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Environmental
Monitoring
Cite this: J. Environ. Monit., 2011, 13, 2042
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Monitoring of pharmaceutically active compounds on the Guadalquivir River
basin (Spain): occurrence and risk assessment
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noz, J. L. Santos,* I. Aparicio and E. Alonso

J. Mart
ın, D. Camacho-Mu~
Received 24th February 2011, Accepted 10th May 2011
DOI: 10.1039/c1em10185d

Guadalquivir River (South of Spain) is among the major freshwater sources of the European Atlantic
basin. Until now scientific efforts have been focused on contamination by heavy metals and some
priority pollutants in Guadalquivir River. However, the presence of ‘‘emerging contaminants’’, such as
pharmaceutically active compounds, has not yet been studied. In this work the occurrence and risk
assessment of sixteen pharmaceutically active compounds, belonging to different therapeutic groups, in
Guadalquivir River during its course through Seville city are reported. Wastewater effluents from four
wastewater treatment plants discharging into Guadalquivir River and river water samples were
analyzed. All studied pharmaceutically active compounds, except sulfamethoxazole, trimethoprim,
estrone and clofibric acid, were detected in effluent wastewaters at concentration levels up to
28.9 mg L
1. Among the pharmaceutically active compounds found in effluent wastewater, seven were
present in Guadalquivir River samples at concentration levels up to 0.75 mg L
1, which indicated an
important dilution from effluent discharge. Environmental risk assessment reveals that potential
ecotoxicological risk cannot be expected on Guadalquivir River at measured concentration levels.
Only, the lipid regulator gemfibrozil showed a medium risk for the environment. The risk for acute
toxic effects in the environment with the current use of active pharmaceutical ingredients is unlikely.
However, the results do not rule out the potential for chronic environmental effects.

1. Introduction persistent owing to their continuous discharge into lakes and

Pharmaceutical residues in the environment have been recog-
nized as one of the emerging research areas in environmental
chemistry. Several studies have reported the inefficiency of
wastewater treatment plants (WWTPs) for the removal of these
compounds from influent wastewater1–6 and, as a result, these
compounds have been detected in effluent wastewaters and in
surface water at concentration levels of several ng or even mg per
litre.7–9 Pharmaceutically active compounds are considered
Department of Analytical Chemistry, High Polytechnic School, University


of Seville, C/Virgen de Africa 7, E-41011 Seville, Spain. E-mail:
JLSantos@us.es; Fax: +34-9-5428-2777; Tel: +34-9-5455-6250
rivers. Moreover, compounds such as carbamazepine or caffeine
have been proposed as anthropogenic markers.10,11
The most important issue of concern about the presence of
pharmaceutically active compounds in the aquatic environment
is the ecotoxicological effect that they may cause.2 Although it is
unlikely that these pollutants would be found at concentrations
high enough to induce acute effects, growing evidence suggests
that they may be present at concentrations able to cause chronic
effects or even lethal effects.1,12–14 For example, diclofenac, which
is widely used to treat livestock across the Indian subcontinent,
has been shown to be the major cause of the decline of three
Indian gyps vulture populations12 and the antiepileptic drug
carbamazepine affects various organs of the common carp

Environmental impact
Effluent wastewater from wastewater treatment plants has been recognized as the main source of pharmaceutically active
compounds to the receiving waters. The distribution of these compounds in surface water in relation with wastewater effluent
discharges has not been sufficiently described. In this paper the distribution and environmental risk of pharmaceutically active
compounds belonging to different therapeutic groups is studied in the receiving water of four wastewater effluents from Seville
(South of Spain). The work contributes to extending the understanding of how wastewater effluents affect the concentration levels of
pharmaceutically active compounds in rivers and the environmental risk caused by these compounds in surface water affected by
major cities.

2042 | J. Environ. Monit., 2011, 13, 2042–2049 This journal is ª The Royal Society of Chemistry 2011

(Cyprinus carpio).15 However, until now the ecological risk
associated with the presence of pharmaceutically active
compounds discharged from WWTPs in receiving waters is not
sufficiently described.16–18
The Guadalquivir River is the second longest river in Spain,
and it is among the major European rivers. With a length of
657 km, it flows southwest through the region of Andalusia, with
a drainage area of 57 527 km2, affecting population regions of
more than 4 million inhabitants, and flowing through major
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cities such as Cordoba and Seville. Its natural environment is one
of the most varied in Europe, being present in half of the most
representative European plants and nearly all from the North
African region.
However, despite its importance, only a few studies have been
carried out about the presence of metals19 in the Guadalquivir
river basin. Moreover, the Guadalquivir Hydrographical
Confederation from the Andalusia Government offers moni-
toring data of several organic compounds such as phenols,
pesticides or polycyclic aromatics hydrocarbons in several river
stations included in the river network for water quality moni-
toring called Integrated Water Quality Network. However, to the
best of our knowledge, no investigations have been carried out
about the presence of pharmaceutically active compounds in the
Guadalquivir river basin.
The objective of the present study is to investigate the occur-
rence of some commonly used pharmaceutically active
compounds in Guadalquivir River, and to further assess the
potential risks to the aquatic organisms in the river. This study
follows on a study carried out in Do~ nana Park (South of Spain)1
in which the occurrence and risk assessment of pharmaceutically
active compounds was evaluated in WWTP treating wastewater
from small communities discharging their effluents to several
streams affecting Do~ nana Park. In this study the occurrence and
risk assessment of pharmaceutically active compounds is studied
in Guadalquivir River, affected by the discharge of wastewater
effluents from the four WWTP that work in Seville city (700 000
inhabitants), from which more than 250 000 m3 of wastewater are
discharged daily. This manuscript advances in the knowledge of
how large cities affect the rivers through the discharge of phar-
maceutically active compounds present in their wastewater.
The studied pharmaceutically active compounds were five
non-steroidal antiinflammatory drugs (diclofenac, ibuprofen,
ketoprofen, naproxen and salicylic acid), two antibiotics (sulfa-
methoxazole and trimethoprim), a b-blocker (propranolol), two
lipid regulators (clofibric acid, metabolite of clofibrate, and
gemfibrozil), an antiepileptic drug (carbamazepine), four estro-
gens (17a-ethinylestradiol, 17b-estradiol, estriol and estrone),
and a nervous stimulant (caffeine).
2. Materials and methods
2.1. Description of the area of study and sampling
In this work we studied a length of about 50 km of the Gua-
dalquivir River. Along its course, about 10 km downstream from
the first sampling point, the river passes through Seville, with
a population of more than 700 000 inhabitants. It is the main
urban and industrial centre of the zone. The wastewaters are
treated before discharging into the river in four WWTPs (named
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North, South, East and West WWTP). The treatment in the four
WWTPs is based on primary (settling) and secondary (activated
sludge) treatments which had a total treatment capacity of
445 000 m3 d
1 (Fig. 1).
Thirty-two effluent wastewater samples were collected
throughout a period of 1 year from January 2008 to January
2009 in four WWTPs located in Seville city. Daily composite
samples were obtained by mixing aliquots collected every hour
by an automatic device. Sample volumes collected each hour
were proportional to the effluent flows. A total sample volume of
2.5 L were transferred to amber glass bottles and stored at 4  C
until analysis.
Two monthly river water samples were collected by two
sampling campaigns carried out in wet (November to December
2008) and dry (from June to September 2009) season. Sampling
sites were selected from upstream to downstream of the discharge
points of each WWTP (Fig. 1). During sampling, a global posi-
tion system (GPS) was used to locate the exact sampling sites.
Sampling point S1 and S2 were located in the North of Seville. S1
(37 270 33.9000 N; 5 590 57.6700 O) was located upstream from the
discharge of the North WWTP and S2 (37 240 35.1200 N;
6 000 43.9100 O) was located 1 km downstream from this
discharge. S3 (37 190 59.7300 N; 6 010 09.4300 O) was located in the
West of Seville, downstream from the discharge of West WWTP
and S4 (37 090 38.5000 N; 6 060 15.4300 O) was located below the
confluence of Guadalquivir River and Guadaira River, which
receives the discharge of East and South WWTPs.
2.2. Materials and standards
HPLC-grade water, acetonitrile and methanol were purchased
from Romil Ltd. (Barcelona, Spain). Hexane, acetone (HPLC
grade) and sulfuric acid of analytical grade were obtained from
Panreac (Barcelona, Spain). Potassium dihydrogen phosphate of
analytical grade was purchased from Scharlau (Barcelona,
Spain). Carbamazepine, diclofenac, ketoprofen, naproxen and
salicylic acid (97–100% purity) were purchased from Sigma-
Aldrich (Steinheim, Germany). Caffeine was obtained from
Merck (Darmstadt, Germany). Clofibric acid, gemfibrozil,
ibuprofen, propranolol hydrochloride, 17a-ethinylestradiol,
17b-estradiol, estriol, estrone, sulfamethoxazole and trimetho-
prim (99% purity) were purchased from Dr Ehrenstorfer
(Augsburg, Germany).
Three millilitres of solid phase extraction (SPE) cartridges,
packed with 60 mg of Oasis HLB, were purchased from Waters
(Milford, MA, USA).
Stock solutions of each pharmaceutically active compound at
concentration of 1000 mg L
1 were prepared in methanol and
stored at 4  C. Working solutions were prepared by diluting the
stock standard solutions in methanol.
2.3. Analytical procedure
Analytical determination was carried out according to a previ-
ously reported method.20 The method was based on sample
treatment by solid-phase extraction and determination by high-
performance liquid chromatography with ultraviolet diode array
and rapid scan fluorescence detectors connected on line.
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Fig. 1 Sampling locations in Guadalquivir River (South of Spain).
Recoveries achieved in sample treatment were from 69 to
116%. Solid phase extraction allows a preconcentration factor of
5000 in wastewater effluent and surface water samples which
leads to limits of detection and quantification ranged from 0.001
to 0.162 mg L
1 and from 0.002 to 0.539 mg L
1, respectively
(Table 1).
2.4. Environmental risk assessment
Potential risks of each pharmaceutical compound were assessed
through the calculation of the risk quotients (RQ) as has been
previously described.14,21 RQs were determined as the ratio
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between measured concentrations of pharmaceutically active
compounds (MEC) and their predicted no-effect concentrations
(PNEC). Concentration levels measured during the monitoring
period were used as MEC values. PNEC values were estimated
from the lowest ecotoxicological data found in the literature
(Effective Concentration, EC50 and Letal concentration, LC50)
for toxicological studies carried out in aquatic organisms and
applying an assessment factor of 1000 which takes into consid-
eration the different sensibilities from one organism to the
next.6,7,21,22 A commonly used risk ranking criteria was applied:
RQ # 0.1 means minimal risk, 0.1 # RQ # 1 means median risk,
and RQ $ 1 means high risk.17
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 View Article Online

Table 1 Recovery and limits of detection (LOD) and quantification (LOQ) of the method in effluent wastewater and surface water samples

Recovery (%)

Pharmaceutical compound Effluent wastewater Surface water LOD/mg L
1 LOQ/mg L
1

Antiinflammatory drugs Diclofenac 101 88.3 0.015 0.049

Ibuprofen 99.9 88.1 0.068 0.228
Ketoprofen 82.4 96.7 0.037 0.124
Naproxen 95.0 92.1 0.001 0.003
Salicylic acid 96.5 95.4 0.008 0.027
Antibiotics Sulfamethoxazole 74.6 87.4 0.008 0.028
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Trimethoprim 70.9 70.9 0.006 0.020

Antiepileptic drug Carbamazepine 71.5 93.1 0.008 0.027
b-Blocker Propranolol 72.9 101 0.001 0.002
Nervous stimulant Caffeine 107 90.5 0.014 0.048
Estrogens 17a-Ethinylestradiol 106 81.3 0.010 0.033
17b-Estradiol 87.8 116 0.022 0.072
Estriol 63.7 68.5 0.003 0.009
Estrone 88.0 80.0 0.162 0.539
Lipid regulators Clofibric acid 78.5 107 0.001 0.002
Gemfibrozil 85.9 79.3 0.008 0.026

3. Results and discussion
3.1. Occurrence of pharmaceutically active compounds in
effluent wastewater
Table 2 shows the results obtained in analyzed effluent waste-
water during the sampling period. Concentration levels of
studied compounds measured in effluent wastewater were from
0.03 mg L
1 (propranolol) to 28.9 mg L
1 (ibuprofen). Pharma-
ceutically active compounds such as caffeine, gemfibrozil, keto-
profen, naproxen, propranolol and salicylic acid were detected in
the 100% of the samples analyzed while others such as clofibric
acid, estrone, sulfamethoxazole and trimethoprim were not
detected in the analyzed effluent wastewater samples. Estrogenic
compounds 17a-ethinylestradiol and estriol were detected in the
75% of the analyzed effluents.
The antiinflammatory drugs were found at the highest
concentration levels, especially ibuprofen and salicylic
acid which were found at concentration levels up to 28.9 and
11.8 mg L
1, respectively. This fact could be associated with the
high consumption of these pharmaceuticals for which medical
prescription it is not necessary. Lipid regulator gemfibrozil and
the nervous stimulant caffeine were present at concentration
levels up to 4.14 mg L
1 and 0.94 mg L
1 while lower concentra-
tion levels were found for carbamazepine, detected in 50% of the
analyzed samples at mean concentration levels of 0.10 mg L
1.
Estrogenic compounds were found at low concentration levels
(mean concentrations from 0.04 to 0.43 mg L
1), however, these
concentrations and their frequent detection in effluent wastewater
(almost one estrogen detected in the 80% of the analyzed effluent)
could be sufficient to induce toxic effects in aquatic organisms.

Table 2 Ranges and mean concentration levels (mg L
1) of pharmaceutically active compounds in wastewater effluents affecting Guadalquivir River
and frequency of detection in river samples

North WWTP South WWTP East WWTP West WWTP

Discharges affecting Discharges affecting Discharges affecting Discharges affecting

S2 S4 S4 S3 Frequency of
Pharmaceutically active detection in river
compound Range Mean Range Mean Range Mean Range Mean water (%)

Diclofenac <LOD-1.14 0.53 0.12–1.44 0.73 <LOD <LOD <LOD-0.37 0.09 0

Ibuprofen 0.61–6.77 3.74 0.59–1.67 1.04 <LOD-9.24 3.17 <LOD-28.9 8.00 0
Ketoprofen 0.30–1.62 1.06 0.34–1.62 1.11 0.33–0.86 0.62 0.52–1.39 0.95 0
Naproxen 1.77–3.20 2.58 0.88–1.23 0.99 0.10–3.21 1.15 0.33–2.49 1.29 100
Salicylic acid 0.13–0.44 0.34 0.06–0.27 0.17 0.09–0.11 0.10 0.12–11.8 3.17 100
Sulfamethoxazole <LOD <LOD <LOD <LOD <LOD <LOD <LOD <LOD 0
Trimethoprim <LOD <LOD <LOD <LOD <LOD <LOD <LOD <LOD 0
Carbamazepine <LOD-0.15 0.06 <LOD-0.28 0.15 <LOD-0.14 0.05 <LOD-0.37 0.13 58
Propranolol 0.03–0.65 0.34 0.19–0.64 0.37 0.14–0.29 0.21 0.10–0.72 0.31 100
Caffeine <LOD-0.81 0.24 <LOD-0.19 0.08 <LOD-0.94 0.37 0.18–0.47 0.30 38
17a-Ethinylestradiol <LOD-0.34 0.12 <LOD-0.13 0.03 <LOD-0.11 0.04 <LOD-0.37 0.18 0
17b-Estradiol <LOD-0.09 <LOQ <LOD-0.16 <LOQ <LOD <LOD <LOD-0.17 <LOQ 0
Estriol <LOD-1.07 0.59 0.10–0.57 0.27 <LOD-0.75 0.43 <LOD-0.61 0.37 42
Estrone <LOD <LOD <LOD <LOD <LOD <LOD <LOD <LOD 0
Clofibric acid <LOD <LOD <LOD <LOD <LOD <LOD <LOD <LOD 0
Gemfibrozil 2.03–4.14 3.07 1.88–3.03 2.47 0.20–3.03 1.52 1.07–3.83 2.16 100

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Fig. 2 Contribution of each studied effluent to the total discharge of pharmaceutically active compounds to Guadalquivir River.
Concentration levels found in this work were consistent with
those reported by other authors in other Spanish regions such as
Galicia24 where concentration levels up to 2.60 mg L
1 were
reported for the ibuprofen and naproxen or Northern Spain
where Gros et al. (2007)7 found a similar distribution of the
therapeutic drugs in seven WWTPs discharging to Ebro River.
Other studies carried out in Europe and United States corrobo-
rate this distribution in wastewater effluents from Finland,4
France,25 Germany,26 Greece25 and Italy.25
Fig. 2 shows contribution of each WWTP to the discharge of
pharmaceutically active compounds to the Guadalquivir River,
taking into account the mean concentration level of each
compound and the volumetric flow of the effluents from each
WWTP. Taking into consideration the discharge of each WWTP,
the highest discharge of pharmaceutically active compounds
were those found in South WWTP (Fig. 2), discharging to
Fig. 3 Mean concentration levels of pharmaceutically active compounds along Guadalquivir River in the four sampling sites. Lines in each bar show
maximum and minimum concentration values (n ¼ 12).
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Guadaira River which affects to S4, followed by North, West
and East WWTP, respectively (discharging to S2, S3 and Gua-
daira rivers, respectively).
These results show that, in spite of the high removal rates
of pharmaceutically active compounds in wastewater
treatment described in several studies,13,23,24 these compounds are
not completely removed from wastewater influent and, as
a result, are present in effluent wastewater discharged to surface
water.
3.2. Pharmaceutical compounds in the receiving water
Among twelve pharmaceutically active compounds found in
effluent wastewater, seven (caffeine, carbamazepine, estriol,
gemfibrozil, naproxen, propranolol and salicylic acid) were
detected in the measured river samples (Fig. 3).
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Fig. 4 Concentration levels of pharmaceutically active compounds measured during winter and summer period (n ¼ 12).

The same pattern of pharmaceutically active compounds
founds in effluent wastewater were found in river water. The
highest concentration levels were found for gemfibrozil (mean:
0.34 mg L
1), followed by the anti-inflammatory drugs naproxen
and salicylic acid and the pharmaceutically active compounds
caffeine, estriol, carbamazepine, and propranolol, in this order.
Concentration levels measured in the sampling point S1, sited
upstream from the discharge of North WWTP, were from 0.013
to 0.610 mg L
1. These concentrations were higher than those
measured downstream, except in sampling point S3. This fact
could be explained by several reasons: the discharge of WWTPs
sited in nearby municipals, the higher flow of the Guadalquivir
River downstream and the degradation of these compounds in
the aquatic environment.27–31 The lowest concentration levels
measured in sampling point S4 could be explained by the high
dilution effect observed by the confluence of Guadalquivir and
Guadaira River.
Except in the case of caffeine, the concentration levels of
studied pharmaceutically active compounds measured during
winter period were higher than those measured during summer
period (Fig. 4). This fact could be explained taking into consid-
eration (1) the increase of the consumption of pharmaceutically
active compounds during this period, especially in the case of
anti-inflammatory drugs for which mean concentration up to
8.40 mg L
1 were measured in effluent wastewater (1.5 mg L
1
found during winter period) and (2) the high volumetric flow of
wastewater effluent discharged during this period.
The results showed in this work put in consideration the
pollution by pharmaceutically active compounds presents in
Guadalquivir River, moreover, the presence of these pharma-
ceutically active compounds is mainly due not only to the
persistence of these compounds in the aquatic environment, but
also to their continuous discharge from the WWTPs.
The results obtained in this work are slightly similar to those
previously reported for other authors in large Spanish Rivers
such as Ebro, Llobregat, Henares, Jarama and Tajo Rivers7,9,31
where concentration levels of pharmaceutically active
compounds up to 0.497 mg L
1 have been reported. In another

Table 3 Ecotoxicological data from the literature applied to the PNEC calculation

Ecotoxicological
Pharmaceutical compound Organism Test data/mg L
1 PNEC/mg L
1 Reference

Antiinflammatory drugs Diclofenac V. fischeri (bacteria) EC50 (15 min) 9.70 9.70 32
Ibuprofen H. attenuata (invertebrate) EC50 (96 h) 1.65 1.65 33
Ketoprofen V. fischeri (bacteria) EC50 (15 min) 15.6 15.6 34
Naproxen H. attenuata (invertebrate) EC50 (96 h) 2.62 2.62 33
Salicylic acid V. fischeri (bacteria) EC50 (15 min) 43.1 43.1 34
Antibiotics Sulfamethoxazole P. subcapitata (algae) EC50 (96 h) 0.15 0.15 35
Trimethoprim D. magna (invertebrate) EC50 (96 h) 121 121 36
Antiepilectic drugs Carbamazepine D. magna (invertebrate) EC50 (48 h) 13.8 13.8 35
b-Blocker Propranolol D. subspicatus (algae) EC50 (48 h) 0.70 0.70 37
Nervous stimulant Caffeine Leuciscus idus (fish) EC50 (96 h) 87.0 87.0 38
Estrogens 17a- S. purpuratus (invertebrate) EC50 0.03 0.03 39
Ethinylestradiol
17b-Estradiol S. purpuratus (invertebrate) EC50 0.01 0.01 39
Estriol S. purpuratus (invertebrate) EC50 1.52 1.52 39
Estrone T. battagliai (invertebrate) LC50 (10 days) 0.10 0.10 40
Lipid regulators Clofibric acid D. magna (invertebrate) EC50 (48 h) 72.0 72.0 35
Gemfibrozil H. attenuata (invertebrate) EC50 (96 h) 1.18 1.18 35

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Fig. 5 Mean risk quotient values (MEC/PNEC) of the detected pharmaceutically active compounds in wastewater effluents and river water. Lines in
each bar show maximum and minimum values.
study carried out in Do~ nana national park, near to the
sampling area and affected by Guadalquivir river,1 concentration
levels higher than those reported in this work were
measured (from 0.03 to 4.55 mg L
1) which could be related to the
dilution effects of effluent wastewater in the studied river and
streams.
3.3. Risk assessment
Acute EC50 values of the pharmaceutically active compounds
differed markedly, from a few mg L
1 for estrogenic compounds
to more than 100 mg L.1 for the antibiotic trimethoprim. These
toxicity data can be interpreted using EU directive 93/67/EEC,
which classifies substances according to the measured EC50
values.32 When this scheme was applied to the data used in the
current study, 17a-ethinylestradiol, 17b-estradiol and estrone
were classified as extremely toxic, having an EC50 < 0.1 mg L
1,
while others such as diclofenac, estriol, gemfibrozil, ibuprofen
and naproxen were classified as toxic, showing an EC50 value
between 1 and 10 mg L
1. Caffeine, carbamazepine, clofibric
acid, ketoprofen and salicylic acid were all classified as harmful
(EC50 between 10 and 100 mg L
1) and trimethoprim was
considered non-toxic (EC50 > 100 mg L
1) (Table 3).
Ecotoxicological risk was evaluated in two scenarios: effluent
wastewater, which takes into account the potential risk of
pharmaceutically active compounds for aquatic organisms after
the wastewater treatment and; surface water, which considers the
potential risk of pharmaceutically active compounds for aquatic
organisms present in the river basin. Fig. 5 shows the risk
quotient calculated using concentration levels of each compound
measured in effluent wastewater and in surface water samples.
Lines in each bar show maximum and minimum risk quotients
values.
17a-Ethinylestradiol, ibuprofen, and gemfibrozil showed high
risk quotients in wastewater effluents while others such as estriol,
naproxen and propranolol showed risk quotients higher than 0.1
and lower than 1 which could be indicative of a medium risk for
the environment.
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As a consequence of the dilution effect observed for the
studied pharmaceutically active compounds in Guadalquivir
River, a decrease in RQ values were observed. These values were
ranged from 0.001 to 0.630. Only the lipid regulator gemfibrozil
showed a medium risk for the environment with a risk quotient
higher than 0.1. Moreover, in spite of the medium risk showed
for the lipid regulator gemfibrozil, other chronic effects such as
reproductive disorders, inhibition of growth or changes in
morphology could be expected. For example, the exposure of
goldfish to concentration levels of gemfibrozil closer than those
measured in Guadalquivir river (1.5 mg L
1) over 14 days
decreased testosterone levels by 50% which provides strong
evidence that this compound may be acting as an endocrine
disruptor in this species of fish.35
These results do not support the existence of a risk for acute
toxic effects in the environment following today’s use of phar-
maceuticals. However, these results do not rule out the potential
for chronic environmental effects. Moreover, these results are
focused on the toxicity of the individual compounds and synergic
effect with other pharmaceuticals present in the environment has
not been considered.
4. Conclusions
An analytical method based on solid phase extraction and
determination by high performance liquid chromatography with
diode array and fluorescence detectors has been applied to the
monitoring of sixteen pharmaceutically active compounds in
effluent wastewater and surface water samples from Gua-
dalquivir river basin. The occurrence and risk assessment of these
compounds in Guadalquivir river basin has been evaluated.
WWTPs were found to be unable to efficiently remove the
studied pharmaceuticals. As a result, all studied pharmaceuti-
cally active compounds, except estrone, clofibric acid, sulfame-
thoxazole and trimethoprim were detected in analyzed
wastewater effluent samples.
In spite of the low concentration levels found in wastewater
effluent and the dilution occurring in Guadalquivir River, seven
This journal is ª The Royal Society of Chemistry 2011

of the pharmaceutically active compounds detected in effluent
wastewaters were found in Guadalquivir River at concentration
levels up to 0.76 mg L
1. The highest concentration levels were
found in the case of gemfibrozil, followed by the anti-inflam-
matory drugs naproxen and salicylic acid, and the pharmaceu-
tically active compounds caffeine, estriol, carbamazepine, and
propranolol, in this order.
Environmental risk assessment showed that, after wastewater
treatment and dilution in surface water acute ecotoxicological
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risk could not be expected and only the lipid regulator gemfi-
brozil showed a medium risk for the environment. However, the
environmental risk assessment carried out in this work has been
focused on the toxicity of individual compounds and the
potential synergic effects have not been taken into consideration.
Acknowledgements
The authors wish to thank the financial support of this work
from the Ministerio de Educaci

on y Ciencia, Spain (project no.
CGL2007-62281) and Programa de Becas de Formaci
on de
Profesorado Universitario (FPU, Ministerio de Educaci
on,
Spain).
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