi:10.1039/C2EM00007E
present at the highest concentrations, followed by the estrogenic
compounds for which mean concentrations up to 1.60 mg L
1
were measured. However, concentrations of pharmaceutical
compounds found in effluent from MBR technologies were
generally lower than those found in effluent from the CAS
process, especially after HF/RO-MBR where only caffeine, car-
bamazepine, diclofenac, ibuprofen, naproxen and salicylic acid
were quantified (concentrations up to 0.09, 0.23, 0.27, 2.35, 0.20
and 0.04 mg L
1, respectively). Similar pattern in influent
wastewater samples was found in effluent samples where anti-
inflammatory drugs were present at concentration levels up to
63.8 mg L
1 (ibuprofen). These results are in agreement with those
published by other authors in MBR systems22 and even in some
cases these are lower than those reported.23

Except the antibiotic trimethoprim and the estrogen estrone,

all pharmaceutical compounds were detected in the analyzed
wastewater. Anti-inflammatory drugs were the most frequently 3.1.2 Priority organic pollutants. Mean and maximum
detected pharmaceutical compounds in influent wastewater concentration levels quantified for LAS, NPE and DEHP in
samples and at the highest concentrations reaching up to 91.4 mg
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influent and effluent samples from the studied MBR technologies

L
1 (ibuprofen) and 57.0 mg L
1 (salicylic acid). This fact could be
associated with the high consumption of these pharmaceuticals
for which medical prescription is not necessary. Estrogens
17a-ethinylestradiol, 17b-estradiol and estriol were found in the
46, 23 and 27% of the influent samples analyzed at mean
concentrations of 2.97, 0.93 and 1.68 mg L
1 respectively, in the
influent that will be treated by the MBR system.
Mean concentrations of pharmaceutical compounds found in
wastewater effluent samples from the CAS process ranged from
0.06 mg L
1 (carbamazepine) to 2.68 mg L
1 (estriol). As
happened with influent wastewater, antiinflammatory drugs were
and from CAS are shown in Tables 4 and 5.
Among the priority organic pollutants evaluated, LAS
homologues showed the highest concentration levels, followed by
DEHP and NPE, in that order. Mean concentrations of LAS
homologues were 893, 1294 and 754 mg L
1 of C11, C12 and C13,
respectively, reaching concentrations up to 1499, 2211 and
2210 mg L
1 in influent wastewater. Only the C10 homologue was
below the limit of detection in all samples from CAS treatment.
These concentrations were close to the percentages found in
cleaning products such as commercials detergents, which points
to the domestic wastewater as the main source of these pollutants

Table 4 Mean and maximum concentrations and standard deviation of the studied organic compounds in influent and effluent wastewater samples
from MBR

Influent wastewater HF-MBR permeate FS-MBR permeate HF/RO-MBR permeate

(n ¼ 100) (n ¼ 100) (n ¼ 100) (n ¼ 6)

Mean/ Max/ SD/ Mean/ Max/ SD/ Mean/ Max/ SD/ Mean/ Max/ SD/
Therapeutic group Compound mg L
1 mg L
1 mg L
1 mg L
1 mg L
1 mg L
1 mg L
1 mg L
1 mg L
1 mg L
1 mg L
1 mg L
1

Pharmaceutical compound
Antiinflammatory drugs Diclofenac 1.09 38.0 4.62 0.13 1.90 0.26 0.26 8.56 0.95 0.10 0.27 0.13
Ibuprofen 24.5 88.6 24.7 3.88 63.8 8.06 4.29 52.2 8.14 0.39 2.35 0.96
Ketoprofen 1.79 44.3 6.84 <LOQ 1.79 0.23 0.19 13.6 1.42 <LOD <LOD —
Naproxen 3.21 19.7 3.33 0.09 2.58 0.28 0.16 2.19 0.35 0.03 0.20 0.08
Salicylic acid 14.0 57.0 14.5 0.30 17.9 1.79 0.15 1.25 0.21 <LOQ 0.04 0.02
Antibiotics Sulfamethoxazole 0.08 4.90 0.53 <LOQ 0.37 0.04 <LOD 0.13 0.01 <LOD <LOD —
Trimethoprim <LOD <LOD — <LOD <LOD — <LOD <LOD — <LOD <LOD —
Antiepileptic Carbamazepine 0.37 2.55 0.49 0.18 1.70 0.28 0.25 7.95 0.84 0.05 0.23 0.09
b-Blocker Propranolol 0.31 3.08 0.40 0.12 1.61 0.21 0.12 0.54 0.15 <LOD <LOD —
Nervous stimulant Caffeine 1.34 22.5 2.84 <LOQ 0.66 0.09 <LOQ 0.60 0.11 <LOQ 0.09 0.04
Estrogens 17a-Ethinylestradiol 2.97 29.2 5.80 0.59 6.92 1.22 0.51 6.88 1.13 <LOD <LOD —
17b-Estradiol 0.93 21.2 2.89 0.11 2.11 0.39 0.11 4.90 0.56 <LOD <LOD —
Estriol 1.68 36.6 4.86 0.81 18.3 2.61 0.56 9.25 1.85 <LOD <LOD —
Estrone <LOD <LOD — <LOD <LOD — <LOD <LOD — <LOD <LOD —
Lipid regulators Clofibric acid 0.40 5.20 1.13 0.10 1.92 0.33 0.12 3.72 0.47 <LOD <LOD —
Gemfibrozil 2.11 5.38 1.54 0.41 12.9 1.38 0.30 2.27 0.48 <LOD <LOD —
Priority organic compound
LAS C10 97.9 1090 177 6.80 98.0 13.7 7.96 134 18.8 3.57 10.8 5.53
C11 309 1286 311 22.3 237 38.5 21.1 299 44.8 5.85 13.1 5.08
C12 242 1759 314 22.1 227 43.9 17.2 281 43.2 5.15 16.5 6.58
C13 179 806 182 26.8 191 48.6 20.2 232 44.0 4.72 10.8 5.24
NPE NP1EO 6.73 146 15.3 2.84 20.6 20.6 3.37 19.3 3.88 <LOQ 1.46 0.60
NP2EO 2.50 59.7 6.14 2.41 12.2 12.2 2.30 15.8 2.51 0.24 1.41 0.58
NP 1.59 28.7 4.24 1.56 24.3 24.3 1.40 26.3 3.35 0.29 0.96 0.45
Phthalate DEHP 37.2 379 70.0 36.0 314 314 33.2 277 66.0 <LOQ <LOQ —

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Table 5 Mean and maximum concentrations and standard deviation of the studied organic compounds in influent and effluent wastewater samples
from CAS (n ¼ 10)

Influent wastewater Effluent wastewater

Mean/ Max/ SD/ Mean/ Max/ SD/

Therapeutic group Compound mg L
1 mg L
1 mg L
1 mg L
1 mg L
1 mg L
1

Pharmaceutical compound
Antiinflammatory drugs Diclofenac 2.56 12.7 4.53 0.20 1.35 0.45
Ibuprofen 22.8 91.4 28.5 2.61 17.8 5.45
Ketoprofen <LOD <LOD — <LOD <LOD —
Naproxen 3.65 7.72 2.57 0.09 0.23 0.06
Salicylic acid 30.1 41.1 8.85 0.19 0.33 0.07
Antibiotics Sulfamethoxazole <LOD <LOD — <LOD <LOD —
Trimethoprim <LOD <LOD — <LOD <LOD —
Antiepileptic Carbamazepine 0.18 1.76 0.56 0.06 0.55 0.17
Published on 04 April 2012 on http://pubs.rsc.org | doi:10.1039/C2EM00007E

b-Blocker Propranolol 1.14 6.52 1.97 0.28 0.41 0.07

Nervous stimulant Caffeine 0.47 4.67 1.48 <LOD <LOD —
Estrogens 17a-Ethinylestradiol 2.87 22.2 6.98 1.47 6.62 2.47
17b-Estradiol 2.78 23.2 7.67 0.22 0.81 0.30
Estriol 10.8 53.0 18.6 2.68 17.2 5.93
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Estrone <LOD <LOD — <LOD <LOD —

Lipid regulators Clofibric acid <LOD <LOD — <LOD <LOD —
Gemfibrozil 2.07 3.48 0.97 0.39 1.35 0.45
Priority organic compound
LAS C10 <LOD <LOD — <LOD <LOD —
C11 893 1499 530 69.0 262 81.6
C12 1294 2211 783 31.9 170 50.6
C13 754 2210 625 58.2 280 90.8
NPE NP1EO 10.3 19.7 5.09 6.04 18.8 6.22
NP2EO 1.97 2.64 0.44 4.00 6.23 1.65
NP 1.39 2.58 0.48 1.35 2.34 0.46
Phthalate DEHP 37.5 105 33.6 77.1 198 70.8

to the environment. The highest concentrations of NPE were
achieved for NP1EO, followed by NP2EO and finally NP.
Maximum concentration levels of these pollutants in influent
samples were up to 19.7, 2.64, and 2.58 mg L
1, respectively, while
DEHP was present at concentration levels between 1.04 and
105 mg L
1.
These levels were reduced during CAS treatment, so mean
concentrations detected in effluents ranged from 31.8 to 69.0 for
LAS and were 1.35, 4.00, 6.04 and 77.1 mg L
1 for NP, NP1EO,
NP2EO and DEHP, respectively.
After MBR treatment mean concentrations decreased signifi-
cantly (approximately 10 times lower) from those found in
influent wastewater. The most significant decrease of concen-
trations was after the HF/RO-MBR system where maximum
concentrations of LAS only reached 10.8, 13.1, 16.5 and 10.8 mg
L
1 of C10, C11, C12 and C13, respectively. Maximum concen-
trations of NPE were reduced to 20.6, 12.2 and 24.3 mg L
1 after
HF-MBR, to 19.3, 15.8 and 26.3 mg L
1 after FS-MBR and more
noteworthy to 1.46, 1.41 and 0.96 mg L
1 after HF-MBR/RO.
These results are in accordance with other studies.4
DEHP was slightly reduced to mean concentrations of
36.0 and 33.2 mg L
1 after HF-MBR and FS-MBR. As it
occurred for the other priority organic pollutants the configu-
ration of HF/RO-MBR was more effective for the removal rate
of this pollutant, being found only in 30% of the analyzed
effluent wastewater samples.
As it can be seen in Tables 4 and 5, concentrations found in
effluent from the MBR system were lower than those found in
effluents from the CAS process, except in the case of NP2EO and
NP for which concentrations in both processes were comparable.
3.2 Removal of organic pollutants in MBR and CAS
Removal of organic pollutants during wastewater treatment is
carried out by biodegradation, sorption in sludge generated, air-
stripping and photo-transformation. However, in the case of the
considered organic pollutants the last two mechanisms are
negligible in wastewater treatment plants.15 Retention in soil can
be considered the major removal mechanism for hydrophobic
compounds while biodegradation is more reasonable for
hydrophilic compounds.1 Compounds can be classified as
hydrophobic when logarithm of pH-dependent n-octanol–water
distribution ratio (log DOW) is 3 or higher.1 According to liter-
ature data (Table 3), pharmaceutical compounds are the most
hydrophilic compounds while NPE and DEHP are the most
hydrophobic.
3.2.1 Pharmaceutical compounds. Table 6 shows mean
removal rates achieved for pharmaceutical compounds
after the MBR treatments and after CAS processes. The
efficiency of removal rates was significantly dependent on
both the pharmaceutical compound and the wastewater
treatment technology applied as it was reported by several
authors.13,14,24
Mean removal rates of pharmaceutical compounds were
higher than 71% for most of studied pharmaceutical compounds
after HF-MBR and FS-MBR. Diclofenac, 17b-estradiol, and
salicylic acid had slightly improved mean removal rates when
FS-MBR was employed instead of HF-MBR. Only carbamaze-
pine showed poor mean removal rates, 25% after HF-MBR and
7% after FS-MBR.

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The addition of RO system after MBR_HF caused an increase
of the mean removal rates for most of the pharmaceutical
compounds detected and removal rates higher than 97% were
achieved for pharmaceutical compounds such as gemfibrozil,
ibuprofen, ketoprofen, naproxen or salicylic acid. Even carba-
mazepine, which has been considered as an anthropogenic
marker due to its low elimination after wastewater treatment and
its persistence in the environment, improved its mean removal
rate significantly, reaching up to 82%. Removal rates of phar-
maceutically active compounds propranolol and clofibric acid
and the estrogens 17a-ethinylestradiol, 17b-estradiol and estriol
were not evaluated in the RO system since these compounds were
not detected in influent wastewater during the sampling period in
Published on 04 April 2012 on http://pubs.rsc.org | doi:10.1039/C2EM00007E
was previously reported by other authors,28 no significant
differences were observed between removal rates measured
during CAS and MBR processes (Table 6).
Removal rates described for HF-MBR and FS-MBR were
similar for NP and its ethoxylates. Both filtration processes
showed a wide range of removal rates, with mean values for
HF-MBR of 19, 42 and 28% and for FS-MBR of 22, 42 and 37%
for NP2EO, NP1EO and NP, respectively. These low removal
rates could be due to the transformation of long chain non-
ylphenol ethoxylates in short chain nonylphenols through the
loss of ethoxide groups.29 In HF/RO-MBR, mean removal rates
for NP2EO, NP1EO and NP were higher than those found in
other processes, reaching mean removal rates of 86, 75 and 51%,

the RO system. These removal rates were considerably higher respectively.

than those measured for CAS treatment where removal rates MBR showed removal rates similar or slightly higher than
were ranged between 14% (diclofenac) and 99% (salicylic acid). those found during CAS treatment (mean removal rates between
As it was reported by other authors,14,25,26 this effect was clearly 6 and 54%) for these compounds. However, low removal rates
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observed in the case of pharmaceutical compounds which show
low removal rates in conventional wastewater treatment, such as
caffeine (17%), estriol (29%) and propranolol (30%).
3.2.2 Removal of priority organic pollutants (LAS, NPE and
DEHP). Table 6 shows mean removal rates achieved for priority
pollutants during the MBR system and the CAS process. In
broad outlines, among all priority organic pollutants studied,
LAS showed the highest removal rates for each of the MBR
treatments evaluated (mean 88%). This high removal rate is
commonly associated to adsorption processes and biodegrada-
tion. LAS with long chain are preferentially adsorbed on sludge
matrix due to their hydrophobic character27 and high sludge
retention time in the MBR system favours biodegradation.4 As
obtained in this study are supported by a convincingly large
number of studies which indicate that removal of NP, NP1EO
and NP2EO is strongly affected by the type and efficiency of
wastewater treatment practiced.30
MBR treatment resulted to be more efficient to remove DEHP
than conventional treatments, reaching mean removal rates of
29% for FS-MBR, 37% for HF-MBR and 70% for HF/RO-
MBR, while mean removal rates did not exceed 3% during CAS
treatment. These removal values were lower than those reported
by other authors for CAS31 and for advanced oxidation
processes.32 It seems that metabolic degradation of DEHP could
be the main removal mechanism, so the isolation of microor-
ganisms from the sludge capable of degrading this plasticiser
appears to give the possibility of efficiently removing such

Table 6 Mean removal rates of pharmaceutical compounds and priority organic pollutants in each of the three MBR systems and in CAS plant

HF-MBR FS-MBR HF/RO-MBR CAS

Therapeutic group Compound Mean (%) RSD (%) Mean (%) RSD (%) Mean (%) RSD (%) Mean (%) RSD (%)

Pharmaceutical compound
Antiinflammatory drugs Diclofenac 54 80 71 46 58 73 57 92
Ibuprofen 77 33 73 36 97 6.3 88 19
a a a
Ketoprofen 93 16 88 25 100
a
Naproxen 94 13 92 17 100 93 11
a
Salicylic acid 67 41 84 31 100 99 0.5
a
Antiepileptic Carbamazepine 25 71 6.7 69 82 37 113
b-Blocker Propranolol 55 47 62 51 a a
29 85
Nervous stimulant Caffeine 95 16 97 8.9 99 3.0 100 13
a a
Estrogens 17a-Ethinylestradiol 72 40 73 43 79 42
a a
17b-Estradiol 46 31 74 23 33 0.4
a a
Estriol 49 71 54 63 85 21
a a
a a a a
Lipid regulators Clofibric acid 84 32 89 30
a
Gemfibrozil 78 27 87 21 100 89 14
Priority organic pollutant
a a
LAS C10 91 14 89 22 95 7.9
C11 87 28 84 83 95 3.9 90 11
C12 85 26 87 27 87 53 99 10
C13 80 36 83 35 95 8.0 90 16
NPE NP1EO 42 80 42 97 75 25 54 67
NP2EO 19 65 22 69 86 44 17 52
NP 28 70 37 109 51 80 5.6 29
Phthalate DEHP 29 85 37 87 70 26 2.6 23
a
Not detected in influent and effluent samples.

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Table 7 Correlation matrix of the variables: solubility, acidity (pKa), hydrophobicity (log KOW and log DOW) and removal rated of the studied
compounds in CAS and MBR technologies

Mw Solubility pKa Log KOW Log DOW % R-MBR % R-CAS

Mw 1.00
0.37 0.50 0.42 0.57
0.39
0.15

Solubility 1.00
0.53
0.77
0.31 0.44 0.28
pKa 1.00 0.46 0.75
0.83
0.60
Log KOW 1.00 0.65
0.47
0.45
Log DOW 1.00
0.67
0.51
% R-MBR 1.00 0.80
% R-CAS 1.00

compound that shows a low rate of hydrolysis and difference of removal rates was observed between FH-MBR and
Published on 04 April 2012 on http://pubs.rsc.org | doi:10.1039/C2EM00007E

photocatalysis.33 FS-MBR; however an improvement was obtained with the use of

the combination of FH-MBR and RO systems.
3.3 Relation between removal rates and physicochemical
properties of the studied compounds
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Correlation analysis was used to evaluate the existence of rela-
tionships between physicochemical properties of the studied
compounds (such as solubility, acidity and hydrophobicity) and
the removal rates achieved during CAS and MBR technologies.
Table 7 shows the correlations between the above-mentioned
parameters which were used as variables to create the correlation
matrix, while the organic compounds were considered as cases.
Positive and negative correlations are written in bold.
As can be seen in Table 7, negative correlation coefficients
were obtained between acidity (pKa) and hydrophobicity (log
KOW and log DOW) of the studied compounds and the removal
rates achieved in both wastewater technologies (MBR and CAS).
In the case of the removal rates achieved and log KOW these
correlations were not significant but a significant correlation
(>
0.6) was obtained between log DOW and the removal rate
reached during MBR technologies.
Higher removal rates were observed in the case of hydrophilic
compounds (low pKa and log DOW values) in both wastewater
treatments which could be indicative that the biodegradation
mechanism is the main removal pathway. This fact could be
favoured due to the high concentration of biomass and long
sludge retention times present in MBR processes17 which could
affect the overall activity of slow growing microorganisms acting
in biodegradation of refractory pollutants.15 Moreover, the high
sludge concentration in MBR technologies contributes to the
high removal of hydrophilic compounds through their accumu-
lation onto sludge via electrostatic interactions with biomass.
4. Conclusions
Occurrence of emerging and priority organic pollutants in MBR
technologies and in CAS treatment has been evaluated. LAS
were the compounds found at the highest concentrations in the
analyzed wastewater, followed by DEHP, NPE, NP and phar-
maceutical compounds. After wastewater treatment an impor-
tant decrease was observed, maintaining a similar distribution in
effluents as was observed in influents. Efficiency of removal rates
was significantly dependent on both the organic compound and
the wastewater treatment technology applied.
The MBR system has been demonstrated to be an acceptable
alternative to provide high-quality water for reuse. No significant
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