Environmental Pollution 164 (2012) 267e273

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Environmental Pollution
journal homepage: www.elsevier.com/locate/envpol

Occurrence and persistence of organic emerging contaminants and priority
pollutants in five sewage treatment plants of Spain: Two years pilot
survey monitoring
M.J. Martínez Bueno a, b, M.J. Gomez b, S. Herrera b, M.D. Hernando c, d, A. Agüera a,
A.R. Fernández-Alba a, b, *
a

Pesticide Residues Research Group, Department of Hydrogeology and Analytical Chemistry, University of Almería, 04120 La Cañada de San Urbano, Almería, Spain
Fundación IMDEA-Agua, C/ Punto Net 4, 2a planta, Edificio ZYE, Parque Científico Tecnológico de la Universidad de Alcalá, 28805 Alcalá de Henares, Madrid, Spain
National Reference Centre for Persistent Organic Pollutants, University of Alcalá, 28871 Alcalá de Henares, Madrid, Spain
d
Instituto Nacional de Investigación y Tecnología Agraría y Alimentaria, INIA, Crta. de la Coruña, km. 7, 28040 Madrid, Spain
b
c

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 7 October 2011
Received in revised form
18 January 2012
Accepted 22 January 2012

This work summarized all results obtained during almost two-years of a monitoring programme carried
out in five municipal sewage treatment plants (STPs) located in the north, centre and south-east of Spain.
The study evaluated the occurrence and persistence of a group of 100 organic compounds belonging to
several chemical groups (pharmaceuticals, personal care products, pesticides and metabolites). The
average removal efficiencies of the STPs studied varied from 20% (erythromycin) to 99% (acetaminophen).
In analysed samples, we identified a large number of compounds at mean range concentrations between
7e59,495 ng/L and 5e32,720 ng/L for influent and effluent samples, respectively. This study also
identified 20 of the mostly detected and persistent compounds in wastewater effluent, of which
hydrochlorothiazide, atenolol, gemfibrozil, galaxolide and three metabolites (fenofibric acid, 4-AAA
and 4-FAA), presented the highest average contribution percentages, in relation to the total load of
contaminants for the different STPs effluent studied.
Ó 2012 Elsevier Ltd. All rights reserved.

Keywords:
Pharmaceuticals and personal care products
Pesticides
Wastewater
LCeMS/MS
GCeMS

1. Introduction
From 1970, thanks to a range of EU environmental directives, the
quality of surface water in Europe has improved significantly. Now,
in the Member States of the European Union, the chemical quality of
surface waters is controlled under the Water Framework Directive
(WFD) 2000/60/EC (Directive 2000/60/EC). Within this framework,
the key strategy adopted, in the area of chemical pollution, was the
Decision 2455/2001/EC which established a list of 33 substances or
groups of substances of priority concern due to their persistence,
toxicity, bioaccumulation and widespread use and detection in rivers,
lakes, transitional and coastal waters. Also, more recently, Directive
2008/105/EC has been a new step in the progress of regulation,
establishing for the first time, quality standards (EQS) for priority
substances and other pollutants of concern, to ensure adequate
protection of the aquatic environment and human health. Among the
objectives, other chemicals, of emerging interest, are being included

* Corresponding author.
E-mail address: amadeo@ual.es (A.R. Fernández-Alba).
0269-7491/$ e see front matter Ó 2012 Elsevier Ltd. All rights reserved.
doi:10.1016/j.envpol.2012.01.038

in a review process for identification as possible “priority substances”
or “hazardous substances” due to their potential risk. Actually, 13
new substances are under a review process (European Parliament
Legislative Resolution, 2008), 7 are pharmaceuticals and 6 are
personal care products.
In the last years, many organic contaminants from anthropogenic
origin, so-called “emerging” contaminants, are being subject of
high concern among the scientific community due to their frequent
detection in aquatic environment. Highlights pharmaceuticals or
personal care products (PPCPs) which are highly consumed by
modern society; these substances are continually introduced in
the aquatic environment, through sewage treatment plants (STPs) or
directly via release from the skin during swimming or bathing
(Daughton and Ternes, 1999). From the consumption standpoint
of these products, a report published by the British Government
compared the consumption of 14 groups of drugs in 14 countries,
revelling that the Spanish people are Europeans that consume more
drugs, only surpassed by the Americans, and followed by France,
Denmark and Australia (Richards, 2010).
To protect the environment from the potential chemical pollution of urban wastewater discharges and emissions from the

during conventional biological wastewater treatment. Information regarding frequency of detection for each compound. most of chemicals were detected at least once time over the campaign developed from the 100 contaminants included in the study. This finding highlights that for certain chemicals such drugs. progress in addressing waste water-related challenges resulting from this regulation.J. Experimental section A detailed discussion of the sample treatment techniques and analytical methods used in this study has been included as supplementary information (see Supplementary Data). All these data obtained over a two year period. In Spain. triple-quadrupole. relatively volatile and thermally stabile substances. diuretics (furosemide.. the contribution of these compounds can vary depending on the characteristics of the WWTPs. That can be due to the proximity of the STP to a major hospital in the area. LCeMS/MS has been the technique most referenced for the analysis of polar and semi-polar organic compounds in environmental samples until currently (Gros et al. the effectiveness of these WWTPs for removing chemicals is limited. paraxanthine (metabolite of caffeine) and four of the main metabolites of the antipyretic drug dypirone. mainly analgesics/anti-inflammatories (diclofenac. As shown Fig.268 M. Zuccato et al. lipid regulators (gemfibrozil). In terms of frequency of detection. 3. 4-FAA and 4-AA). For determination of non-polar analytes. one chemical under review process for its identification as “priority and/or hazardous substances”.. Martínez Bueno et al. 2. Pharmaceuticals Recently. 2 shows a summary of the mean removal efficiency for some of the most representative compounds detected. caffeine and its metabolite or all the main metabolites of the antipyretic drug dypirone (4-MAA. couple with mass spectrometry (LCeMS or GCeMS). a discussion regarding seasonal and monthly variation in the average total load of contaminants has been included as supplementary information (see Supplementary Data). 2010). which represent a very important amount of the total load. S2). LCeMS/MS and GCeMS were chosen as multi-residue analytical techniques to carry out the screening of wastewater samples. demonstrating their persistence. 3. 1991). Further discussion of these and other compounds of interest in this study are given below. / Environmental Pollution 164 (2012) 267e273 industry. confirm that most of these contaminants are only partially eliminated during the secondary treatment usually used in STPs. 2008) or liquideliquid extraction (LLE) (Gómez et al. 2009. probably is of higher concern to monitor metabolites generated in the human body or during the water treatment. Fig. codeine. Tandem mass offers higher performance than single-quadrupole instruments. followed by separation and determination using liquid (LC) or gas chromatography (GC). Furthermore. 90 were detected in at least one occasion in influent samples and 88 in the effluents. ion trap or hibrid triple quadrupole-ion trap systems are one of the most frequently chosen techniques for analysed organic compounds in complex matrices. So. in many cases. in quantity and quality of water. It is also remarkable the presence at very high concentrations of a group of metabolites such as fenofibric acid (metabolite of fenofibrate). 2010). GCeMS has usually been the analytical methodology applied in these types of matrices (Robles-Molina et al. 4-FAA and 4-AA. 2006). pharmaceutical products have become “new environmental contaminants” or so-called “emerging contaminants”. where the results obtained are presented by families of compounds. 2007). 4-MAA. Results and discussion A comprehensive overview of the validation results obtained has been included as supplementary data (see Table S1). However. a large number of organic contaminants escape to treatments becoming ubiquitous contaminants in the environment. In this work.1. This study has been focused on a group of 100 organic compounds that includes 7 “priority substances”. has been to obtain information during almost two-years of monitoring sampling. a seasonal and monthly variation from the discharged effluent of WWTPs were also worthy of investigation in this study.. it is noteworthy that a group of only 20 compounds is responsible for 83% of the total load of pollutants in the effluent (see Fig. at relatively high concentrations. is the synthetic fragrance galaxolide.M. concentration ranges and mean concentrations detected in effluents after applied a secondary treatment in the 5 STPs selected in this study. therefore. their contribution in the total load of pollutants in the effluent vary depending of the STP characteristics. However. Moreover. naproxen. antibiotics (ofloxacin. can be seen in Table S2. solid-phase microextraction (SPME) (Rodriguez et al. hydrochlorothiazide). b-blockers (atenolol). Bueno et al. 4-AAA. 2009).. specially when drug metabolism rates are high and whose presence in the environment can be the cause. Removal of pollutants by the STP varies. 2005). The main objective of the present article. a considerable progress has been made following the implementation of the Directive 91/271 (UWWD) (Directive of the European Communities. 4-AAA. which although ubiquitous in all effluent treatment plants studied.. in order to achieve the identification and quantification of a high number of organic compounds from several chemical groups. ciprofloxacin. of a higher risk than that expected from the original compounds. stir bar sorptive extraction (SBSE) (Roldil and Moeder.. depending on the physicochemical properties of each compound. and 92 “emerging” contaminants. The most common procedures used to carry out the determination of organic compounds in aquatic environmental matrices applied sample preconcentration steps. These compounds presented not only a high concentration but also a high frequency of detection. there are pollutants such as atenolol. in terms of sensitivity and selectivity. The two primary causes are: (i) their habitual presence in environmental water (by their continuous input in aquatic system or an incomplete removal in STPs) and (ii) the concern about their possible effects on organisms or environmental impact on wildlife and humans. in some cases. Given this wide range of concentrations.. . The highest average total load was detected in the WWTP located in the south-eastern from Spain (Almería). included among the most abundantly detected contaminants. ulcer healings (ranitidine) and the stimulant caffeine.. Therefore. being discarded those compounds that had high concentrations occasionally. erythromycin). has ensured notable improvements. Mean concentrations detected for the analytes identified ranged from 7 ng/L to 59 mg/L in influent samples and from 5 ng/L to 32 mg/L in effluents. by secondary treatment processes. Monitoring information is presented analysing the results in terms of average total load of contaminants detected in each STPs selected and mean contribution of each analyte against the total load of contaminants in the sewage effluents. 1. in order to evaluate removal efficiency of five STPs of Spain and the presence of chemicals in WWTP effluents that are discharges to the environment. 2007. ibuprofen). The sole representative of the PCPs group. such as solid-phase extraction (SPE) (Martínez Bueno et al. In this group are included 13 pharmaceutical. developed as a part of an ambitious research programme (TRAGUA) financed by the Spanish Government. such as biological filters and activated sludge (Gómez et al.

(* ) (*) (* ) (*) 70 60 (* ) (* ) ( *) (*) B al HT ax o To lide na lid e 4M AA G ph e N ic n o ct tin o e Pa cr ra yle xa ne nt Si hin e m a An zin tip e yr in e 2EH M C C Sa affe 3.3 and 180. Mean removal efficiency for some of the most representative compounds in the whole set of WWTPs under investigation. are widely used. / Environmental Pollution 164 (2012) 267e273 269 Fig. .in D AA i M aze A ep p i am M vac et ro ain e n B id ez az a o Fu fib le ro rat G sem e em fib ide C ar r b.M. whereby paracetamol is the 3. Average total load (ng/L) of contaminants in the effluent of the 5 WWTPs studied.A flo A xa c 4.J.1.5 mg/L).1 ol 1E o l Su p o lfa xid e di az in e Removal efficiency (%) (*) * Compounds (*) in o Removal efficiency (%) (* ) 100 90 80 70 60 50 40 30 20 10 0 detected in most STP effluents studied at concentrations above 1 µg/L (mean concentrations were between 19. This fact can be explained according to data base submitted by the Spanish Agency for Medicines and Health Products in 2009 (Ministerio de Sanidad. within this group. calculated from samples collected over a period of almost two-years monitoring program. Acetaminophen was the drug. política social e igualdad). 1.licy ine B en lic zo a c ph i d en o C hl Co ne t or i fe ni n n e M vin us ph o k xy s N len ap e r Fl oxe uo n xe tin Te e rb ut Tr alin ic lo e Ib sa n u p C hl ro or fe op n he At ne ra zi ne High O ta m Ac e (*) (*) ( ) * 50 40 Medium 30 20 10 0 (* ) 50 45 40 35 30 25 20 15 10 5 0 (*) (* ) 4FA A A m az ep in e O flo xa ci n K et or M ol ef ac en am ic ac Er id yt hr om yc in ba Su C ar e lfa py r Su id e in lfa e m et ha zi e ne Fe no fib ra te H N yd ad ro ol ch ol lo ro th ia In zi do de m et ha ci Fe ne no fib ric ac id K et op ro fe n e ia zo l Su (* ) Low lfa th Removal efficiency (%) Pi D ren ic lo e fe Su lfa Ra na m nit c et id h in Is oxa e e o p zo ro le tu ro O So n m ta ep lo l M raz et ol op e ro C Di lol ip u ro ro C flo n lo x fib ac r i c in d C aci Pr o de d op in Tr ra e im no et lo S a ho l l b pri ut m am o N 4 l or . 2.M.1. At ozi 10 en l . Analgesics/anti-inflammatories These kinds of drugs used to alleviate the pain present in almost all diseases. Bueno et al. detected at higher concentration in the wastewater influent Fig.

Germany.3 mg/L for raw sewage. Similar values have been reported for ofloxacin and sulfamethoxazole in Taiwan (Yu-Chen Lin et al. conducting to maximum concentrations ranging from 0. 2009). 1998. Bueno et al.5e14 mg/L and 0... 2009) or Taiwan (Yu-Chen Lin et al. respectively. and 1.5 mg/L (diclofenac).3 mg/L. were lower than those obtained in this study (Ternes. it was quantified in all analysed samples.270 M.8 mg/L).4. This fact is related with the different removal efficiency obtained for this compound in different WWTPs. 2009) for erythromycin and metronidazole. Fenofibric acid is the active metabolite of the lipid regulators fenofibrate.. naproxen.. 2. The rapid biodegradation of paracetamol during a conventional wastewater treatment has been also reported by other authors (Gómez et al. The rest of target b-blockers were also frequently found in all WWTPs studied. 2009). the products detected at high concentrations. Similar values have been previously reported by other authors in different STPs from United Kingdom (Kaspryk-Hordern et al.M. 2008). They also presented incomplete removal.. higher than 59% in all cases. 2009). Kaspryk-Hordern et al. Some authors have suggested different explanations to this fact. especially for clinical use. 2005) at concentration levels ranging from ng/L to mg/L. as mentioned above. Most of these analytes show acceptable removal rates. between 2. 2010). Besides.. Maximum concentrations were in the mg/L range.08e13. which is further transformed to 4-FAA.. 2002) or (ii) changes in the adsorption behaviour to particles during the treatment process. These four main metabolites represent w60% of the administered dose excreted in urine..9 mg/L for inlet and 0. However.8 and 0. among the compounds that contribute most to the total load of contaminants in the effluents.. in Spain. 5. 2010.. ranging from 0. The second group of substances more commonly detected in wastewater were the metabolites of dipyrone. Presence of these compounds has been widely reported not only in wastewater.01 to 0. 2. this compound was also detected at high concentration in effluents (0. which was only eventually detected in two plants in southern and northern Spain. with the exception of erythromycin in influents (approx. Antibiotics These pharmaceuticals are considered as “pseudopersistent” contaminants because of their continual input into the environment and permanent presence. 2.. ofloxacin and sulfamethoxazole were the antibiotics found at the highest concentration levels and also with the highest frequencies of detection. in both influents and effluents.9. for influent and effluent. However. Although dipyrone is banned in many countries of the European Union.2.. 2009) or Germany (Pal et al. such as (i) deconjugation of conjugated metabolites during the treatment process (Miao et al. 55%). Generally speaking this substance shows little or no removal during conventional biological processes (<20%).1 to 15 mg/L for wastewater effluent.. with a frequency of detection higher than 85% in all cases. in some cases reaching concentrations up to 11. but also in surface water or groundwater (Martínez Bueno et al. in both influent (85e100%) and effluent samples (79e100%) during the sampling campaign.9 mg/L.1. 3..5 mg/L (naproxen).. 2007).8 mg/L (ketoprofen) in effluent samples at different WWTPs studied. 2008). Hernando et al.. ketorolac and ketoprofen were the following therapeutic drugs quantified at lower levels due to their lower usage in Spain. dipyrone is rapidly hydrolyzed to the active 4-MAA. metronidazole and trimethoprim were. mean removal efficiencies found for the most commonly detected antibiotics in this study ranged from 40% for ofloxacin to 65% for sulfamethoxazole. 2005).07 to 1 mg/L for output sewage. 1.. 1. these metabolites have been detected in the effluents.5 mg/L in output wastewater. verifying the limited degradation for these types of compounds using activated sludge technology. 2009). 3... similarly to observed by other authors. These results are in concordance with data reported by Kaspryk-Hordern (Kaspryk-Hordern et al. 2007) and are consistent with the incomplete removal obtained for this analytes during the biological treatment.2 and 1. UK (Kaspryk-Hordern et al.. These results are in agreement with data previously reported (Gómez et al. occasionally presenting higher concentration in the final effluent than in the influent (Gulkowska et al. Gros et al. Gómez et al. although in this case their frequency of detection and concentration level detected do not show a pattern. Italy. / Environmental Pollution 164 (2012) 267e273 most popular non-opioid analgesic sold in Spain in the last years. These values are also in agreement with data found in literature by applying activated sludge biological treatment (Kaspryk-Hordern et al.. respectively. 2005).. 2009). 2009. As it is shown in Fig. in a second order. most of them have been detected in rivers of different countries such as Spain (Martínez Bueno et al. Erythromycin. As a consequence of the . with the exception of nadolol. 2009. 2007). Lower concentration levels of erythromycin (<6 ng/L) have been however reported in WWTPs in North-East of Spain (Gros et al. ranging from 0. Hungry and Portugal it is still one of the most consumed prescription drugs because of its effective analgesic properties. with the exception of ketoprofen (40%) and ketorolac (37%).2 mg/L (ketorolac) and 0. diclofenac. codeine. This fact can explain the high concentration detected in influents. Spain (Rodil et al. bezafibrate and gemfibrozil ranged from 50 to 60%. being. Due to this incomplete removal in the WWTPs. The average concentrations in the treated wastewater for the other target regulators detected in this study ranged from 0. respectively. respectively. 1..01 to 0. Their concentrations varied from 0. 2010)..7 mg/L in the effluent (see Table S2). The results varied for different WWTPs from 50% (nadolol) to 63% (sotalol). Fenofibrate was detected at very lower levels than its polar metabolite. 1998) or Spain (Gros et al. Finally. 2009) and ciprofloxacin in UK (Kaspryk-Hordern et al. The complete hydrolysis of the original drug to fenofibric acid occurs immediately after intake. In addition. Atenolol was the b-blocker found at the highest concentration levels. An incomplete removal of these compounds during the sewage treatment has been obtained. Ciprofloxacin. with maximum concentration levels up to 0.7e2 mg/L. 3.5 to 8.1. 2009).. Maximum mean concentrations found were 14 and 5 mg/L. During metabolization. Ibuprofen was the second anti-inflammatory drug and the third active compound most consumed in Spain.7 to 25 mg/L for influent and 1. from 46% for 4-FAA to 69% for 4-MAA. The results were at the same order of magnitude than those reported by Gros (Gros et al.1 mg/L in the effluents.. only about 50% (Zuccato et al.J. The removal efficiencies obtained for clofibric/fenofibric acid. 2009) in treated wastewaters in north-east Spain. the same authors observed lower concentrations of atenolol. Detection frequencies were similar to the antibiotics previously mentioned.. Metropolol and propanolol showed concentration levels at the same order of magnitude than those found in UK (Kaspryk-Hordern et al. 2009) or Italy (Zuccato et al. 4-AA and 4-AAA (Gomez et al.1 to 3.1 mg/L and 32 mg/L in STP effluents. mean concentration values reported for gemfibrozil and fenofibric acid. Lipid regulators Fenofibric acid and gemfibrozil were the lipid regulators detected at higher concentrations and with a higher detection frequency in all WWTPs studied. Anti-hypertensive (b-blockers/diuretics) Hydrochlorothiazide and furosemide were the diuretics detected in higher concentrations in raw wastewater. These values are similar than those obtained by other researchers from Germany (Ternes. 2007). influencing the ratio between influent/effluent water (Lindberg et al.1. concerning to number of packs sold in 2009 (Ministerio de Sanidad). Despite the high removal efficiency found for acetaminophen (99%).3.6 mg/L (codeine). The maximum mean concentrations were 3.3.

ranged from 1 to 150 n/L in surface water. similar values were reported by other authors from Italy (Zuccato et al. While the chemical salbutamol was rarely detected in surface waters with maximum values reported to 2. venlafaxine. caused by a reduction reaction of nicotinic acid with NADPH (Friesen and Leete. 1998) observed higher values of carbamazepine in German STP effluents (2. In spite of the high removal efficiency found for this compound family (>80%). 2010). 1981) reported concentrations in STP effluents from Japan comparable with those obtained in this study.. showing a poor elimination in most of cases (<50%). amitriptyline and citalopram were only sporadically detected. Spain. 2010. but at concentration levels in raw waters higher than in treated.1.7. such as Germany (Quednow and Puttmann. Bronchodilators Salbutamol and terbutaline were detected in wastewater but at much lower concentrations than the before mentioned pharmaceuticals. In particular. both inlet and output sewage. which was detected at concentrations up to 1 mg/L in Spanish rivers (Martínez Bueno et al. except cotinine in effluent samples of one sewage treatment plant studied.1. sludges and biota. 2008) or Switzerland (Rodil et al.8 to 9 mg/L for galaxolide and from 0. In this study.. 1998). All they have been detected in surface water at concentration levels ranging from ng/L to mg/L (Martinez Bueno et al. All they were well removed during secondary treatment. Italy (Kaspryk-Hordern et al. but also to adsorption onto solid surfaces (Carballa et al. on average 60% removal was observed in WWTPs from Spain (Gros et al.2. with the exception of fluoxetine (74%).6. France (Togola and Budzinski. 2009). directly into recreational waters or into the air by volatilization. in output sewage. Poor removal of carbamazepine was obtained in all STPs studied (<44%). However. persistent or ubiquitous compounds simply because of their continual infusion into aquatic media via STP effluents. Carballa (Carballa et al.9 mg/L for tonalide.1... Ulcer healings Ranitidine and omeprazole were detected in almost all the analysed samples at concentration levels lower than 1 mg/L. However. UV filters Benzophenone-3 (BP-3) filter was detected at the highest concentrations in most wastewater effluent. Yamagishi (Yamagishi et al. The anxiolytics are currently one of the groups of drugs most commonly used by the population.5 mg/L). 2009). 2004). Musk ketone and musk xylene were only occasionally detected in the analysed samples but at lower concentration levels than polycyclic musks.. Their removal can be attributed not only to biodegradation. any scientific publication on the detection of terbutaline in surface water has been found. In 1981. 2009) published similar results for ranitidine. 2005) or even up to 1 mg/L in Germany (Ternes. Little data on concentration levels and removal efficiency in STPs have been reported for these compounds. Bueno et al.J. Ternes (Ternes.. Caffeine was the compound detected at higher concentration levels in wastewater influent (up to 59 mg/L). with the exception of gemfibrozil. in final treated waters. Antidepressants/psychiatric drugs The maximum concentrations of carbamazepine quantified were 160 ng/L (inlet) and 270 ng/L (output). 3. can be also formed again by other compounds present in wastewater. between 70 and 85% for galaxolide and 75e90% for tonalide. 2005) and 4 ng/L in Spain (Martínez Bueno et al. some publications have reported studying nicotine biosynthesis in cell-free systems at the enzymatic level. around 100 ng/L level in treated waters. Synthetic fragrances These chemicals began to be identified in environmental samples almost 30 years ago. in both raw and treated wastewater. up to 370 ng/L and 116 ng/L. paroxethine. 11 epoxy-carbamazepine. Gros (Gros et al. with removal efficiency of around 70%. Martínez Bueno et al. Other members of this family. Zuccato et al. 3. 2010). 2010). apart by the chemical properties of specific compounds. Concentrations in STP effluents ranged from 1. ranging from 48 to . no removal of salbutamol was reported by Castiglioni (Castiglioni et al. Therefore. The mean removal efficiencies found for ranitidine and omeprazole were 66% and 63%. 2006). Concentrations for caffeine and its metabolite (<8 mg/L) were up to an order of magnitude higher than those values for nicotine and cotinine (<0.5 ng/L in Italy (Zuccato et al. they have been detected in surface waters at concentrations not exceeding 50 ng/L.1. 10. ranging from 10 to 77 ng/L. by microbial activity and environmental conditions.1 to 0. galaxolide and tonalide were the most frequently detected polycyclic musks and at the highest concentration levels.. 2009.. it is assumed that they could act as 3. 2009). nicotine was detected at higher concentration than its metabolite. 3.M. 2008) or Taiwan (Yu-Chen Lin et al.5. according with data presented by Gomez (20%) (Gómez et al... The efficiency of removal during activated sludge treatment was slightly higher than b-blockers. although nicotine is transformed to cotinine. 3. Wastewater treatment processes not resulted to be effective to remove these kind of compounds. This increase in the effluent has also been observed in other publication. with the exception of carbamazepine drug. To date. Concerning the other members analysed of this family. cotinine. it is demonstrated to occur in the environment because of the conversion of carbamazepine glucoronides and other conjugated metabolites to the parent compound by enzymatic processes taking place during the sewage treatment (Kaspryk-Hordern et al.1 mg/L). fluoxetine. 2007) or by Ternes (7%) (Ternes. From this group. lansoprazole and loratadine were scarce and only occasionally detected in some STPs. respectively. was also detected in most of the analysed samples. This fact can be explained because the degradation of the original drug to metabolite by bacterial action during the activated sludge biological treatment. once again. / Environmental Pollution 164 (2012) 267e273 271 incomplete removal these compounds have also been found in river waters. so they tend to accumulate in sediments. ranged from 25 to 36 ng/L for musk xylene and from 140 to 410 ng/L for musk ketone.. 3. 3. This research group obtained similar removal efficiencies.2.. showing a frequency of detection higher than 90%. Paraxanthine was found at levels lower than caffeine (<8 mg/L and 5 mg/L. 1990). Certain musks are of concern due to its highly lipophilic. This is because.2. at concentration levels <900 ng/L.M. was detected at concentration levels up to 80 ng/L and with a high frequency of detection (>73%) in sewage effluents. In contrast to the current research. nicotine and theirs metabolites were quantified in most of the wastewater samples analysed. 1998). 2005). famotidine. respectively) in treated waters. However.. Their removal efficiencies are influenced. Personal care products These substances differ from pharmaceutical products in that large amounts can be directly introduced to the environment. 2006) observed a varied efficiency depending on season (39e84%) during biological treatment in Italian STPs. the adsorption and biodegradation phenomena.1.. respectively.2. 2011). The major metabolite of carbamazepine. which has been quantified at concentrations up to 200 ng/L in rivers from Wales. Psychostimulants Caffeine.. However....8. synthetic fragrances have been detected in surface waters from different countries. 2004) explains this high elimination rate of musks due to. while Castiglioni (Castiglioni et al.. diazepam. 58% for salbutamol and 74% for terbutaline.

in the range of ng/L. such as antioxidants or flame retardants were scarce and only occasionally detected above their quantification limits (see Supplementary Data). none of them were quantified at maximum allowable concentrations.7 and 0. according with the data previously reported by Gomez (Gómez et al. respectively.9e1. Pesticides Diuron. lindane and isoproturon were the only pesticides occasionally detected in the other STPs studied..7 mg/L in effluents (Daughton and Ternes.0e6.8e8. Currently. Ternes.8e9.. both influents and sewage effluents. hydrochlorothiazode. Gómez. caffeine. toothpaste. / Environmental Pollution 164 (2012) 267e273 e140 ng/L.. Llompart. Carballa.3.J. 2009) and 1e5 ng/L (Kaspryk-Hordern et al. the lipid regulator gemfibrozil (1.3 mg/L).. after to apply secondary treatment.272 M. These three products were effectively removed from wastewater. Behavior of pharmaceuticals. 169 ng/L and 78 ng/L. implying the continuous input into the aquatic environment of these compounds and thereby confirming that the discharges of effluent from WWTPs are among the main pathway responsible for pollution of surface water. S. but at a lower frequency. Journal of Chromatography A 1174.2 mg/L).. but also several others from various therapeutic categories were detected in high concentrations. Chlorfenvinphos. Nevertheless. M. F. with mean values around 50%. the water framework directive (WFD) 2000/ 60/EC (Directive 2000/60/EC) includes these chemicals into the list of priority substances. This fact can be explained because the occurrence of sunscreen agents varies significantly. From the analysis data obtained over a two year period of monitoring in the selected STPs.. acetaminophen. it has been also observed that. 2-EHMC and octocrylene. with values of around 70%. Appendix. The concentration values of triclosan and chlorophene found in this study were in concordance with the results previously obtained by some authors up to 0. 4-AAA. García-Jares. 3. which showed concentration up to mg/L. both in influent and effluent. analgesics/antiinflammatories or disinfectants (>70%). 2007). being mainly detected in surface water at concentrations in the range of a few ng/L. It is worth emphasising that. Lopez-Mahía.M. such as river waters and even seawater (Martínez Bueno et al. 2007. J. 2010. At the same time it has been observed in this study that the presence of priority compounds selected is in compliance with the Water Framework Directive.. such as analgesics.. but also some compounds highly degradated.. They were well removed during the secondary treatment.. However. Supplementary data Supplementary data associated with this article can be found. Macrolide antibiotics and the anti-epileptic carbamazepine presented poor or no elimination. between 24e157 ng/L (Gómez et al. gemfibrozil. Bueno et al. respectively. Water Research 38.. References Benito Quintana. despite the secondary treatments applied. In spite of the relatively high degradation.M. This could be associated to the fact that to this plant receives important contributions of wastewater from greenhouses and agricultural areas. 2009).. Concentrations of these pesticides in effluent samples decreased in the following order: diuron > atrazine > simazine..3. 27e39. some researches have revealed the presence of UV agents in surface waters from several countries. in wastewater influent from a region in Spain. Lema.5e2.envpol. such as in rivers from UK (<160 ng/L) (Kaspryk-Hordern et al. established as EQS under water framework policy.2. 2009)... with levels up to 48 ng/L. T. with the exception of some compounds. PradaRodrıguez. ibuprofen. naproxen. 4-FAA or fenofibric acid. The elimination of triclosan once again is subject to adsorption in sludge and biodegradation processes. with rates exceeding 86%. D. 2007).. triclosan and chlorophene have been detected in river waters.8 mg/L) and the diuretics hydrochlorothiazide and furosemide (1. Other PCPs Other chemicals. However. but at lower concentration levels regarding to STP from Almeria.. hospital hand-soap and also recently it is being incorporated into plastic products from children’s toys or kitchen utensils such as cutting boards. 2004. Antibiotics and analgesics/anti-inflammatories were the most frequently drugs we measured. effluents from the STPs can still contain a large number of emerging pollutants that continuously are being discharged into bodies of water. in the removal of stimulant compounds (>80%). P. not only have been detected those compounds with lower removal rates. 2-EHMC and octocrylene were other agents quantified but at lower levels (<60 ng/L). 2007). This fact could be explained due to all of them remained relatively high concentrations in the effluent samples analysed.2. Acknowledgements The authors wish to acknowledge the Spanish Ministry of Education and Science (Programa Consolider Ingenio 2010 CE-CSD2006-00044 and Proyect CTM2007-65544/TECNO) for their economic support. diuretics and b-blockers showed medium removal rates. such as the b-blocker atenolol (1e15 mg/L). With this study. R. atrazine and simazine. Multiresidue analysis of acidic and polar organic contaminants in water samples by stir-bar sorptive extraction-liquid desorption-gas chromatography-mass spectrometry. 1999. comparatively among the different chemical families studies. stimulants or anti-inflammatory drugs. M. Most of lipids regulators. Chlorophene was also detected at high levels in effluents (up to 1. in the online version. diclofenac. 2009) reported lower concentrations of BP-3. .01. galaxolide. both in raw and treated wastewater. these compounds have been detected into different natural aquatic systems. ofloxacin. Disinfectants/antiseptics Triclosan was the antiseptic agent more frequently detected (>80%).4. codeine. Muniategui-Lorenzo.0 mg/L). at doi:10. (Rodil et al.. 2009).6 mg/L. Omil.1e0. C. paraxanthine.2012. most of the pesticides studied here were detected with a relatively high frequency and at high concentration levels in the STP localized to south-east of Spain (Almería). at concentration ranges between 0. Rodríguez. 2009) or Spanish rivers (<59 ng/L) (Benito Quintana et al...038. That fact can be explained due to this chemical is used in a wide variety of commercial products which includes footwear. cosmetics and hormones in a sewage treatment plant. 2918e2926.. 4. J. I. as illustrated in Table S2..1016/j. activated sludge biological treatment was more effective. were the only pesticides detected in all STPs. such as atenolol. Rodil et al. despite the relatively high removal found with the conventional biological treatment processes (>61%). due to their significant risk towards aquatic organism. even when were detected at higher concentration levels in some samples of wastewater effluent. which showing their widespread presence in five STPs studied. due to their habitual presence in the effluents. 3. the synthetic fragrance galaxolide (1. at least one time in the samples. Thus. the intensity of recreational activities and on season (Giokas et al. depending on the sampling location. Rodil.7 and 0. Gómez et al. for instance. acne creams. UV filters (>86%) and some synthetic fragrances. It is interesting to observe that. 3. and BP-3 was only detected in treated waters (<22 ng/L). Conclusions Levels detected in wastewaters of emerging contaminants were in the ranging from a few ng/L to few hundred ng/L. M.

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