water research 44 (2010) 417–426

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Occurrence and removal of pharmaceuticals, caffeine and

DEET in wastewater treatment plants of Beijing, China

Qian Sui, Jun Huang, Shubo Deng, Gang Yu*, Qing Fan
POPs Research Centre, Department of Environmental Science & Engineering, Tsinghua University, Beijing 10084, China

article info abstract

Article history: The occurrence and removal of 13 pharmaceuticals and 2 consumer products, including
Received 14 January 2009 antibiotic, antilipidemic, anti-inflammatory, anti-hypertensive, anticonvulsant, stimulant,
Received in revised form insect repellent and antipsychotic, were investigated in four wastewater treatment plants
5 July 2009 (WWTPs) of Beijing, China. The compounds were extracted from wastewater samples by
Accepted 8 July 2009 solid-phase extraction (SPE) and analyzed by ultra-performance liquid chromatography
Available online 15 July 2009 coupled with tandem mass spectrometry (UPLC–MS/MS). Most of the target compounds were
detected, with the concentrations of 4.4 ng L1–6.6 mg L1 and 2.2–320 ng L1 in the influents
Keywords: and secondary effluents, respectively. These concentrations were consistent with their
Pharmaceuticals consumptions in China, and much lower than those reported in the USA and Europe. Most
Wastewater compounds were hardly removed in the primary treatment, while their removal rates ranging
Removal efficiency from 12% to 100% were achieved during the secondary treatment. In the tertiary treatment,
Advanced treatment different processes showed discrepant performances. The target compounds could not be
Risk assessment eliminated by sand filtration, but the ozonation and microfiltration/reverse osmosis (MF/RO)
China processes employed in two WWTPs were very effective to remove them, showing their main
contributions to the removal of such micro-pollutants in wastewater treatment.
ª 2009 Elsevier Ltd. All rights reserved.

1. Introduction released to the aquatic environment, and consequently found

With the progress of sensitive analytical techniques, the
frequent detection of various pharmaceuticals in the aquatic
environment has received global concerns of both the
academic community and the public (Daughton and Ternes,
1999; Jones et al., 2005). After intake by humans or animals,
the pharmaceuticals will be partially converted to metabo-
lites, however, partially excreted unchanged or as conjugates,
and finally delivered to the wastewater treatment plants
(WWTPs). As there is no unit specifically designed to remove
these compounds, the elimination by most WWTPs seems to
be inefficient (Ternes, 1998; Castiglioni et al., 2006; Lishman
et al., 2006; Nakada et al., 2006; Santos et al., 2007; Vieno et al.,
2007b; Xu et al., 2007; Gulkowska et al., 2008; Paxeus, 2004).
Together with treated wastewater, these compounds are
to contaminate the receiving water bodies (Lindqvist et al.,
2005; Kasprzyk-Hordern et al., 2009), or even raw water sour-
ces of drinking water treatment plant (Ternes et al., 2002;
Vieno et al., 2007a; Radjenovic et al., 2008). Meanwhile, results
of toxicology studies have revealed that some pharmaceuti-
cals are suspected to have direct toxicity to certain aquatic
organisms (Ferrari et al., 2003; Jjemba, 2006; Grung et al., 2008;
Quinn et al., 2008). Besides, their continual but undetectable
effects could accumulate slowly, and finally lead to irrevers-
ible change on wildlife and human beings (Daughton and
Ternes, 1999). Therefore, the occurrence and behavior of
pharmaceuticals in the WWTPs, which are both the sink and
source of the compounds, should be focused on. So far,
concentrations of pharmaceuticals from various therapeutic
classes in the WWTPs have been well documented in the

* Corresponding author. Tel.: þ86 10 62787137; fax: þ86 10 62794006.

E-mail address: yg-den@tsinghua.edu.cn (G. Yu).
0043-1354/$ – see front matter ª 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.watres.2009.07.010
418 water research 44 (2010) 417–426
North America (Thomas and Foster, 2005; Lishman et al.,
2006), Japan (Nakada et al., 2006) and some European countries
(Ternes, 1998; Castiglioni et al., 2006; Santos et al., 2007; Vieno
et al., 2007b; Jones et al., 2007; Paxeus, 2004). Reported species
and concentrations of pharmaceuticals varied from country to
country, and plant to plant, owing to the different usage
patterns. Meanwhile, the removal efficiencies of pharmaceu-
ticals also varied much (Nakada et al., 2006; Gulkowska et al.,
2008), indicating that the removal could be affected by both
the compound-specific properties, and the factors concerning
specific WWTPs, such as types of treatment processes, solids
retention time (SRT), hydraulic retention time (HRT),
temperature, etc. In recent years, very few studies about the
situation in China have been reported. Only one specific
therapeutic class, antibiotics, has been investigated by limited
previous studies (Xu et al., 2007; Gulkowska et al., 2008; Chen
et al., 2008). Therefore, it is necessary and important to
investigate the occurrence and removal of pharmaceuticals
from different therapeutic classes in the WWTPs of China.
Due to the low efficiency of conventional wastewater
treatment processes, some advanced treatment technologies
have been evaluated. Ozonation was found to be effective to
remove pharmaceuticals in real municipal WWTPs of Japan
(Nakada et al., 2007; Okuda et al., 2008) and Germany (Ternes
et al., 2003). Nanofiltration (NF) and reverse osmosis (RO)
membrane filtration, the well-proven technologies to remove
pharmaceuticals from different kinds of waters, have also been
applied at bench, pilot and full scale (Khan et al., 2004; Nghiem
et al., 2005; Drewes et al., 2005; Al-Rifai et al., 2007; Watkinson
et al., 2007; Comerton et al., 2008; Radjenovic et al., 2008).
Retention behavior of pharmaceuticals during the processes
associated with physicochemical properties of pharmaceuti-
cals, membranes as well as the solution chemistry, and
mechanisms of pharmaceutical rejection have been discussed
in Kimura et al. (2004), Nghiem et al. (2005), Nghiem and
Coleman (2008) and Comerton et al. (2008). Recently, consid-
ering the requirement of reclaimed water, several advanced
treatment facilities have been installed in the WWTPs of
Beijing. However, the removal efficiency of micro-pollutants,
such as pharmaceuticals, has not been evaluated yet.
In the present study, we investigated the contamination
levels of 13 pharmaceuticals and 2 consumer products from 8
classes (i.e. antibiotic, antilipidemic, anti-inflammatory, anti-
hypertensive, anticonvulsant, stimulant, insect repellent and
antipsychotic) in four WWTPs of Beijing, China, which have
different advanced treatment units, and evaluated the elimi-
nation efficiencies of the target pharmaceuticals. To the best
of our knowledge, this is the first report on the occurrence and
removal of pharmaceuticals and consumer products from
multiple classes in the WWTPs of China, especially for the
situation during the advanced treatment processes.
2. Materials and methods
2.1. Chemicals
All the standards including chloramphenicol (CP), nalidixic
acid (NA), trimethoprim (TP), bezafibrate (BF), clofibric acid
(CA), gemfibrozil (GF), diclofenac (DF), indometacin (IM),
ketoprofen (KP), mefenamic acid (MA), metoprolol (MTP),
carbamazepine (CBZ), caffeine (CF), N,N-diethyl-meta-tolua-
mide (DEET) and sulpiride (SP) (Appendix) were of analytical
grade (>90%), and purchased from Sigma–Aldrich (Steinheim,
Germany). Isotopically labeled compounds, used as internal
standards, were 13C-phenacetin obtained from Sigma–
Aldrich, and 3D-mecoprop from Dr. Ehrenstorfer (Augsburg,
Germany). HPLC grade methanol, acetone, dichloromethane,
hexane, as well as formic acid were provided by Dikma (USA),
and ultra-pure water was produced by a Milli-Q unit (Millipore,
USA). Stock solutions of individual compound were prepared in
methanol and mixture standards with different concentrations
were prepared by diluting the stock solutions before each
analytical run. All the solutions were stored at 4  C in the dark.
2.2. Sample collection
Four full-scale municipal WWTPs, referred as A, B, C and D,
were selected in our study. These WWTPs employ similar
conventional treatment processes: primary treatment to
remove particles coupled with secondary biological treat-
ment. For the secondary biological treatment processes,
WWTPs A and D employ anaerobic/anoxic/oxic (A2/O) acti-
vated sludge process, anoxic/oxic (A/O) activated sludge
process is adopted in WWTP B, and WWTP C employs oxida-
tion ditch (OD). Other detailed information on each WWTP,
such as inhabitants served, daily flow, HRT and SRT are shown
in Table 1. Part of the secondary effluents was further treated
in WWTPs A, B and D, by the processes of ultrafiltration
(UF)/ozone, sand filtration (SF) and microfiltration/reverse
osmosis (MF/RO), respectively. In WWTP A, a dead-end
ultrafiltration system (Zenon GE) is used. The whole system
has 6 trains of Zee-Weed 1000 membrane. Each train contains
9 cassettes of 57–60 modules per cassette. The membrane,
with the pore size of 0.02 mm, is made by PVDF. The module is
operated in an outside/in configuration at a constant flow of
23 L (m2 h)1 and the total treatment capacity reaches
80,000 m3 d1. The membrane is hydraulically backwashed at
a constant flow rate of 34 (m2 h)1, and 29 times per day. The
backwash phase lasts for 1 min. Maintenance cleaning is
conducted once per day. Membranes are soaked in the sodium
hypochlorite solution (50 mg L1) for 25 min. For the ozonation
process, gaseous ozone is generated from an ozone generator
(Mitsubishi Electric). The ozone dosage and contact time in the
reaction tank is 5 mg L1 and 15 min, respectively. The pH of
the wastewater before ozonation ranges 6.5–8.0 and shows no
significant change after ozonation. As the heart of the
advanced treatment in WWTP D, a spiral-wound crossflow
module is employed for the reverse osmosis (RO) membrane
filtration. The RO membrane (Filmtec, DOW) is made from
a thin-film composite polyamide material. Each module is
designed to operate at a water flux of 1.3 m3 h1, and a product
water recovery of 75–80%. The trans-membrane pressure is
between 0.04 and 0.06 MPa, and the salt rejection remained at
the level of 99%. Every 3–6 months, normally when the trans-
membrane pressure reaches above 0.06 MPa, the membrane is
cleaned with 0.1%(w) sodium hydroxide solution (for organic
foulants), 2%(w) citric acid (for inorganic foulants) and 0.5%(w)
formaldehyde (as biocide). Schematic diagram of treatment
processes in the four WWTPs is shown in Fig. 1.
 water research 44 (2010) 417–426 419

Table 1 – Information of the WWTPs investigated.

WWTP Inhabitants Daily flow HRT (h) SRT (d) Secondary treatment Tertiary treatment
served  103 (103 m3)

A 814 400 11 12–15 A2/O UF/ozone

B 2400 1000 11 20 A/O SF
C 480 200 15 12–16 OD –
D 2415 600 10.67 15 A2/O MF/RO

The samples were collected once from the four WWTPs
during June and July 2008, with no compensation for HRT. All
of them were collected as grab samples in duplicate (500 mL
for influents and 1000 mL for the others) in prewashed amber
glass bottles, kept in the cooler and transported to the labo-
ratory. Immediately after delivery to the laboratory, they were
filtered through prebaked (400  C, >4 h) glass microfiber filters
(GF/F, Whatman) to remove particles and stored at 4  C before
extraction.
2.3. Sample extraction and analysis
The method for the extraction and analysis of pharmaceuti-
cals and consumer products is presented elsewhere (Sui et al.,
in press) and briefly described here. After the solid-phase
extraction (SPE) cartridges (Oasis, HLB, 200 mg, 6 mL) were
conditioned, wastewater samples, added with internal stan-
dards and adjusted to pH ¼ 7, were introduced to the cartridge
via a PTFE tube, at a flow rate of 5–10 mL min1. After washing
by 5 mL of 5.0% methanol solution, the cartridge was dried
under vacuum for 2 h and eluted with 5 mL of methanol. The
extract was then concentrated to 0.4 mL under a gentle
nitrogen stream and stored at 4  C for analysis. Concentra-
tions of the target compounds were analyzed using ultra-
performance liquid chromatography coupled with tandem
mass spectrometry (UPLC–MS/MS). Analytes were separated
using Waters Acquity UPLC system (Waters Corporation, USA)
equipped with Acquity UPLC BEH C18 column (50  2.1 mm,
particle size of 1.7 mm), and detected by Quattro Premier XE
tandem quadrupole mass spectrometry (Waters Corp., USA)
equipped with an electrospray ionization source. The analysis
was carried out in multiple reaction monitoring (MRM) mode,

a Ultrafiltration Ozonation
WWTP A
Tertiary
Effluent

Influent
Grit A/O Secondary
Removal treatment Clarifier Secondary Effluent
Screen

b WWTP B Sand Filtration

Tertiary
Effluent

Influent
Grit Primary A2/O Secondary
Removal Clarifier treatment Clarifier
Secondary Effluent
Screen

c WWTP C

Influent
Grit Oxidation Secondary
Removal Ditch Clarifier
Secondary
Screen Effluent

Tertiary
MF RO
Effluent
d WWTP D `

Influent
Grit Primary A2/O Secondary
Removal Clarifier treatment Clarifier Secondary Effluent
Screen

Fig. 1 – Schematic diagram of the treatment processes in the four WWTPs and sampling site location (C).
420 water research 44 (2010) 417–426

and in general, two precursor ion/product ion transitions were concentrations of some target compounds (i.e. caffeine, DEET,
monitored for one compound with the purpose of quantifi- carbamazepine) resulted in slightly higher deviations.
cation and confirmation.

2.4. Quality control 3. Result and discussion

For each sampling, 500 mL Milli-Q water in an amber glass
bottle as a field blank was brought to the WWTPs, exposed to
the environment where the samples were taken from, and
then delivered back to the laboratory with samples. For each
set of samples (normally 10 samples), at least one procedural
blank was prepared from ultra-pure water in the laboratory.
Both the field blanks and procedural blanks were run identi-
cally to the wastewater samples, and the concentrations of
target compounds were below the limit of quantification
(LOQ). The absolute recoveries, calculated by comparing the
concentrations of target compounds in spiked and unspiked
wastewaters, were proved to be 73–102% and 50–95% in the
effluent and influent for most compounds, respectively. While
for several compounds (i.e. sulpiride, gemfibrozil, mefenamic
acid), the absolute recoveries were not satisfactory. However,
13
C-phenacetin and 3D-mecoprop, the surrogate standards
used for positive and negative ion mode respectively were able
to compensate for the loss of most analytes, and relative
recoveries were 67–130% for all the analytes in the effluent
and 79–140% in the influents except mefenamic acid (251%)
and nalidixic acid (178%). Therefore, the concentrations of
these two compounds in the wastewater influents were not
quantitatively determined and reported. The LOQs were
0.3–5.5 ng L1 and 0.7–20 ng L1 in the effluent and influent,
respectively. Detailed information about the calibration,
recoveries, LOQ, matrix effects, etc. were described in Sui et al.
(in press), and briefly listed in Table 2. As duplicate samples
were collected at each sampling site, mean concentrations
were adopted. In most cases, deviations of duplicate samples
were less than 20%. For some tertiary effluent samples, low
3.1. Influents
As shown in Fig. 2, 12 target compounds were detected in all
the influent samples from the four WWTPs, while ketoprofen
was below LOQ in all wastewater samples. The most
abundant compounds detected were the consumer products,
caffeine (3.4–6.6 mg L1) and N,N-diethyl-meta-toluamide
(0.6–1.2 mg L1), probably due to the large consumption of
drinks containing caffeine (i.e. coffee, tea, etc.) and wide
application of insect repellent during the summer time when
we sampled. Diclofenac, trimethoprim, sulpiride, carbama-
zepine, indometacin and metoprolol showed relatively high
concentrations (Fig. 2). A similar composition distribution
was observed among all the influents of the four WWTPs.
The concentrations of target pharmaceuticals except
diclofenac and trimethoprim, were much lower than those
reported in the European and North American countries
(Thomas and Foster, 2005; Lishman et al., 2006; Vanderford
and Snyder, 2006; Santos et al., 2007; Gomez et al., 2007; Vieno
et al., 2007b; Huerta-Fontela et al., 2008). For instance, the
concentrations of ketoprofen in the wastewater influents
were recorded to be 2.0  0.6 mg L1 in Finland (Lindqvist et al.,
2005), 200 ng L1 in Australia (Al-Rifai et al., 2007), and
300–1360 ng L1 in Spain (Santos et al., 2007), while in the
influents of four WWTPs in Beijing, it could not be detected.
Concerning gemfibrozil, which is used to lower cholesterol
and triglyceride levels in the blood, the contamination level
found in the present study was 24–140 ng L1, even 1 or 2 order
of magnitude lower than those in the USA (4770 ng L1,
Vanderford and Snyder, 2006) and Canada (418 ng L1,

Table 2 – Instrumental quantification limit (IQL), limit of quantification (LOQ), absolute recovery (AR), relative recovery (RR)
and matrix suppression of target compounds.
Compounds IQL (pg) LOQ (ng L1) AR (n ¼ 6, %) RR (n ¼ 6, %) Matrix effect (%)
a a a a
Effluent Influent Effluent Influent Effluent Influent

BF 0.5 0.3 0.7 74 (3) 58 (5) 94 (4) 94 (10) 27

CA 10 5.4 16 74 (4) 50 (4) 94 (6) 82 (8) 30
CBZ 2.5 1.0 2.8 100 (4) 71 (12) 130 (6) 133 (23) 6
CF 2.5 1.7 3.3 60 (3) 61 (37) 77 (4) 114 (70) 49
CP 2.5 1.0 2.3 98 (7) 86 (9) 124 (10) 140 (17) 39
DEET 2.5 1.3 3.2 76 (3) 63 (6) 99 (5) 118 (14) 24
DF 10 4.7 9.4 86 (12) 85 (19) 109 (16) 139 (32) 4
GF 10 4.2 20 95 (12) 40 (11) 120 (16) 65 (18) 28
IM 2.5 1.3 2.8 80 (12) 73 (13) 101 (16) 119 (22) 1
KP 10 5.5 18 69 (9) 44 (3) 87 (12) 72 (7) 46
MA 10 5.5 5.2 73 (11) 154 (24) 92 (15) 251 (41) 13
MTP 2.5 1.1 3.3 88 (3) 60 (3) 115 (5) 113 (9) 15
NA 2.5 1.1 2.1 91 (9) 95 (9) 118 (12) 178 (20) 3
SP 0.5 0.4 1.0 51 (5) 42 (3) 67 (7) 79 (7) 63
TP 2.5 1.0 2.7 102 (7) 74 (16) 132 (9) 139 (31) 5

a Value in the brackets refers to the deviation of the recovery.

 water research 44 (2010) 417–426 421

Lishman et al., 2006). The low levels of target pharmaceuticals

a 10000
were probably due to the lower per capita consumption in
Influents
China than in the countries with higher socioeconomic
statuses, where medical care is more prevalent (Thomas and
1000 Foster, 2005). The per capita consumption rate of gemfibrozil
Concentration (ng L-1)

in China is estimated to be 0.036 mg person1 d1 (Table 3),

lower than those in Germany (0.2 mg person1 d1, Ternes,
100 1998) and Canada (0.2 mg person1 d1, Lishman et al., 2006).
Since the levels of target pharmaceuticals were somewhat
different from those of European and North American
countries, we theoretically calculate the concentration of
10
pharmaceuticals in the wastewater influent by the following
equation (Lindqvist et al., 2005; Nakada et al., 2006)

T  e%  I  1012
1 Cpred ¼ (1)
365  P  Q
DEET

CF

CP

TP

BF

CA

GF

DF

IM
MTP

CBZ

SP
where Cpred is the predicted concentration of the pharma-
Pharmaceuticals & Consumer Products ceutical in wastewater influent (ng L1); T is the total produc-
tion of a pharmaceutical both for human and animal use in
b 10000
China per year (ton year1), P is the population of China, e% is
Secondary effluents the amount of the pharmaceutical excreted unchanged, I is
the number of inhabitants served and Q is the influent flow
1000 (m3 d1). The predicted concentrations of gemfibrozil, diclo-
Concentration (ng L-1)

fenac, indometacin, ketoprofen, carbamazepine, and sulpir-

ide were comparable to those measured in the influents
(Table 3). Much lower measured concentration than predicted
100
concentration of chloramphenicol was probably because it
had been forbidden for use in food and aquaculture in China
since 2005, and the available data about the production of
10 pharmaceuticals were based on the year of 2004. It should be
noticed that since there is no available data on the total
consumption of any pharmaceutical, we used figures for total
production of individual pharmaceutical instead. Therefore,
1
the differences between the amounts actually produced and
DEET

CF

CP

TP

BF

CA

GF

DF

IM

MA

MTP

CBZ

SP

applied as well as the amount used in human and veterinary

Pharmaceuticals & Consumer Products medicine could not be distinguished, which might result in
overestimation of the theoretical concentration. Neverthe-
Fig. 2 – Concentrations of target pharmaceuticals in less, the comparability between the predicted concentrations
wastewater influents (a) and secondary effluents (b) of four and measured concentrations illustrates the overall reason-
WWTPs in Beijing. ability of the approach.

Table 3 – Outputs, per capita consumption, predicted concentrations (PECs) and measured concentrations (MECs) of some
pharmaceuticals in the wastewater influents of WWTPs investigated.
Compound Outputa Per capita Excreted PEC MEC
(tons year1) consumption unchangedb (%) (ng L1) (mean, ng L1)
(mg person1 d1)

CP 1929 4.051 5–10 844 31

TP 2352 4.939 45 6173 400
GF 17 0.036 76 76 60
DF 328 0.689 15 287 318
IM 277 0.582 10–20 242 129
KP 92 0.193 2.7 15 n.d.c
CBZ 395 0.830 2–3 58 113
SP 98 0.206 15–70 243 157

a From CMEIN (2005).

b From Bolton and Null (1981), Ternes (1998), Khan and Ongerth (2004), Niwa et al. (2005), Nakada et al. (2006), Jjemba (2006).
c n.d. ¼ Not detected.
422 water research 44 (2010) 417–426

3.2. Secondary effluent

Table 4 – Measured concentrations in the effluent
samples, predicted no-effect concentrations and risk
Similar to the influent samples, ketoprofen was below the LOQ quotients (MEC/PNEC) of target compounds.
in all the secondary effluent samples. Nalidixic acid and
Compound MECeff (ng L1) PNECa (ng L1) MEC/PNEC
chloramphenicol were detected only in one WWTP, with the
concentration of 8.1 and 19 ng L1, respectively. The mean CF 15 182,000 0.0001
TP 140 16,000 0.0087
concentrations of the other 12 compounds ranged from 5 to
BF 4.7 6000 0.0007
200 ng L1 (Fig. 2). Diclofenac, N,N-diethyl-meta-toluamide,
CA 13 42,000 0.0003
trimethoprim, sulpiride and indometacin showed high DF 204 100 2.0440
concentrations in the secondary effluents. Carbamazepine KP n.d. 306,000 –
and metoprolol followed, with the concentrations ranging MTP 79 31,000 0.0025
from 69 to 120 ng L1, and 60 to 108 ng L1, respectively. Other CBZ 108 420 0.2574
compounds, such as caffeine, gemfibrozil and mefenamic a From Santos et al. (2007), Lindqvist et al. (2005), Grung et al.
acid, occurred at the lowest levels. Despite of a wide variation (2008), Ferrari et al. (2003), Huschek et al. (2004).
of trimethoprim from different WWTPs, the composition
profiles of target pharmaceuticals in secondary effluents from
the four WWTPs were quite similar (Fig. 3). the dominant contributor in the wastewater effluent, the risk
The concentration levels of most pharmaceuticals and quotient was higher than 1, implicating a risk to the aquatic
consumer products detected in the secondary effluent were environment.
also lower than those reported in the Europe. They were over
100 ng L1, in some cases even up to 500 ng L1 in the waste- 3.3. Removal efficiency of conventional treatment
water effluents of the European countries (Santos et al., 2007;
Gomez et al., 2007; Ternes, 1998; Vieno et al., 2007b). While in The removal efficiency during the primary treatment was low,
the present study, 10 out of 15 compounds were less than indicating no significant adsorption of target compounds to
100 ng L1, and none of them exceeded 400 ng L1 in any the particles removed in this stage (Fig. 4). Most of the phar-
effluent samples (Fig. 2). Our results were in agreement with maceuticals and consumer products have log Kow values of
those in Japan (Nakada et al., 2006), Korea (Kim et al., 2007) and less than 3.0, so they are not expected to adsorb significantly
some other cities of China (Xu et al., 2007; Gulkowska et al., to the particles. Other pharmaceuticals with higher Kow
2008; Chen et al., 2008). For instance, the concentrations of values, such as gemfibrozil, have much lower pKa values than
chloramphenicol in the effluents of 4 WWTPs in Guangzhou the pH of wastewater. Therefore, they are dissociated and
were <LOQ-17 ng L1 (Xu et al., 2007), while their concentra- expected to be >98% in the aqueous phase (Thomas and
tions in our study were <LOQ-19 ng L1. Carbamazepine was Foster, 2005), and not bound to the particles.
detected in the wastewater effluents of Korea and Taiwan, During the secondary treatment, the average removal rate
with the concentration of 73–729 and 290–960 ng L1, respec- for different compounds ranged from 12% to 100% (Fig. 4).
tively (Chen et al., 2008; Kim et al., 2007), which were Caffeine, bezafibrate, trimethoprim and DEET were effectively
comparable with those in the effluents of Beijing. removed, with the average efficiency of 100  0%, 88  12%,
The environmental risk caused by these pharmaceuticals 76  24% and 69  21%, respectively. These results were
can be calculated by dividing the measured environmental comparable with those found in the previous studies (Ternes,
concentration (MEC) by the predicted no-effect concentration 1998; Okuda et al., 2008; Thomas and Foster, 2005; Castiglioni
(PNEC) of individual compound (European Environment et al., 2006). Caffeine was proved to be readily biodegradable
Agency, 1998). Thanks to the low levels of pharmaceuticals (Okuda et al., 2008; Thomas and Foster, 2005; Huerta-Fontela
studied, the risk quotients for most compounds were below 1
in the wastewater effluents (Table 4). However, for diclofenac,
120
Primary treatment
100 Secondary treatment

D 80
Others
Removal efficiency (%)

GF 60
MTP
C IM 40
WWTP

CBZ
SP 20
B TP
DF 0
DEET

CF

TP

BF

CA

GF

DF

IM

MTP

CBZ

SP

DEET
-20
A
-40

0 20 40 60 80 100 -60
Pharmaceutical Compostion (%) Pharmaceutical

Fig. 3 – Composition profiles of target pharmaceuticals in Fig. 4 – Removal efficiencies of target pharmaceuticals
secondary effluent samples from four WWTPs in Beijing. during the conventional treatment.
 water research 44 (2010) 417–426 423

et al., 2008; Gomez et al., 2007). The removal rate of bezafibrate

Table 5 – Removal efficiencies (%) of target
was found to be 87% in six Italian WWTPs in summer time pharmaceuticals and consumer products by advanced
(Castiglioni et al., 2006), very similar to that observed in our treatment processes in studied WWTPs.
study. The concentrations of DEET were decreased by more
Compound WWTP A WWTP B WWTP D
than 80% during the biological treatment in the WWTP of
Japan (Okuda et al., 2008), slightly better than our results. A UF Ozone SF MF/RO
second group of pharmaceuticals, including three anti- DEET 0–50 50–80 0–50 >90
inflammatory drugs, clofibric acid, gembrozil, metoprolol and CF <0 50–80 <0 50–80
sulpiride, had lower removal rates with large variation in TP 0–50 >90 80–90 >90
different WWTPs studied. For instance, 28–53% of diclofenac, BF 0–50 0–50 0–50 >90
CA <0 50–80 <0 80–90
a representative of the anti-inflammatory drugs, was removed
GF 0–50 80–90 50–80 >90
by secondary treatment in the WWTPs, which was between
DF 0–50 >90 <0 >90
26% in Finland (Lindqvist et al., 2005) and 69% in Germany IM 0–50 >90 <0 >90
(Ternes, 1998). The elimination of these compounds may be MA 0–50 80–90 <0 0–50
highly dependent on the configurations and operation condi- MTP 0–50 80–90 <0 >90
tions of individual WWTP as well as wastewater characteris- CBZ <0 >90 0–50 >90
tics, and thus no definitive conclusion could be reached. SP 0–50 >90 0–50 >90

Higher load of carbamazepine was found in the secondary

effluent than in the primary effluent, indicating negative
removal efficiency during the secondary treatment. Some
carbamazepine was found to be excreted as the form of
conjugates (Vieno et al., 2007b), which was biodegraded to
carbamazepine by enzymatic processes during the secondary
treatment, resulting in additional amounts of carbamazepine
in the secondary effluent. However, as the calculations of all
the removal efficiencies were based on grab samples that were
not sampled with a hydraulic lag in the present study, some
error might be brought in due to diurnal variation of the
concentration. Therefore, the present study only provided
a snapshot of the removal of pharmaceuticals and consumer
products in the WWTPs of Beijing. To better illustrate that,
24-h composite samples that are lagged by HRT should be
collected and analyzed in further studies.
It has been reported that high HRT (>12 h) and SRT (>10 d)
may contribute to an increased removal rate of pharmaceu-
ticals (Jones et al., 2007; Vieno et al., 2007b). In the present
study, the WWTP C, in which the HRT was higher than the
others, was the best in removing these compounds, due to
increased contact time of target compounds and the micro-
organisms. On the other hand, the different SRTs did not have
significant effects on the removal efficiency, probably because
the SRTs in all the four WWTPs were relatively high (>10 d),
and without large differences. In addition, it is noteworthy
that the WWTP C employed oxidation ditches, which showed
better removal of natural estrogens and estrogenic activity
than A/O (Hashimoto et al., 2007). It also could be the reason
for the higher removal efficiencies in the WWTP C. Further
investigation for different types of WWTPs is necessary to
confirm the results mentioned above.
3.4. Removal efficiency in advanced treatment processes
The removal efficiencies of the pharmaceuticals during the SF,
UF/ozonation, as well as MF/RO treatment in three corre-
sponding WWTPs are listed in Table 5.
Generally, sand filtration was not effective for these
compounds. Only trimethoprim, DEET and gemfibrozil were
removed slightly during this treatment process. It should be
noticed that these compounds were efficiently removed in the
secondary treatment, indicating that the biodegradation on
the biofilm present on the sand particle, rather than the
removal with particles, may be the main reason for their
elimination (Gobel et al., 2007).
The results showed that ozonation is effective in removing
most of the target compounds, probably due to the operation
conditions employed in WWTP A (ozone dosage: 5 mg L1,
contact time: 15 min). Carbamazepine, diclofenac, indo-
methacin, sulpiride and trimethoprim were significantly
eliminated, with the removal rates of above 95%. The double
bond in the azepine ring of carbamazepine and pyrrole ring of
indomethacin, and the non-protonated amine of diclofenac
and trimethoprim were susceptible to ozone attack (Vieno
et al., 2007a; Nakada et al., 2007; Westerhoff et al., 2005). The
removal efficiencies of DEET and metoprolol were modest.
The amide group, which is not reactive with ozone, could be
the reason for the modest removal of DEET (Nakada et al., 2007).
Low removal efficiencies were found for bezafibrate, clofibric
acid, as well as caffeine. Only 14% of bezafibrate disappeared
in the ozone process, consistent with its low rate constants
with ozone (590  50 M1 S1, Huber et al., 2003). The reaction
site of bezafibrate is the R-oxysubstituent (–O–C(CH3)2COOH)
on one of the aromatic rings. However, as the pKa of bezafi-
brate is 3.6, the R-oxysubstituent cannot be deprotonated and
consequently the overall rate constant at pH > 4 is much lower
(Huber et al., 2003). It should be noticed that during the
ozonation, most of the pharmaceuticals were not mineralized
but transformed to the oxidation products. For instance, three
oxidation products containing quinazoline-based functional
groups were identified during the ozonation of CBZ (Mcdowell
et al., 2005).
The good performance of ozonation in the present study
was consistent with Ternes et al. (2003), Huber et al. (2005)
and Okuda et al. (2008). When 5 mg L1 ozone was applied to
the effluent of a municipal WWTP in Germany (contact time:
18 min), target compounds, such as trimethoprim, carba-
mazepine, indomethacin, clofibric acid, were removed by
more than 50% (Ternes et al., 2003). Huber et al. (2005)
conducted a pilot study on the oxidation of pharmaceuticals
during ozonation of conventional activated sludge (CAS) and
membrane bio-reactor (MBR) effluents with various ozone
dosages, and found that macrolide and sulfonamide antibi-
otics, estrogens, and acidic pharmaceuticals diclofenac,
424 water research 44 (2010) 417–426

naproxen and indomethacin were oxidized by more than

a Tertiary treatment
90–99% for ozone doses 2 mg L1 in all effluents. Conventional treatment
120
The elimination by ultrafiltration in the WWTP A was low
for all the investigated compounds. The molecular weight cut-

Removal Contribution (%)

100
off (MWCO) of UF membranes was much higher than 1000 Da,
80
thus UF membranes showed poor retention of all the inves-
tigated pharmaceuticals, of which the molecular weight are 60
less than 400 Da. The removal of individual target compound
was less than 50%, and might be due to the adsorption onto 40

the membrane. It has been also demonstrated that UF 20

membrane typically had less than 40% retention of 27 PPCPs,
and the mass balances calculated based on the concentration 0

DEET

CF

CP

TP

BF

CA

GF

DF

IM

MTP

CBZ

SP
of each compound in feed, permeate and retentate showed
-20
the observed retention was significantly governed by adsorp-
tion (Yoon et al., 2006). Pharmaceutical
In contrast, MF/RO employed in WWTP D was very effec-
tive. In the effluent of MF/RO, all the target compounds except b 180 Tertiary treatment
caffeine were not detected. Generally, one or combination of

Contribution to removal efficiency (%)

160 Secondary treatment
three basic mechanisms could be involved during the rejec- 140 Primary treatment
tion of solute by NF/RO membrane: steric effect, charge 120
exclusion and adsorption (Radjenovic et al., 2008). For most 100
pharmaceuticals, the rejections were considered to be domi- 80
nated by steric interaction in ‘‘tight’’ NF or RO membrane 60
filtration (Nghiem et al., 2005; Radjenovic et al., 2008). As most 40
investigated compounds have molecular weights about 20
200–400 Da, smaller than MWCO of RO membrane applied, 0
DEET

CF

TP

BF

CA

GF

DF

IM

MTP

CBZ

excellent rejection of most pharmaceuticals by RO membrane
was observed in this study as well as in previous studies
(Kimura et al., 2004; Al-Rifai et al., 2007; Radjenovic et al.,
2008). Besides, membrane fouling and the presence of organic
matter in the wastewater effluents likely contributed to higher
rejections of pharmaceuticals, especially for some hydro-
phobic ionogenic compound (Nghiem and Coleman, 2008;
Comerton et al., 2008).
Nevertheless, the rejections of two compounds, caffeine
and mefenamic acid were slightly lower (i.e. 50–80% and
0–50%, respectively). The concentration of mefenamic acid in
feed wastewaters of MF/RO membrane process was very low,
only a bit higher than its LOQ in the wastewater effluent,
which could be the reason for the low rejection rate. The low
retention of caffeine in the present study was inaccordance
with Drewes et al. (2005). They found that in two full-scale RO
facilities, target EDCs and PPCPs were efficiently rejected to
below detection limit except for caffeine, still detected in the
permeates. The physiochemical properties might explain the
low rejection rate of caffeine. As a representative of hydro-
philic and non-ionic compounds, the rejection driven by
charge exclusion and adsorption is negligible, and steric
exclusion is solely responsible for the retention of caffeine
(Nghiem et al., 2005). However, the molecular weight of
caffeine is 195 Da, smaller than other target compounds, and
might result in the decreased removal efficiency during the RO
membrane filtration process.
Compared to the other two, the WWTPs employing ozone
and RO membrane filtration as advanced treatment were
more efficient in removing pharmaceuticals. For these
WWTPs, the advanced treatment made a significant contri-
bution to the total elimination of most pharmaceuticals
(Fig. 5). Therefore, the utility of efficient advanced treatment
could be considered as a tool to reduce pharmaceuticals in the
SP
-20
-40
-60
Pharmaceutical
Fig. 5 – Contributions of primary, secondary (or
conventional treatment) and tertiary treatment to the total
elimination of selected pharmaceuticals in WWTP A (a)
and WWTP D (b).
municipal wastewater treatment plants. However, the prob-
lems of membrane fouling and further treatment or disposal
of retentate challenge the application of RO membrane
filtration (Van der Bruggen et al., 2008). For ozonation, as most
of the pharmaceuticals could not be mineralized, and oxida-
tion products are formed from parent pharmaceutical
compounds (Mcdowell et al., 2005), more research is required
to identify the oxidation products and their potential toxicity
during the partial oxidation process (Nakada et al., 2007).
Besides, economic feasibility should be evaluated by esti-
mating the energy consumption and investment and
operation costs for both advanced treatment processes (Joss
et al., 2008).
4. Conclusion
13 out of 15 pharmaceuticals and consumer products from
eight classes were detected at four WWTPs in Beijing, China.
The concentrations of most compounds in the influent and
secondary effluent were lower than those reported in the USA
and Europe, but consistent with the production profile of the
 water research 44 (2010) 417–426
pharmaceuticals in China. According to the result of risk
assessment for the secondary effluent, only diclofenac might
pose a risk to the aquatic environment. The removal effi-
ciencies by the conventional treatment varied for different
compounds, depending on their chemical structures, physi-
ochemical properties, as well as the specific treatment
processes utilized at each WWTP. Further removal could be
achieved by adopting some advanced treatment processes,
such as ozonation and MF/RO. However, others, such as
sand filtration, showed low efficiency in removing these
compounds from secondary effluent.
Acknowledgement
This study was supported by the National Science Fund for
Distinguished Young Scholars (No. 50625823).
Appendix.
Supplementary data
Supplementary information related to this article can be
found at doi:10.1016/j.watres.2009.07.010.
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