Science of the Total Environment 481 (2014) 280–295

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Science of the Total Environment journal homepage: www.elsevier.com/locate/scitotenv

Review

Emerging organic contaminants in surface water and groundwater: A first overview of the situation in Italy Raffaella Meffe a,⁎, Irene de Bustamante a,b a b

IMDEA Agua, Madrid Institute for Advanced Studies in Water, Parque Científico Tecnológico de la Universidad de Alcalá, 28805 Alcalá de Henares, Madrid, Spain University of Alcalá, Geography and Geology Department, 28871 Alcalá de Henares, Madrid, Spain

H I G H L I G H T S • • • • •

The occurrence of 298 EOCs in Italian surface water and groundwater has been reviewed. Data reveals a serious contamination by EOCs of a number of Italian water resources. Contamination of SW and GW in Southern Italy is poorly or not at all characterized. Pesticides, industrials and pharmaceuticals were detected in the highest concentrations. Future EOC studies should be prioritized based also on results of similar reviews.

a r t i c l e

i n f o

Article history: Received 11 December 2013 Received in revised form 6 February 2014 Accepted 11 February 2014 Available online 4 March 2014 Keywords: Emerging organic contaminants Surface-groundwater Pesticides Industrials Pharmaceuticals Estrogens

a b s t r a c t This paper provides the first review of the occurrence of 161 emerging organic compounds (EOCs) in Italian surface water and groundwater. The reported EOCs belong to the groups of industrials, pharmaceuticals, estrogens and illicit drugs. Occurrence of 137 pesticides was also reported. The reviewed research works have been published between 1997 and 2013. The majority of the studies have been carried out in Northern Italy (n. 30) and to a lower extent in Central Italy (n. 13). Only a limited number of research studies report EOC concentrations in water resources of Southern Italy. The EOCs that have been more frequently studied are in the following descending order, pesticides (16), pharmaceuticals (15), industrials (13), estrogens (7) and illicit drugs (2). Research activities investigating the EOC occurrence in surface water are more numerous than those in groundwater. This is consistent with the higher complexity involved in groundwater sampling and EOC detection. Among the reported EOCs, industrials and pesticides are those occurring in both surface water and groundwater with the highest concentrations (up to 15 × 106 and 4.78 × 05 ng L−1, respectively). Concentrations of pharmaceuticals in surface water reach a maximum of 3.59 × 103 ng L−1, whereas only the antimicrobial agent josamycin has been encountered in groundwater with a concentration higher than 100 ng L−1. Both estrogens and illicit drugs appeared in surface water with concentrations lower than 50 ng L−1. Groundwater concentrations for estrogens were measured to be below the detection limits, whereas illicit drugs have so far not been studied in groundwater. The present review reveals the serious contamination status of Italian surface water and groundwater especially by pesticides, industrials and to a lower extent by pharmaceuticals and the necessity to foster the research on EOC occurrence in Italian water resources, in particular in Southern Italy where a limited number of investigations currently exist. © 2014 Elsevier B.V. All rights reserved.

Contents 1. 2. 3.

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . Overview of geographical distribution in Italy of the research studies Occurrence of EOCs in surface water and groundwater of Italy . . . 3.1. Pesticides . . . . . . . . . . . . . . . . . . . . . . . . 3.1.1. Review of published research studies on pesticides . 3.1.2. Occurrence . . . . . . . . . . . . . . . . . . .

⁎ Corresponding author. Tel.: +34918305962. E-mail address: [email protected] (R. Meffe).

http://dx.doi.org/10.1016/j.scitotenv.2014.02.053 0048-9697/© 2014 Elsevier B.V. All rights reserved.

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3.2.

Industrials . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.2.1. Review of published research studies on industrials . . . . 3.2.2. Occurrence . . . . . . . . . . . . . . . . . . . . . . 3.3. Pharmaceuticals . . . . . . . . . . . . . . . . . . . . . . . . 3.3.1. Review of published research studies on pharmaceuticals . 3.3.2. Occurrence . . . . . . . . . . . . . . . . . . . . . . 3.4. Estrogens . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.4.1. Review of published research studies on estrogens . . . . . 3.4.2. Occurrence . . . . . . . . . . . . . . . . . . . . . . 3.5. Illicit drugs . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.5.1. Review of published research studies on illicit drugs . . . . 3.5.2. Occurrence . . . . . . . . . . . . . . . . . . . . . . 4. Relating EOC physico-chemical properties to their environmental occurrence 5. Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

1. Introduction The rapid population growth and the increment of agricultural and industrial activities result in an increased water demand and wastewater production. Consequently, water resources are increasingly exposed to contamination by many sources such as leakage from sewer networks and septic tanks, application of fertilizers on agricultural fields, intentional or inadvertent waste disposals, discharges of wastewater effluents, and urban and rural storm water run-off (Slack et al., 2005; Osenbrück et al., 2007; Barnes et al., 2008). In recent years, a large number of microorganic contaminants have been encountered worldwide in surface and ground water (Swartz et al., 2006; Godfrey et al., 2007; Barnes et al., 2008; Kasprzyk Hordern et al., 2008; Peng et al., 2008; Strauch et al., 2008; Loos et al., 2009, 2010; Reinstorf et al., 2009; Teijon et al., 2010; Valcárcel et al., 2011; Cabeza et al., 2012; Meffe et al., 2013). The presence of these xenobiotic substances raises concern especially when water is used for drinking water production. Among the microorganic contaminants, there are those referred as “emerging organic contaminants” (EOCs). EOCs are defined as natural or synthetically occurring substances that are not commonly monitored in the environment but that can induce known or suspected undesirable effects on humans and ecosystems (Stuart et al., 2012). EOCs are not necessarily newly developed compounds; they may have been present in the environment for long time but their presence and implication for the environment's integrity are only recently recognized (Daughton, 2004). The advances in analytical techniques result in the detection of EOCs at very low concentration in water samples (Richardson and Ternes, 2011). EOCs include different chemical classes of pollutants such as disinfectants, industrials, pharmaceuticals, detergents, personal care products, and “life-style compounds” and the list of EOCs is expected to expand with the development of new analytical methods for their detection. In the European context, surface water and groundwater quality standards are regulated under the Water Framework Directive (EC, 2000), the Groundwater Daughter Directive (EC, 2006) and the Directive 2008/105/EC (EC, 2008). These directives require monitoring of “priority” organic contaminants in the aquatic environment such as certain pesticides and their degradation products, chlorinate solvents, polycyclic aromatic hydrocarbons, disinfection by products, volatile organic compounds and biocides (Lapworth et al., 2012). However due to the lack of information on toxicity and environmental impacts, a large number of contaminants, especially organic compounds, are not included in the list of chemicals to be monitored. The number of compounds that are currently regulated by the legislation is therefore likely to grow. Although EOC concentrations encountered in the environment are quite low, ranging between ng L− 1 and μg L− 1, a continuous exposure of the aquatic communities may result in potentially harmful effects. This is especially true for pharmaceutical compounds that are specifically designed to regulate

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endocrine and immune systems and that have therefore potential consequences as endocrine disruptors (Daughton and Ternes, 1999). An additional concern is related to the effects that mixtures of EOCs can have on the aquatic biota (Daughton and Ternes, 1999). In recent years, there have been a number of reviews dealing with the occurrence at national, European and worldwide scale of a vast array of EOCs in fresh water resources. These studies investigated the presence of EOCs in surface water (Murray et al., 2010; Pal et al., 2013) and in groundwater (Jurado et al., 2012; Lapworth et al., 2012; Stuart et al., 2012). None of these reviews report concentrations of EOCs in Italian water resources. To the best of our knowledge, the only existing work on the occurrence of EOCs in Italian environment has been provided by Zuccato et al. (2006). In their paper, Zuccato et al. (2006) presented a reconnaissance study of some pharmaceuticals in surface water, drinking water and effluents of wastewater treatment plants (WWTPs). Therefore, the present paper intends to furnish a comprehensive overview of the occurrence of a number of EOCs (including pesticides) in Italian surface water and groundwater which is not available in the literature. We aim at identifying those contaminants that represent a major concern for Italian water resources. Furthermore, we wish to recognize the areas which have so far not being the subject of investigation and where therefore more studies are particularly needed. The EOCs reviewed in this work belong to the classes of pharmaceuticals, estrogens, industrials and illicit drugs. Pesticide concentrations have also been addressed in this review. In the following, we will refer to EOCs including the class of pesticides. 2. Overview of geographical distribution in Italy of the research studies This study reviews 47 articles that have been published between 1997 and 2013 and reported concentrations of 298 EOCs (including pesticides) in Italian surface water and groundwater (Table A1). Fig. 1a–e shows the distribution and number of studies concerning EOCs in both surface water and groundwater considered in this paper. Compared to other European countries (England, Germany, Spain), the studies of the occurrence of EOCs in Italian aquatic environment are rather scarce. This holds true especially for studies in groundwater. The majority of the research activities have been carried out in Northern Italy (Fig. 1a–e). The most frequently investigated river is the Po River, the longest surface water course of Italy (652 km) with an average flow rate at its mouth of 1540 m3 s−1. The Po River has a wide watershed (71,000 km2) where most of the agricultural and industrial activities of the country are located. However, only industrial contaminants have been investigated in Po River tributaries covering a vast area of its watershed (Fig. 1b). Tiber River, the main river of Central Italy, has been often investigated to determine the occurrence of all the EOC

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Fig. 1. Distribution and number of EOC studies in Italian surface water and groundwater divided in contaminant classes: a) Pesticides, b) Industrials, c) Pharmaceuticals, d) Estrogens, e) Illicit drugs. (*) The pesticide national survey of ISPRA (2013) was not represented in the map.

classes, except illicit drugs, considered in this review (Fig. 1a–e). Sampling of surface water of Southern Italy for EOC determination has been rarely addressed, with only a single study of pesticides in surface waters of the Calabria Region, carried out by Curini et al. (2001). Groundwater studies are less frequent than surface water studies. This

correlates with a higher difficulty of groundwater sampling for which a monitoring well is needed and with the necessity of an analytical method able to detect concentrations that are generally lower than those in surface water. Pesticides represent the class of EOCs that have been more extensively investigated in groundwater. In fact, the

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groundwater of 10 Italian regions has been collected for pesticide determination. The number of groundwater studies progressively decreases to 5, 4, 1 and 0 for industrials, pharmaceuticals, estrogens and illicit drugs, respectively. Similarly to surface water studies, available groundwater studies have been mainly carried out in Northern Italy (Fig. 1a–e). 3. Occurrence of EOCs in surface water and groundwater of Italy For this review, we compiled data considering exclusively EOC maximum concentrations. The reasons for this choice are that maximum concentrations are reported more frequently in the publications and due to the limited number of collected samples, the mean values are often not a reliable indicator (Stuart et al., 2012). Several studies considered in this review report also concentrations of priority substances defined in the Directive 2008/105/EC and belonging to the class of pesticides and industrials that are considered in this paper. Published works reported in this review do not always provide water sampling methods. Only few papers specify that surface water has been collected as grab samples (Davì and Gnudi, 1999; Baronti et al., 2000; Patrolecco et al., 2006; Sbrilli et al., 2005; Viganò et al., 2006; Loos et al., 2007; Ferrari et al., 2011) or as composite samples (Laganá et al., 2004; Vitali et al., 2004; Zuccato et al., 2005a,b, 2008b, 2010). The sampling period of the 47 cited references is very variable. There have been studies that monthly monitored water quality during one or more years (Griffini et al., 1997; Pasti et al., 2007) and studies during which samples were collected seasonally (i.e. Pacioni et al., 2010). The majority of the publications involved sampling periods that were limited to one or two seasons during 1 year (i.e. Marchese et al., 2003; Guzzella et al., 2006; Sagratini et al., 2007). The number of collected water samples varies, depending on the sampling sites and monitoring periods. However, when specified, the number of samples can vary between 3 (Patrolecco et al., 2013) and 648 (Pecoraino et al., 2008). An exception is represented by the monitoring program for pesticides of Ispra (2013) during which more than 20,000 surface water and groundwater samples were collected. 3.1. Pesticides Pesticides represent a wide range of chemical compounds used to limit, inhibit and prevent the growth of harmful animals, insects, invasive plants, weeds, bacteria and fungi (Bottoni et al., 2013). They are frequently used in agriculture, in industry, in gardening and domestic activities. According to their use, pesticides are divided into four categories: herbicides, fungicides, insecticides and bactericides. About 2.4 × 109 kg of pesticides was used worldwide in 2007 (Gruber et al., 2011) and according to the Statistical Office of the European Commission Eurostat (Eurostat, 2012), the use of pesticides in Italy in 2006 reached 81.5 × 106 kg, more than any European country. In Italy, the presence of pesticides in water resources became a national concern in the early 80s when several studies reported the widespread distribution of a number of pesticides such as atrazine, simazine and cyanazine, among others (Bottoni et al., 2013). Both atrazine and simazine belong

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nowadays to the list of priority substances reported in the Directive 2008/105/EC. Maximum admissible concentrations in surface water and in groundwater are 100 ng L−1 for a single pesticide and 500 ng L−1 for a mix of pesticides (Directives 2006/118/EC and 2008/105/EC). 3.1.1. Review of published research studies on pesticides Researches on pesticides are conducted by research institutes, national environmental institutes (i.e. ISPRA) and regional water catchment agencies. Research reports from the latter are often not readably accessible and, when available, they tend to collect general information. For example, available online reports provide pesticides relative average concentrations in surface water and/or groundwater without differentiating among compounds. Such data could not be used to identify which and how much a certain pesticide is widespread in the Italian environment and therefore they have not been considered in this review. Available research papers report pesticide contamination of surface water and groundwater more often in Northern and Central Italy (Fig. 1a). The first published research work has been carried out by Readman et al. (1997) that analyzed several fungicides in the estuarine water of the Po River at 90 km from its mouth. Water from the Po River and adjacent canals was sampled 10 years later for pesticide determination by Pasti et al. (2007). Triazines and their metabolites were investigated in three minor rivers belonging to the Po River watershed by Benvenuto et al. (2010). Between 1992 and 1995, Griffini et al. (1997) monitored 45 pesticides (32 herbicides, 11 insecticides, 1 fungicide and 1 acaricide) in the Arno River (Tuscany, Central Italy). Herbicide concentrations in the same river were also investigated by Bono and Magi (2013). Sbrilli et al. (2005) and Pacioni et al. (2007, 2010) reported concentrations of pesticides in surface water and groundwater of Tuscany and Fucino Plain (Abruzzo, Central Italy), respectively. In southern Italy, surface waters from 10 rivers of the Calabria region were studied by Curini et al. (2001). Loos et al. (2007) conducted a study of contamination of surface water and groundwater around the Maggiore Lake, the second largest lake of Italy, by several EOCs including polar herbicides (atrazine, atrazine-desethyl, simazine, terbuthylazine, isoproturon, linuron and diuron). Concerning groundwater, Barra Caracciolo et al. (2005) sampled 20 surficial aquifers nearby farms with high agricultural activities in the provinces of Bergamo and Lodi (Lombardy, Northern Italy) to investigate the occurrence of the herbicides metolachlor and diuron. Successively, Guzzella et al. (2006) conducted a two-year monitoring campaign to evaluate herbicide contamination of surficial water in the Padan Plane (Northern Italy). Otto et al. (2007) collected water from 70 wells in alluvial aquifers north of the city of Vicenza (Veneto, Northern Italy). Pesticides were also investigated in groundwater from aquifers of Piedmont, Friuli V.G., Emilia R., Tuscany, Umbria and Sicily by Fava et al. (2010) and Fait et al. (2010). Laini et al. (2012) reported concentrations of the herbicide terbuthylazine and desethylterbuthylazine in lowland springs of the Po River. A reconnaissance study of contamination of several aquifers of Marche (Central Italy) was carried out by Sagratini et al. (2007). An important contribution in assessing occurrence of pesticides in Italian surface water and groundwater has been recently

Table 1 Rivers, lakes and regional groundwaters (GW) where pesticides were investigated. The national reconnaissance carried out by Ispra (2013) is not included in the table. Pesticides

Nr. of investigated pesticides

Rivers/Lakes

GW-regions

Herbicides

79

Lombardy, Piedmont, Friuli V.G., Veneto, Emilia R., Tuscany, Umbria, Marche, Abruzzo, Sicily

Fungicides

32

Po River, Arno River, not specified rivers of Tuscany, Maggiore Lake and its tributary rivers, surface waters of Fucino Plain, Lura Stream, Gordonella Stream, Seveso River, Livescia Stream, Trionto River, Passante River, Sinni River, Lese River, Cardone River, Telese River, Crocchio River, Corace River, Neto River, Alaca River Po River, Arno River, not specified rivers of Tuscany, surface waters of Fucino Plain

Insecticides

26

Algicides

1

Po River, Arno River, not specified rivers of Tuscany, Corace River, Neto River, Alaca River, Trionto River, Passante River, Sinni River, Lese River, Cardone River, Telese River, Crocchio River

Piedmont, Veneto, Tuscany, Umbria, Abruzzo, Sicily Piedmont, Veneto, Tuscany, Umbria, Sicily

Marche

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provided by the National Institute for Protection and Environmental Research (ISPRA previously APAT) (ISPRA, 2013). This very detailed survey includes the monitoring of hundreds of pesticides in water resources all over the entire Italian territory that has been carried out in the biennium 2009–2010 with a total of 21,576 collected samples. A summary of the rivers and regional groundwaters where pesticides were investigated is given in Table 1. More detailed information on investigated sites are available in supplementary material (Table A2). 3.1.2. Occurrence Among the reported maximum concentrations, 54.3% and 46.6% of the values in surface water and groundwater, respectively, are far above the environmental quality standards defined in the Directives 2006/118/EC and 2008/105/EC. The highest concentrations in surface water have been observed for the metabolite of glyphosate AMPA (167 × 103 ng L−1), the herbicides terbuthylazine (70 × 103 ng L−1),

diuron (30 × 103 ng L− 1), 2,4-DB (28 × 103 ng L− 1), 2,4-D (20 × 103 ng L−1), terbutryne (18 × 103 ng L−1) and metolachlor (16.47 × 103 ng L−1), the insecticide malathion (16 × 103 ng L− 1) and the herbicide linuron (13.13 × 103 ng L−1) (Fig. 2a). Whereas the highest concentrations in groundwater have been detected for the insecticide dieldrin (478.03 × 103 μg L−1), the priority substance simazine (221 × 103 ng L−1), the herbicide terbuthylazine (29.05 × 103 ng L−1), the insecticide cadusafos (24.96 × 103 ng L− 1), the fungicide azoxystrobin (18.96 × 103 ng L− 1), the herbicides bentazone (16 × 103 ng L− 1), pendimethalin (15.36 × 10 3 ng L − 1) and metolachlor (12.5 × 103 ng L− 1), the insecticide endosulfan sulfate (10.71 × 103 ng L−1) and the herbicide alachlor (10.2 × 103 ng L−1) (Fig. 2b). However of the 139 pesticides that have been studied, 64 in surface water and 56 in groundwater have been encountered with concentrations higher than the environmental limits defined in the Directive 2008/105/EC (100 ng L−1) (Table A1). According to ISPRA (2013), pesticide residues

Fig. 2. Pesticides with a maximum concentration N1000 ng L−1 in surface water (a) and in groundwater (b).

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belonging to different classes were encountered in 30.5% of surface water samples and 21.8% of groundwater samples. These percentages clearly point to the serious state of Italian surface water and groundwater contamination by pesticides. The 4 most ubiquitous compounds in surface water were in the following descending order: AMPA, glyphosate, terbuthylazine and terbuthylazine-desethyl. In groundwater, the pesticides more frequently detected were in the following order: the terbuthylazine metabolite terbuthylazine-desethyl, the atrazine metabolite atrazine-desethyl, terbuthylazine and atrazine (ISPRA, 2013). Results from the report of ISPRA (2013) indicate that the major number of samples with concentrations above the admissible environmental concentration occurred in the Po Valley which presents a very intensive agricultural activity. However, studies in other Italian regions, from north to south, such as Piedmont, Friuli V.G., Tuscany, Lazio, Marche, Abruzzo, Campania, Calabria and Sicily also provide evidences for pesticide concentrations in surface water and groundwater that are far above the environmental standard limits (Curini et al., 2001; Sbrilli et al., 2005; Guzzella et al., 2006; Sagratini et al., 2007; Fait et al., 2010; Fava et al., 2010; Pacioni et al., 2010; ISPRA, 2013). The herbicide metolachlor was detected by Barra Caracciolo et al. (2005) in 6 of the 20 investigated surficial aquifers of the provinces of Bergamo and Lodi (Lombardy, northern Italy). However, only two samples exceeded the maximum admissible concentration (110 ng L−1 and 140 ng L−1). Much higher concentrations of metolachlor have been encountered in the groundwater of Marche Region by Sagratini et al. (2007) (12.5 × 103 ng L−1) and in the Arno River by Griffini et al. (1997) (3.68 × 103 ng L−1). In the catchment area of the Arno River (approx. 8200 km2) pesticides are extensively used for agricultural activities. Increasing pesticide concentrations have been observed after intense rainfall events indicating the impact of pesticide run-off from the surrounding areas to the river (Griffini et al., 1997). The priority compound atrazine was the most ubiquitous contaminant in the groundwater of the Bergamo and Lodi provinces. It was found that in all investigated aquifers and, in 20% of collected samples, concentrations were higher than 100 ng L− 1 (Guzzella et al., 2006). According to Guzzella et al. (2006), the second most diffuse contaminant was the herbicide terbuthylazine (max. concentration 3.43 × 103 ng L−1). The presence of transformation products of atrazine and terbuthylazine in groundwater were also investigated by Guzzella et al. (2006). The s-triazine metabolite deethylterbuthylazine (DET), the dealkylated main transformation product of terbuthylazine, was often detected with concentrations higher than the standard limits (max. concentration 280 ng L−1). Other transformation products such as the atrazine metabolites disopropyl-atrazine (DIA) and atrazine-desethyl (DEA) were encountered with trace concentrations in the majority of samples (Guzzella et al., 2006). Groundwater concentrations of triazine reported by Guzzella et al. (2006) occurred in an intensive cultivated area where the depth to the water table varies between 0 and 40 m, the aquifers have a high transmissivity and the high permeability of the top soil horizons facilitates infiltration of pesticides towards groundwater. The most abundant herbicides reported by Loos et al. (2007) in the surface water of the Maggiore Lake (Lombardy and Piedmont) were terbuthylazine (max. concentration 7 ng L− 1), atrazine (5 ng L− 1), simazine (16 ng L− 1), diuron (11 ng L−1) and atrazine-desethyl (11 ng L−1). Similar concentrations were encountered by the same authors for tap water produced from this lake. This indicates incomplete removal by sand filtration and chlorination used in the waterworks of the Maggiore Lake for production of tap water. The same herbicides, except diuron, were encountered by Loos et al. (2007) also in tap water produced from groundwater nearby the Maggiore Lake. Here, concentration of atrazine was 12 ng L−1, terbuthylazine was 50 ng L−1, atrazine-desethyl was 20 ng L−1 and simazine was 6 ng L−1. As shown by Loos et al. (2007), pesticide maximum concentration in the area of the Maggiore Lake never exceeds the environmental limits (100 ng L− 1) reflecting the scarce agricultural land use of the territory. Bono and Magi (2013) reported that the terbuthylazine and desethylterbuthylazine

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concentrations in the Arno River were 14.20 and 6.71 ng L−1, respectively. Surface water of the Calabria Region (Southern Italy) has been shown to be severely contaminated by pesticides (terbuthylazine, 2,4D, 2,4-DB, terbutryne, diuron, and malathion) with concentrations ranging between 5.7 × 103 and 70 × 103 ng L−1 (Curini et al., 2001). Similarly to what was reported by Griffini et al. (1997) for the Arno River, increasing pesticide concentrations in the Calabria rivers have been observed by Curini et al. (2001) after intense precipitations over areas cultivated for forage and corn crops. According to these data, pesticides and their metabolites infiltrate towards groundwater endangering the safety of Italian aquifers that represent the major source for drinking water. It is worthwhile to remark that the application of atrazine in Italy has been prohibited since the early 1990s (Bottoni et al., 2013) and that, for example, all waterworks withdrawing surface water from the Po River had to adopt a filtration through active carbon as end-of-pipe-treatment to remove such pesticide. Nonetheless these strategies, atrazine and its metabolites are frequently found in Italian water resources. This is in agreement with several European studies that describe the presence of atrazine in groundwater and surface water (Garrido et al., 2000; Loos et al., 2010) and with investigations that report low degradation rates of herbicides in groundwater (Johnson et al., 2000; Franzmann et al., 2000). Another common pesticide found in Italian water resources is terbuthylazine and its metabolites. Its widespread occurrence is due to its use in Italy as atrazine substitute and its persistence in soil (Guzzella et al., 2006). 3.2. Industrials Thousands of compounds are used as intermediates in chemical factory industry (plasticizers, dyes, resins) or as food additives, antioxidants, surfactants and detergents. Consequently, these substances can be found in the environment due to industrial and domestic wastewater effluent discharges. Some of these which are known to cause serious problems to aquatic life either being toxic or acting as endocrine disruptors (hydrocarbons, nonylphenols and phthalates) have already been classified as priority pollutants. However, potential adverse effects of many others are unknown and they can therefore be considered as emerging contaminants. This review collects data on surfactants, flame retardants, plasticizers, antioxidants, chlorinate solvents and perfluoroalkylated compounds. 3.2.1. Review of published research studies on industrials We have identified that since 1997, 13 research works investigating the occurrence of industrials in both surface water and groundwater have been published. The most frequently investigated compounds were bisphenol A (n. 5), nonylphenol (n. 5) and some chlorinated solvents (n. 3). Table 2 reports a summary of investigated surface water and groundwaters. More detailed information on sampling sites of each single investigated industrial is given in Table A2. Clorurate solvents have been monitored in groundwater of the city of Ferrara (Emilia R.) by Gargini and Pasini (2007), of the city of Biella (Piedmont) by Piancone et al. (2011) and in several aquifers of Sicily (Pecoraino et al., 2008). Bacaloni et al. (2008) carried out a monitoring campaign for flame retardants and plasticizers in surface water of three volcanic lakes in Central Italy and in groundwater around one of these lakes. Aromatic amines were investigated in groundwater from an industrialized area of Milan by Müller et al. (1997). Phenolic compounds used as surfactants and detergents were studied in the surface water of the Po River and its tributary, the Lambro River by Davì and Gnudi (1999), Viganò et al. (2006) and Loos et al. (2007). The alkylphenols bisphenol A and nonylphenol, and related compounds were monitored in the Tiber River (Laganá et al., 2004; Patrolecco et al., 2006) and in three Ligurian rivers (Magi et al., 2010). Nonylphenol isomers were also analyzed in surface waters of the Velino River watershed in the Rieti district (Central Italy) by Vitali et al. (2004). An intensive sampling

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Table 2 Rivers, lakes and regional groundwaters (GW) where industrials were investigated. Industrials

Nr. of investigated Rivers/lakes industrials

Chlorinated solvents Flame retardants, plasticizers Intermediates of chemical factory industry Detergents Antioxidants Perfluoroalkylated compounds

22 11 9 8 6 5

Surfactants

3

GW-regions

Piedmont, Emilia R., Sicily Albano Lake, Martignano Lake, Vico Lake Lazio Po River, Lambro River, Seveso River, rivers of Liguria, Tiber River Lombardy, Sicily Lambro River, Seveso River, Tiber River Po River, Albano Lake, Martignano Lake, Vico Lake Lazio Po River, Adda River, Lambro River, Olona River, Dora Baltea River, Sesia River, Tanaro River, Ticino River, Stura di Lanzo River, Oglio River, Mincio River, Secchia River Po River, Lambro River, Seveso River, Tiber, River, Turano River, Velino River, Salto River, Tronto River, S. Susanna River, Corese River, Farfa River, Peschiera River, Turano Lake, Salto Lake, Lungo Lake, Ventina Lake

campaign of the Po River and its tributaries for monitoring perfluorinated organics has been carried out in 2007 by Loos et al. (2008). 3.2.2. Occurrence In general, industrials are reported to occur in both surface water and groundwater with concentrations that are higher than those of the other classes of EOCs presented in this review (Fig. 3a,b; Table A1). Among the reported maximum concentrations, 61.0% and 42.1% of the values in surface water and groundwater, respectively, are higher than 100 ng L−1. Exceptionally high concentrations were detected in groundwater for the priority substance benzene (15 × 106 ng L−1), tetrachlorethylene (N10 × 106 ng L−1) and vinyl chloride (1.09 × 106 ng L−1). Such high concentrations of benzene were detected in a Sicilian aquifer as consequence of petrochemical industrial activities (Pecoraino et al., 2008). The high concentrations of tetrachloroethylene found in surficial aquifer of the city of Biella (depth between 5 and 30 m) are associated to the activity of a dry cleaner company (Piancone et al., 2011). Vinyl chloride has been encountered in the Ferrara aquifer and it derives from the leaching of settlement ponds filled by industrial residues (Gargini and Pasini, 2007). According to published data, almost all analyzed chlorinated solvents appear in groundwater with maximum concentrations higher than 100 ng L− 1 . Indeed, trichloroethylene and 1,2dichloroethylene were found in groundwater with concentrations of 6 × 10 5 and 3 × 103 ng L− 1 , respectively (Gargini and Pasini, 2007; Pecoraino et al., 2008). The high concentrations of trichloroethylene were found in the Castellacio Mount groundwater body, a karstic aquifer in the Palermo area (Sicily) that is highly affected by anthropogenic activities. Such a contamination level also relates to the high aquifer vulnerability caused by karstic conduits which facilitate infiltration and a fast groundwater flow and therefore a rapid contaminant propagation (Sicilian Region Presidency, 2009). As for vinyl chloride, the presence of 1,2-dichloroethylene in the groundwater of Ferrara aquifer is due to the leaching of industrial residues (Gargini and Pasini, 2007). As reported by Gargini et al. (2004), the aquifer of Ferrara in the locality of Pontelagoscuro is considered as a vulnerable water body affected by excavations on the surface and basin impoundments (Gargini et al., 2004). Concentrations higher than 100 ng L− 1 have also been detected in Milan groundwater for two aromatic amines (2,4-dichloroaniline and 2,5-dichloroaniline) (Müller et al., 1997). Antioxidants in the Po River have been encountered with concentrations ranging between 6.4 × 10 3 and 128 × 10 3 ng L − 1 (Davì and Gnudi, 1999). During the three year monitoring campaign, Davì and Gnudi (1999) pointed to a constant presence of these contaminants in the Po River as a consequence of a continuous input from domestic waste. Abrupt variation of concentrations in the river water reported by the same authors has been interpreted as the effect of industrial waste discharges. Among the perfluoroalkylated compounds, perfluorooctanoate (PFOA) showed the highest concentration in the Tanaro River, one of the main Po River tributaries (1.27 × 103 ng L−1) (Loos et al., 2008). Although the exact origin of PFOA in the Tanaro River cannot be established,

Loos et al. (2008) suggested that it may come from industrial sources in its watershed. With only two exceptions, the majority of investigated detergents appeared in surface water of the Lambro River with a concentration between 1 × 103 and 3.6 × 103 ng L−1. Concentrations of same compounds in the Tiber River were considerably lower (b500 ng L−1) along its course in rural areas (agricultural and small domestic waste inputs), in the urban area of the city of Rome (industrial and domestic waste discharge) and close to its mouth before reaching the Tyrrhenian Sea. Almost all the flame retardants and plasticizers investigated by Bacaloni et al. (2008) were detected in surface water of the three volcanic lakes, Albano, Vico and Martignano (Lazio). Concentrations of these compounds showed a noticeable seasonal variation with higher values during summer when touristic activity is at its maximum. Among the three lakes, the Martignano Lake is the less polluted which reflects the relatively lower anthropogenic activity in its proximity. 3.3. Pharmaceuticals Pharmaceuticals can reach the environment through human excretion, improper disposal of unused and expired products and runoff from farm and livestock (Zuccato et al., 2000; Stuart et al., 2012). Several studies report occurrence of pharmaceuticals in surface water (Schwab et al., 2005; Moldovan, 2006) and groundwater (Barnes et al., 2008; Loos et al., 2010). According to the Center for Promotion of Imports from developing countries (CBI, 2009), Italy was in 2007 the third largest pharmaceutical market in the European Union (EU), accounting for 12% of the total EU consumption. 3.3.1. Review of published research studies on pharmaceuticals Among the EOCs considered in this review, pharmaceuticals are those that have been more intensively studied together with pesticides (Table A1). To date, 15 studies investigating the occurrence of 67 pharmaceuticals in surface water and groundwater have been published between 2000 and 2013. However as shown in Fig. 2c, studies reporting pharmaceutical concentrations in groundwater are limited to the region of Piedmont and Lombardy in Northern Italy and Apulia in Southern Italy. Reported compounds belong to the following categories: antibiotics (n. 34), anti-inflammatory (n. 11), lipid regulators (n. 5), β-blockers (n. 4), anxiolytics and anticonvulsants (n. 3), ulcer healings (n. 2), diuretics (n. 2), anti-cancer drugs (n. 2), analgesics (n. 2), antihypertensives (n. 1), anti- diabetics (n. 1), bronchodilators (n. 1), and mosquito repellents (n. 1) (Table 3). As for the other EOCs, groundwater studies are significantly less frequent than surface water studies (Table 3, Tables A1 and A2). The majority of the studies report concentrations of pharmaceuticals in the Po River and its tributaries Adda and Lambro rivers (Zuccato et al., 2000, 2005a, 2010; Calamari et al., 2003; Loos et al., 2007; Calza et al., 2010, 2011, 2013; Ferrari et al., 2011). Several studies have been also dedicated to monitor pharmaceutical contamination in the Tiber River (Lazio) upgradient and downgradient the city of Rome (Patrolecco et al., 2013), inside the city close to an hospital effluent (Perret et al., 2006) and downgradient a WWTP (Grenni et al., 2013). Several analgesics were reported by Marchese

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Fig. 3. Industrials with a maximum concentration N100 ng L−1 in surface water (a) and in groundwater (b).

et al. (2003) in the Tiber River without specifying the exact sampling site. The presence of a series of antibiotics was studied in the River Arno, the second longest river of Central Italy, by Zuccato et al. (2010). The occurrence of antibiotics, anti-inflammatories and lipid regulators was also investigated in three smaller rivers (Treste, Liri and Trigno rivers) and lakes (Campotosto, Trasimeno, Bolsena, Scanno, Sinizzo lakes) of Central Italy by Perret et al. (2006), in the Maggiore Lake (Lombardy) by Loos et al. (2007) and in two volcanic lakes of Lazio (Vico and Albano

lakes) by Marchese et al. (2003). Only 4 of the 15 studies report pharmaceutical concentrations either directly in groundwater (Barra Caracciolo et al., 2011) or in drinking water provided by local aquifers (Zuccato et al., 2000) or also in spring waters (Perret et al., 2006; Loos et al., 2007). In particular, Perret et al. (2006) investigated sulfonamide antibiotic occurrence also in natural mineral waters that are commercially available in Italy. Mineral natural water is directly collected at the point of emergence of groundwater without any treatment (Perret

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Table 3 Rivers, lakes and regional groundwaters (GW) where pharmaceuticals were investigated. Pharmaceuticals

Nr. of investigated pharmaceuticals

Rivers/Lakes

GW-Regions

Antimicrobial agents

34

Lombardy, Piedmont, Apulia

Anti-inflammatories

11

Lipid regulators β-blockers Psychiatric drugs

5 4 3

Analgesics Ulcer healings Anticancer drugs Diuretics Anti-hypertensives Anti-diabetics Bronchodilators Mosquito repellents

2 2 2 2 1 1 1 1

River Po, Lambro River, Adda River, Maggiore Lake and its tributary rivers, Arno River, Tiber River, Treste River, Trigno River, surface waters of Emilia R., Liri River, Treste River, Trigno River, Scanno Lake, Campotosto Lake, Bolsena Lake, Sinizzo Lake, Trasimeno Lake Po River, Lambro River, Adda River, Maggiore Lake and its tributary rivers, Tiber River, Bracciano Lake, Vico Lake, surface waters of Emilia R. Po River, Lambro River, Adda River, Maggiore Lake and its tributary rivers, Tiber River, Po River, Lambro River, Adda River, surface waters of Emilia R. Po River, Lambro River, Adda River, Maggiore Lake and its tributary rivers, surface waters of Emilia R., Tiber River Po River, Tiber River, Bracciano Lake, Vico Lake Po River, Lambro River, Adda River Po River, Lambro River, Adda River Po River, Lambro River, Adda River, surface waters of Emilia R. Po River, Lambro River, surface waters of Emilia R. Surface waters of Emilia R. Po River, Lambro River, Adda River, surface waters of Emilia R. Po River

et al., 2006). We considered therefore pharmaceutical concentrations of these waters as representative of the contamination status of the corresponding aquifers. 3.3.2. Occurrence Of the 66 pharmaceuticals reported for surface waters 13 compounds, in majority sulfonamide antibiotics, were never detected. Two antimicrobial agents (sarafloxacin and roxthromycin) were not quantified due to the use of inappropriate solid phase extraction (SPE) procedure (Loos et al., 2007) (Table A1). For other 6 compounds (azithromycin, trimethoprim, indomethacin, metoprolol, lorazepam, glibenclamide) data were estimated by interpretation of plots presented by Al Aukidy et al. (2012). The highest concentrations (N200 ng L−1) of pharmaceuticals in surface water have been detected for paracetamol (3.59 × 103 ng L− 1), furosemide (605 ng L− 1), sotalol (504 ng L−1), carbamazepine (345 ng L− 1), ofloxacin (306.1 ng L− 1), naproxen (264 ng L− 1), hydrochlorothiazide (255.8 ng L− 1), lincomycin (248.9 ng L− 1), atenolol (241.9 ng L− 1), sulfadiazine (236 ng L− 1), ibuprofen (210 ng L− 1), salicylic acid (205 ng L− 1) and bezafibrate (202.7 ng L−1) (Fig. 4). The majority of these high values were encountered in the Po River and in its tributary, Lambro River. The Po River

Lombardy, Piedmont Lombardy, Piedmont Lombardy Lombardy, Piedmont

Lombardy Lombardy

Lombardy

collects wastewater from a catchment area of about 71,000 km2 in the most densely and industrialized area of Italy (Calamari et al., 2003). The Lambro River receives wastewater from Milan, a city with more than a million of inhabitants that until 2004 did not have any WWTP. All the other major towns and animal farms along the Po River are equipped with secondary sewage treatment plants. The Po River drains sewage from about half of all the animal settlements in Italy (Calamari et al., 2003). Moreover, several authors describe how in the Po River pharmaceutical concentration increases from source to mouth reflecting the increase of loads of urban discharges (Zuccato et al., 2010) and the impact of manure run-off over pasture and surrounding agricultural lands. In almost all studies, water from the Tiber River was collected in the proximity of wastewater treatment plant effluents of the city of Rome and therefore, although the mitigation effects were caused by dilution with river water, the presence of pharmaceuticals as wastewater residues was expected (Al Aukidy et al., 2012). The compounds occurring with maximum concentrations higher than 100 ng L− 1 were anti-inflammatories (naproxen, ibuprofen, ketoprofen, diclofenac) downgradient the city of Rome (Patrolecco et al., 2013), sulfonamide antibiotics (sulfamethoxazole, sulfadiazine, sulfapyridine) in the Rome city center proximal to an

Fig. 4. Pharmaceuticals with maximum concentrations N100 ng L−1 in surface water.

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hospital effluent (Perret et al., 2006) and analgesics (salicylic acid) (Marchese et al., 2003) in an unspecified Tiber river stretch. Antiinflammatory and analgesic compounds have been also encountered in two volcanic lakes, Bracciano and Vico lakes (Lazio) (Marchese et al., 2003) with maximum concentrations ranging between 1 and 205 ng L− 1. Among these pharmaceuticals, those with the highest concentrations were salicylic acid (205 ng L− 1) and ibuprofen (201 ng L− 1). However as shown by the data of Marchese et al. (2003), there is a high seasonal variability of compound concentrations. The increasing pharmaceutical consumption during winter, especially of antibiotics, triggers an increase in their environmental concentrations (see also Castiglioni et al., 2006a). Lower pharmaceutical concentrations were reported in the Maggiore Lake by Loos et al. (2007) where carbamazepine, sulfamethoxazole and triclosan presented the following highest concentrations, 9.3, 9.5 and 4.1 ng L−1, respectively. According to Perret et al. (2006), sulfonamide antibiotics were not detected in surface water of the Liri River (Lazio) and in several lakes of Umbria, Lazio and Abruzzo regions (Trasimeno, Bolsena, Scanno, Sinizzo and Campotosto lakes). In the Arno River, the most abundant compounds were clarithromycin, ciprofloxacin and erythromycin-H2O with the highest maximum concentrations ranging between 30.52 and 44.76 ng L−1. Similarly to the case of the Po River, concentrations of pharmaceuticals increased from source to mouth as a consequence of discharge of treated wastewater (Zuccato et al., 2010). Concerning groundwater, only a minority of investigated pharmaceuticals was detected (only 13% of the total) and generally, concentrations in groundwater were significantly lower than those detected in surface water for a given compound. Only the antibiotic josamycin has been encountered with concentrations higher than 100 ng L−1. Barra Caracciolo et al. (2011) in their investigation of the effects of pharmaceutical waste disposals on bacterial communities detected this antimicrobial agent with a concentration of 150 ng L−1 in the groundwater near the city of Brindisi (Apulia). The josamycin contamination results from a disused open calcarenite quarry that was active for about 10 years for waste disposal by a pharmaceutical company that produced antibiotics. Groundwater in the proximity of the Maggiore Lake was found to be free of antibiotics and antiinflammatories (Loos et al., 2007). Drinking water collected by Zuccato et al. (2000) in the cities of Varese, Milan and Lodi (Lombardy) is abstracted by wells in local aquifers. Here, only 3 of the 16 investigated pharmaceuticals were detected with maximum concentrations ranging between 1.7 and 23.5 ng L−1. These compounds were the anticonvulsant diazepam (23.5 ng L−1), the bezafibrate metabolite clofibric acid (5.3 ng L− 1) and the antimicrobial agent tylosin (1.7 ng L− 1). Among the 11 sulfonamide antibiotics investigated by Perret et al. (2006), only 3 were encountered in natural mineral waters. These are sulfamethoxazole (80 ng L− 1), sulfadimethoxine (11 ng L−1) and sulfamethixole (9 ng L−1). 3.4. Estrogens The presence of estrogens in waters implies a risk for the health of wildlife (Wise et al., 2011). Indeed, estrogens together with other classes of compounds such as pesticides, polycyclic aromatic hydrocarbons, phthalate plasticizers, certain polychlorinated bisphenyls, dioxins, furans, and alkylphenols are endocrine disruptors (EDs) (Laganá et al., 2004). As EDs, they may interfere with the endocrine and reproductive activities of animals. The main source of estrogens in the environment is domestic wastewater. Between 10 and 100 μg of estradiol, ethinylestradiol, estriol and estrone are excreted daily by women through menstrual cycle (Baronti et al., 2000). The excretion of estrogens in pregnant women can reach the 30 mg per day. Estrogens are excreted in humane urine as conjugates of sulfuric acid and glucuronic acids (Laganá et al., 2004). However, estrogens can also derive from animal manure (Andaluri et al., 2012). According to Verlicchi et al. (2012) which carried out a review of the occurrence of pharmaceuticals,

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including estrogens, in urban wastewater, estrogen concentration after secondary treatments ranges between 0.2 and 110 ng L−1. As conjugates, these compounds have not direct biological activity but they may be converted in free estrogens by microbial transformation (Laganá et al., 2004). Among female estrogens, there are synthetic ones used as contraceptive and estrogens that are naturally synthesized by plants such as the phytoestrogens and mycoestrogens. 3.4.1. Review of published research studies on estrogens To the best of the author's knowledge, the occurrence of estrogens in Italian waters has been reported in 7 studies published since 2000. Among the 12 estrogens reported in these works, the synthetic estrogen 17α-ethinylestradiol (n. 6), and the female hormones, estrone (n. 6) and estriol (n. 4), have been the most frequently investigated (Table A1). As for the other classes of EOCs, surface water has been more often analyzed for estrogen occurrence than groundwater. Loos et al. (2007) is the only study reporting estrogen concentration in groundwater emerging from mountain springs between Piedmont and Lombardy (Northern Italy). Concentrations of female hormones, estradiol, estrone and 17α-ethinylestradiol, were monitored in the Tiber River 1 km away from its mouth (Baronti et al., 2000), downstream of a sewage treatment plant (Laganá et al., 2004) and upstream and downstream of the city of Rome (Patrolecco et al., 2013). Laganá et al. (2004) also monitored the occurrence of the mycoestrogen zearalenone and its two metabolites (α-zearalanol and β-zearalanol) and of three phytoestrogens (genistein, daidzein, biochanin A). Zuccato et al. (2005a) and Viganò et al. (2006) measured concentrations of female estrogens in the Po River upstream and downstream the confluence with its tributary Lambro River, close to the cities of Mezzano and Piacenza (Emilia R.) and Cremona (Lombardy). They also collected samples from the Lambro River for the analysis of the same compounds. As for pharmaceuticals, surface waters from the Maggiore Lake (Piedmont and Lombardy) and from its tributary rivers were collected by Loos et al. (2007) for measurements of estriol, 17α-ethinylestradiol, estrone, estradiol and diethylstilbestrol. Estrone, 17α-ethinylestradiol and 17β-estradiol were also measured in three rivers of the Liguria region by Magi et al. (2010). However, Magi et al. (2010) used in their monitoring campaign the polar organic chemical integrative sampler (POCIS), a passive sampler that provides timeweighted average concentrations of chemicals over deployment periods (ranging from weeks to months). Concentrations of target compounds in surface water were then recalculated by taking into account the mass of sorbent in the POCIS, the sampling rate and the sampling period (Magi et al., 2010). 3.4.2. Occurrence Maximum concentrations of estrogens in surface water of Italy were not very high (≤ 50 ng L− 1). The highest maximum concentrations (N10 ng L− 1) were reported for estradiol (50 ng L−1) and estrone (47 ng L−1) in the Lambro River by Viganò et al. (2006) and for 17βestradiol (12.9 ng L− 1) in surface water of Liguria by Magi et al. (2010) (Table A1). The sampling locations and names of the rivers investigated by Magi et al. (2010) were not provided. The only information that was reported is that sampled rivers are used for production of drinking water in the Liguria region. All the other analyzed estrogens were not detected or detected with maximum concentrations not higher than 7 ng L− 1. The most abundant compounds in the Tiber River were estrone and the phytoestrogen genistein with maximum concentrations of 12 and 7 ng L−1, respectively (Laganá et al., 2004). The effects of phytoestrogen on human and wildlife is an important discussion topic (Laganá et al., 2004). They have been reported to have beneficial health impacts including a lowered risk of osteoporosis, heart disease and breast cancer (Patisaul and Jefferson, 2010). However, some studies haves suggested that these compounds have estrogenic properties like those of natural human hormones (Miksicek, 1993). They are structurally and functionally similar to 17β-estradiol (Laganá

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et al., 2004). Maximum concentrations of estrone, estriol and 17βestradiol in the Po River were low, ranging between 1 and 6 ng L− 1 (Viganò et al., 2006). The synthetic hormone 17α-ethinylestradiol was never detected (Zuccato et al., 2005a; Viganò et al., 2006). Surface water of the Maggiore Lake and its tributary rivers showed a maximum concentration of estrone of 0.4 and 0.2 ng L−1, respectively (Loos et al., 2007). All the other compounds investigated by Loos et al. (2007) were not detected in lake and rivers waters, with the exception of estradiol that occurred in surface water with a concentration of 0.9 ng L− 1. According to Loos et al. (2007), groundwater collected in a mountain spring in the proximity of the Maggiore Lake was estrogen free. 3.5. Illicit drugs Illicit drugs (IDs) are the latest group of emerging pollutants to be identified in the aquatic environment which are receiving a special attention (Boleda et al., 2009). As pharmaceuticals, many of IDs have potent pharmacological effect and their presence as complex mixtures may have toxic effects. The European Monitoring Centre of Drugs and Drug Abuse (EMCDDA) reports a drug use prevalence in Italy in 2012 of 3.5%, similar to Portugal, Austria, Slovakia and Slovenia. This data include adults with age between 15 and 64 that has been consuming cannabis, cocaine, heroin, amphetamines, ecstacy and hallucinogens. According to the report of the Policy Drug Department of the Italian Parliament (2012), the average number of ID consumers in Italy in 2010 was about 2,327,335. The estimated number includes both occasional and addicted consumers of cocaine, heroin, cannabis, amphetamines, ecstacy and hallucinogens. 3.5.1. Review of published research studies on illicit drugs The recent interest towards these contaminants is reflected by a limited number of publications (Table A1). The majority of present studies deals with the occurrence of IDs in urban wastewater (Castiglioni et al., 2006b, 2011; Zuccato et al., 2008a, 2011; Mari et al., 2009) confirming that treatments at the WWTPs are not able to eliminate these pollutants. Concentrations of IDs in Italian urban wastewater are in the order of ng L−1 and therefore it is likely that these compounds, traveling long distances, may contaminate surface water and groundwater. The first comprehensive work in Europe was carried out by Zuccato et al. (2005b). They estimated cocaine usage by measuring concentrations of cocaine and its main human metabolite benzoylecgonine (BE) in Italian urban wastewater and in the Po River. According to Ambre (1985), 45% of cocaine is excreted in urine by the human body mainly as BE and only a minor part is excreted as the parent drug. Zuccato et al. (2005b) monitored cocaine and BE concentrations in WWTP effluents of 4 Italian cities (Varese, Cuneo, Latina, Cagliari) with a population equivalent (number of persons producing 60 g d−1 of biological oxygen demand) between 45,000 and 270,000. Samples for cocaine and BE analysis were also collected from the Po River at Mezzano, Pavia (Lombardy). Zuccato et al. (2008b) extended their research to a series of illicit drugs such as opioids, amphetamine and cannabis derivatives. They monitored concentrations of these substances in surface waters of Lombardy (Po River, Olona River, Lambro River, Maggiore Lake, Varese Lake) and Tuscany (Arno River) (Fig. 1e, Table A2). To date, studies concerning concentrations of IDs in Italian groundwater are not available (Fig. 1e). 3.5.2. Occurrence Only three (amphetamine, 6-acetylmorphine and 6-acetylcodeine) of the fifteen investigated IDs were not detected in the surface water of the Po, Lambro, Olona and Arno rivers and of the Varese and Maggiore lakes. Cocaine and its metabolites (BE and norbenzoylecgonine), codeine, and methadone and its metabolite (2-ethylidene-1,5-dimethyl3,3-diphenylpyrrolidine) (EDDP) were encountered in 100% of surface water samples collected in the Po River. Results from Zuccato et al. (2005b) reported average concentrations in the Po River of cocaine

and its metabolite BE of 0.001 and 25 ng L−1, respectively. The higher concentration for BE corroborates that it is the major metabolite of cocaine, however the cocaine/BE ratio was lower (0.05 ± 0.02) than expected suggesting an additional degradation pathway for cocaine. By considering the Po River flow rates, BE/cocaine molar ratio and the average fraction of cocaine excreted as BE (45%), Zuccato et al. (2005b) estimated a cocaine equivalent per day of almost 4 kg. As expected, concentrations in urban WW were much higher than in the Po River with maximum average concentrations measured in the WW of the treatment plant of Latina (Lazio, Central Italy) where concentrations for cocaine and BE were 120 and 750 ng L− 1, respectively. Among the investigated rivers (Po, Lambro, Olona and Arno rivers), the study from Zuccato et al. (2008b) shows that in general, concentrations of cocaine, BE, morphine, codeine, methadone and its metabolite EDDP ranged between 3 and 183 ng L−1; whereas methamphetamine, the cannabis metabolite 11-nor-9-carboxy-delta9-tetrahydrocannabinol and other cocaine metabolites (norbenzoylecgonine, norcocaine, cocaethylene) were detected in lower concentrations (between 2 and 8 ng L−1). The Po River resulted to be the less polluted. Here, measured cocaine and BE concentrations were lower than those obtained in the field campaign carried out by the same authors in 2004 (Zuccato et al., 2005b). This confirmed findings of Castiglioni et al. (2006a,b) that reported an increased efficient illicit drug removal at the WWTP of Milan. The highest concentrations in the Po River were detected for BE (5 ng L−1), codeine (3 ng L−1) and EDDP (2 ng L−1). The two tributaries of the Po River, Olona and Lambro rivers resulted to be heavily polluted (Zuccato et al., 2008b). In both rivers, compounds with higher concentrations were BE (between 50 and 183 ng L−1), cocaine (between 15 and 44 ng L− 1), morphine (between 4 and 38 ng L− 1), codeine (between 12 and 51 ng L−1) and EDDP (between 10 and 18 ng L−1). The Arno River showed concentrations that were in general higher than in the Po River. Similarly to the Po River, the highest maximum concentrations in the Arno River have been detected for BE (37 ng L−1), codeine (9 ng L−1) and EDDP (7 ng L−1). On the other hand, lakes were found to be less contaminated with BE and EDDP being the only detected contaminants with concentrations in the order of pg L−1. 4. Relating EOC physico-chemical properties to their environmental occurrence The presence of EOCs in the Italian water resources depends on several factors related to the physico-chemical parameters of the compounds and on the characteristics of the environmental media. To correctly interpret the reason why a certain EOC has been encountered in the sampling location, further data on the characteristics of the environmental compartments would be needed. Considering only the physico-chemical properties of EOCs, without taking into account the nature of the environmental media, is not sufficient to understand their fate in the environment. However, we believe that it is worthwhile providing a brief description of compounds and environmental characteristics that play an important role in the fate and distribution of such contaminants. To constrain such interpretation to the most detected EOCs, we selected those compounds that have been encountered in surface and/or groundwater at least at three sampling sites with a maximum concentration higher than 100 ng L−1. This concentration limit is the one defined for individual pesticides and we applied such a threshold value also for the other contaminant classes considered in this review. The 52 contaminants selected according to these criteria are listed along with the physico-chemical parameters influencing their environmental fate in Table 4. Concerning physico-chemical properties of compounds, the octanol-water partitioning coefficient (Kow) and the solubility in water (Sw) can both give an indication of compound mobility and affinity to sorption (Pal et al., 2013). Substances with a log Kow b 4 are hydrophilic and those with a log Kow N 4 are hydrophobic. Hydrophobic compounds show in general a high sorption affinity especially onto organic matter (Pan et al., 2009). The

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Table 4 Most detected EOCs in surface water and/or groundwater with their physico-chemical properties and maximum concentrations. EOCs in italic are priority substances defined in the Directive 2008/105/EC. EOC Classes

Use

Compounds

Log Kowa

Sw (mg L−1)a

GUS

SW (ng L−1)

GW (ng L−1)

Pesticides

Herbicide

Terbuthylazine Atrazine Metolachlor Simazine Linuron Desethylterbuthylazine Atrazine-desethyl Diuron Alachlor Atrazine-desisopropyl Oxadiazon Bentazone Propyzamide Metribuzine 2,4-D Dicamba Oxyfluorfen Terbutryne AMPA Glyphosate Carbofuran Propoxur Malathion Metalaxyl Procymidone Oxadixyl Dichloran Ciprofloxacin Clarithromycin Lincomycin Ibuprofen Naproxen Diclofenac Bezafibrate Atenolol Carbamazepine Salicylic acid Furosemide Hydrochlorothiazide Bisphenol A 4-Nonylphenol Nonylphenol 4-Nonylphenol mono-ethoxylate 4-Nonylphenol di-ethoxylate Vinyl chloride Chloroform Perfluorooctanoate Tripropyl phosphate Triphenyl phosphate Triisobutyl phosphate Tributyl phosphate Tris(2-butoxyethyl) phosphate

3.40 2.61 2.18 3.20

5.00–9.00 34.70 −2.81d 6.20 75.00

2.93 2.68 3.52

8.60 42.00 240.00

1.90b 3.75c 3.32c 3.35c 2.03c 3.80b 4.50b 1.83c 2.19c

4.80 2.80 3.43 1.70 2.81 2.21 4.73 3.74

0.70 500.00-570.00 15.00 1050 677.00 4500-8310 0.12 25.00

−3.40 2.32 1.52 2.36 1.65 3.30e 0.65f 2.80 0.28 3.16 0.20 3.97 3.18 4.51

10,500 320.00 1860 145.00 8400 1470-3,070e 3,400f 6.30 30,000 1.69 927.00 21.00 15.90 2.37

0.16 2.45 2.26 2.03 3.32 5.76 5.71

130,000 18.00 2240 73.10 722.00 120–300 7.00 6.35

1.62 1.97 6.30 1.87g 4.59 3.60g 4.00 3.75

2700–8800 7950 9500 6,450g 7.3 × 10−7 16.20g 280.00 1100

70,000 2800 16,470 620.00 13,130 4750 2670 30,000 440.00d 200.00 4000 1800 1800 3600 20,000 2200 150.00 18,000 167,000 2800 1200 240.00 16,000 1440 170.00 370.00 2330 124.00 128.00 248.90 210.00 264.00 158.00 202.70 241.90 345.00 205.00 605.00 255.80 494.00 700.00 158,000 1300 3600 / 8700 1270 651.00 21.00 380.00 784.00 127.00

29,050 2700 12,500 221,000 100.00 3150 480.00 100.00 10,200 110.00 7790 16,000 450.00 80.00 n.d. n.d. / n.d. n.d. n.d. 1200 90.00 n.d. 7500 820.00 4110 650.00 No data available / n.d. n.d. / n.d. n.d. n.d. n.d. / n.d. / / / / / / 1093 × 103 4800 / 5.00 164.00 10.00 10.00 53.00

Insecticide

Fungicide

Pharmaceuticals

Antimicrobial agent

Anti-inflammatory

Lipid regulator b-blocker Psychiatric drug Analgesic Diuretic Industrials

Intermediate of chemical factory industry Surfactant Detergent Chlorinated solvent Perfluoroalkylated compound Flame retardant, plasticizer

0.86d 2.55c 3.55d 2.70d 5.55d −1.54e 1.13 −0.63e 4.56d 3.73d −1.28c 4.26d 0.70d

n.d.: not detected; a Hazardous Substances Data Bank (HSDB) from the U.S. National Library of Medicine, Toxnet (2013). b Bottoni et al. (1996). c Köck-Schulmeyer et al. (2012). d Calculated according the formula: logDT50 × (4-log Koc) with the data presented by Vogue et al. (1994). e Fao (2001). f Complex Molecular Database for Environmental Protection (2011). g Marlund (2005).

opposite occurs for compounds that are hydrophilic. Another important parameter for pesticides is the Groundwater Ubiquity Score (GUS) index which gives an estimate of the compound leachability. This method uses the soil organic carbon-water partitioning coefficient (Koc) and the half-life in soil (DT50) (Gustafson, 1993). The selected contaminants belong to the classes of pesticides (n. 27), pharmaceuticals (n. 12) and industrials (n. 13). With the exception of vinyl chloride which was investigated only in groundwater, all the contaminants of Table 4 have been encountered in surface water. On the other hand, they have been less frequently detected in groundwater. Most of

pesticides and 50% of industrials have been found also in groundwater, whereas pharmaceuticals were not encountered or they were not investigated at all in this environmental compartment (i.e. salicylic acid). Among pesticides, herbicides, and in particular triazines, have been detected by several authors in different Italian water resources. The widespread contamination by these compounds appears to correlate with their log Kow values and GUS indexes. Indeed, all these pesticides can be considered rather hydrophilic with a potential for leaching from moderate to high. The pesticides that have not been detected in groundwater are terbutryne, glyphosate and malathion.

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Their absence in groundwater can be related more to the GUS indexes than to the log K ow. GUS indexes indicate low leaching potentials (GUS b 1.8) and consequently a scarce probability to encounter such contaminants in groundwater. Concerning pharmaceuticals, antimicrobial agents and anti-inflammatories have been most frequently detected in surface water. This is in accordance with their physicochemical properties that point to relatively high hydrophilic characters and high water solubilities. Recently, EOC sorption affinity has been showed to also depend on their surface charge (Schaffer et al., 2012). Depending on the environmental pH, the EOCs can be either neutral or positively or negatively ionized (Schaffer et al., 2012). The degree of their ionization affects the sorption that can occur by interaction with mineral surfaces (surface complexation) and with organic matter (Martínez-Hernández et al., 2014). At the typical environmental pH range (5–8), the three anti-inflammatories and the analgesic salicylic acid almost entirely exist in the anion form and have therefore a lower tendency to be sorbed to clay minerals and organic matter of the sediments. Carbamazepine has been recognized as a persistent environmental contaminant by several authors (Löffler et al., 2005; Williams et al., 2009; Martínez-Hernández et al., 2014). Negligible carbamazepine sorption affinity for sediments can be interpreted as a consequence of its low hydrophobicity and to the fact that it mainly occurs in the environment in its neutral form. Among industrials, phenolic compounds have been more frequently detected in surface water and organophosphorus plasticizers in both surface water and groundwater. According to their hydrophobic character and low water solubility, these contaminants should not be readily encountered in the aquatic compartment. Chlorinated solvents have been found with very high concentrations (thousands of ng L−1) in urban groundwater affected by leaching of ponds filled with industrial residues and in groundwater contaminated by petrochemical activities (Gargini and Pasini, 2007; Pecoraino et al., 2008). Their groundwater occurrence is therefore not surprising and it correlates also with their physico-chemical properties which point to a high water solubility and to a hydrophilic character. By considering solely the most detected compounds with concentrations higher than 100 ng L−1 (Table 4), concentration in groundwater is generally lower than the concentration in surface water suggesting natural attenuation processes. Higher EOC groundwater concentrations generally occur with very persistent contaminants (i.e. herbicides) or as consequence of severe contamination events produced by industrial activity directly into the groundwater (i.e. chlorinated solvents). EOCs in the environment are also subject to microbial degradation. Concerning these processes, the redox conditions of the environment have shown to play an important role for the fate and distribution of several EOCs. Most of the EOCs are electron donors and they can undergo oxidation by microbial metabolism (Bouwer and Zehnder, 1993). Redox reactions can also occur inorganically, but many of them only proceed at significant rates when the reactions are microbially catalyzed (e.g. Appello and Postma, 2007). Recently, several EOCs have also been shown or suspected to be redox sensitive (Massmann et al., 2008; Tuxen et al., 2006; Heberer et al., 2008; Reineke et al., 2008; Meffe et al., 2012; Burke et al., 2013). The importance of biodegradation processes is indicated by the occurrence of several EOC metabolites in surface water and groundwater that has been reported in this review. This should strengthen researches on the identification of EOC metabolites in water resources since no occurrence of the parent compounds could lead to a wrong evaluation of their contamination status. 5. Discussion The first observation arising from this review is that there is a nonhomogeneous distribution of EOCs studies in the Italian territory (Fig. 1a–e). With the exception of the national reconnaissance of ISPRA (2013), only 4 studies report investigations in Southern Italy out of the 47 publications considered here. For all EOC classes, the

majority of the studies reports concentrations in Northern Italy (nr. of studies: 30) and to a lower extent in Central Italy (nr. of studies: 13). Research about these contaminants requires advanced detection methods and the use of state of the art instruments requiring significant economical investments. However, many Southern Italian regions suffer of severe water stresses due to the increase of the water demand, the lack of adequate management practices and the decrease in mean precipitations (OECD, 2013). Such conditions should require a water resource protection policy that includes a monitoring program to cope with water resource deterioration. The EOCs that were more intensively studied in terms of the number of published research studies are in the following descending order: pesticides (16), pharmaceuticals (15), industrials (13), estrogens (7) and IDs (2). In terms of distribution of the studies over the national territory, the most investigated compounds are pesticides followed by industrial, pharmaceuticals, estrogens and IDs. Estrogens were studied in groundwater only in Northern Italy (between Piedmont and Lombardy regions) and in surface water of few Italian rivers (Po and Tiber rivers and 3 non-specified rivers of Liguria) and of one of the main Italian lakes (Maggiore Lake). On the other hand, IDs have been investigated only in surface water of Maggiore Lake and of 5 rivers of Northern Italy. In general, studies in groundwater are less frequent than in surface water reflecting the more elaborated sampling procedure and the necessity of more sophisticated analytical techniques with lower detection limits. Data presented in this review point to a serious contamination by EOCs of a number of Italian water resources. This holds true especially for pollutants such as pesticides, industrials and to a lower extent pharmaceuticals. The pesticide compounds that represent the most severe threat for the Italian water resources (environmental concentrations of thousands of ng L−1) are dieldrin, AMPA, simazine, terbuthylazine, diuron, 2,4-DB, 2,4-D, terbutryne, cadusafos, endosulfan sulfate, azoxystrobin, malathion, metolachlor, pendimethalin, bentazone, alachlor and linuron. Maximum concentrations of pesticides reported here are far above the environmental limits defined in the 2006/118/EC and 2008/105/EC Directives. Pesticide highest concentrations in Italian surface water and groundwater show values up to 167 × 103 and 478 × 103 ng L−1, respectively (Ispra, 2013). Such high values are reported more frequently in the Po Valley, however also surface water and groundwater of other Italian areas are characterized by high concentrations (Curini et al., 2001; Sbrilli et al., 2005; Guzzella et al., 2006; Sagratini et al., 2007; Fait et al., 2010; Fava et al., 2010; Pacioni et al., 2010; ISPRA, 2013). As reported by several authors (Johnson et al., 2000; Franzmann et al., 2000; Hu et al., 2009), many pesticides are persistent and can therefore bioaccumulate, travel long distances and infiltrate towards groundwater without being significantly attenuated. The same occurs for several industrials that have been found in Italian surface water and groundwater with maximum concentrations up to 158 × 103 and 15 × 106 ng L−1, respectively (Davì and Gnudi, 1999; Pecoraino et al., 2008). The industrials occurring with concentrations higher than 10 × 103 ng L− 1 are benzene, tetrachloroethylene, vinyl chloride, trichloroethylene, nonylphenol, 4-tert-octylphenol and a series of antioxidants. Pharmaceutical maximum concentrations in surface water are in general lower (up to 3.59 × 103 ng L− 1) and in groundwater only one substance (the antimicrobial agent josamycin) has been encountered with concentrations higher than 100 ng L−1. The pharmaceuticals that mostly contribute to the contamination of Italian surface water are paracetamol, furosemide, sotalol, carbamazepine, ofloxacine, naproxen, hydrochlorothiazide, lincomycin, atenolol and sulfadiazine. Estrogens and IDs were both detected in surface water with maximum concentrations up to about 50 ng L−1. Groundwater concentrations for estrogens were always below the detection limits, whereas IDs have so far not been studied in groundwater. Similar contamination profiles were outlined by Murray et al. (2010) and Lapworth et al. (2012) for worldwide freshwater environments and by Jurado et al. (2012) for Spanish groundwater. These authors identified that among the investigated EOCs, those that are more often

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encountered in water resources with the highest concentrations are pesticides followed by industrials and pharmaceuticals. The occurrence of attenuation processes during infiltration and transport in the saturated zone is confirmed for those EOCs that show groundwater concentrations lower than those in surface water. However, there are cases (i.e. for industrials) in which concentrations in groundwater are exceptionally high (thousands of ng L−1) and of the same order of magnitude of surface water concentrations. Such concentrations are often related to the aquifer vulnerability (i.e. karstic aquifers with plenty of conduits or shallow groundwater tables with high aquifer transmissivity) and to severe contamination events over long periods of time. As reported in this review, pesticide contamination is strictly correlated to the agricultural activities occurring in the watersheds and several authors reported that pesticide concentrations in surface water have increased following rain events as a consequence of runoff from surrounding areas (Griffini et al., 1997; Curini et al., 2001). Contamination by pharmaceuticals and estrogens derived mainly from wastewater effluents discharges and manure run-off from pasture and agricultural lands in the river watershed. Industrials are primarily released into the environment through industrial wastewater effluents and leakage of industrial residual waste. Once in the environment, EOCs can undergo several processes such as, for instance, dilution with river water, sorption and biodegradation. Depending on their physico-chemical properties, EOCs are more or less likely to be encountered in the environment. As reported in this review, the detection of some EOCs seems to correlate with their log Kow, solubilities and GUS indexes (herbicides and antimicrobial agents). On the other hand, there are cases in which such correlation cannot be recognized. Such inconsistency is not totally unexpected since the analysis was based solely on EOC properties without taking into account the source of contamination and the characteristics of the environmental media can be incomplete and misleading. 6. Conclusions This review presents data on the occurrence of a vast range of EOCs (298) in surface water and groundwater of Italy which was not available in the literature. Through the review of 47 published researches, a first insight of the EOC contamination status of Italian water resources has been pointed out. Concerning pesticides, the 54.3% and 46.6% of maximum concentrations in surface water and groundwater, respectively, are far above the environmental quality standards defined in the Directives 2006/118/EC and 2008/105/EC. With respect to industrials, 61.0% and 42.1% of reported maximum concentrations in surface water and groundwater, respectively, have values higher than 100 ng L−1. According to the currently available studies, contamination of Italian water resources by estrogens and IDs appears to not represent a significant problem. However, given the limited number of available studies such a conclusion is premature and additional investigations are needed. Concentrations of both pesticides and industrials in surface water and groundwater concentrations are generally in the same order of magnitude whereas pharmaceutical concentrations in groundwater appear lower than in surface water. This is due to different contamination sources and pathways and it also could be related to the different degradation rates affecting EOCs in the subsurface. Indeed, several EOC metabolites were encountered in surface water and groundwater highlighting the role of microbial processes in the EOC environmental fate. For this reason the identification of the degradation pathways to which EOCs undergo once released in the environment becomes crucial. It is important to remark that contamination of water resources in Southern Italy is poorly or not at all characterized. Apart from the national reconnaissance study of ISPRA (2013), groundwater of several regions from Southern Italy (i.e. Campania, Molise, Basilicata, Calabria and Sardinia regions) has so far not been collected for EOC determination. Excluding pesticides, the same applies for surface water even if surface water studies are more numerous than groundwater studies. These

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data reflect the necessity to foster investigations on EOC occurrence especially in the Southern Italian regions. Moreover, drinking water and environmental quality standards are likely to be defined for more EOCs in the near future and therefore a better understanding of their spatial and temporal occurrence should become a priority. Besides EOC ecotoloxical effects, consumption rates, persistency and bioaccumulation, future researches on EOCs should also be prioritized based on EOC occurrence review studies which identify those contaminants that are frequently detected with environmentally significant concentrations and that therefore represent a potential threat for water resources. Supplementary data to this article can be found online at http://dx. doi.org/10.1016/j.scitotenv.2014.02.053. Acknowledgments The authors wish to acknowledge the geologist, Mauro Roma, of the ISPRA Institute for his advices during the elaboration of the cartographical documents and the Ph.D. students Alberto Blanco González and María de las Virtudes Martínez Hernández of the IMDEA Water Institute (Madrid, Spain) for their help with the GIS software. References Al Aukidy M, Verlicchi P, Jelic A, Petrovic M, Barceló D. Monitoring release of pharmaceutical compounds: occurrence and environmental risk assessment of two WWTP effluents and their receiving bodies in the Po Valley, Italy. Sci Total Environ 2012;438:15–25. Ambre J. The urinary excretion of cocaine and metabolites in humans: a kinetic analysis of published data. J Anal Toxicol 1985;9(6):241–5. Andaluri G, Suri RP, Kumar K. Occurrence of estrogen hormones in biosolid, animal manure, and mushroom compost. Environ Monit Assess 2012;184(2):1197–205. Appello CAJ, Postma D. Geochemistry, groundwater and pollution. A.A. Balkema Ed.Amsterdam: The Netherlands: A.A. Balkema Ed.; 2007. Bacaloni A, Cucci F, Guarino C, Nazzari M, Samperi R, Laganà. Occurrence of organophosporus flame retardant and plasticizers in three volcanic lakes of central Italy. Environ Sci Technol 2008;42:1898–903. Barnes KK, Kolpin DW, Furlong ET, Zaugg SD, Meyer MT, Barber LB. A national reconnaissance of pharmaceuticals and other organic wastewater contaminants in the United States — I) groundwater. Sci Total Environ 2008;402:192–200. Baronti C, Curini R, D'Ascenzo G, Di Corcia A, Gentili A, Samperi R. Monitoring natural and sythetic estrogens at activated sludge sewage treatment plants and in a receiving river water. Environ Sci Technol 2000;34(24):5059–66. Barra Caracciolo A, Giuliano G, Grenni P, Guzzella L, Pozzoni F, Bottoni P, et al. Degradation and leaching of the herbicides metolachlor and diuron: a case study in an area of Northern Italy. Environ Pollut 2005;134:525–34. Barra Caracciolo A, Grenni P, Falconi F, Caputo MC, Ancona V, Uricchio VF. Pharmaceutical waste disposal: assessment of its effects on bacterial communities in soil and groundwater. Chem Ecol 2011;27(1):43–51. Benvenuto F, Marín JM, Sancho JV, Canobbio S, Mezzanotte V, Hernández F. Simultaneous determination of triazines and their main transformation products in surface and urban wastewater by ultra-high-pressure liquid chromatography–tandem-mass spectrometry. Anal Bioanal Chem 2010;397:2791–805. Boleda R, Galceran T, Ventura F. Monitoring of opiates and cannabinoids and their metabolites in wastewater, surface water and finished water in Catalonia, Spain. Water Res 2009;43:1126–36. Bono L, Magi E. Fast and selective determination of pesticides in water by automated on-line solid phase extraction liquid chromatography tandem mass spectrometry. Anal Lett 2013;46:1–10. Bottoni P, Keizer J, Funari E. Leaching indices of some major triazine metabolites. Chemosphere 1996;32(7):1401–11. Bottoni P, Grenni P, Lucentini L, Barra Caracciolo A. Terbuthylazine and other triazines in Italian water resources. Microchem J 2013;107:136–42. Bouwer EJ, Zehnder JB. Bioremediation of organic compounds — putting microbial metabolism to work. Trends Biotechnol 1993;11:360–7. Burke V, Richter D, Hass U, Dünnbier U, Greskowiak J, Massmann G. Redox-dependent removal of 27 organic trace pollutants: compilation of results from tank aeration experiments. Environ Earth Sci 2013. http://dx.doi.org/10.1007/s12665-013-2762-8. Cabeza Y, Candela L, Ronen D, Teijon G. Monitoring the occurrence of emerging contaminants in treated wastewater and groundwater between 2008 and 2010. The Baix Llobregat (Barcelona, Spain). J Hazard Mater 2012;239–240:32–9. Calamari D, Zuccato E, Castiglioni S, Bagnati R, Fanelli R. Strategic survey of therapeutic drugs in the rivers Po and Lambro in Northern Italy. Environ Sci Technol 2003;37: 1241–8. Calza P, Marchisio S, Medana C, Baiocchi C. Fate of antibacterial spiramycin in river waters. Anal Bioanal Chem 2010;396:1539–50. Calza P, Medana C, Raso E, Giancotti V, Minero C. N,N-diethyl-m-toluamide transformation in river water. Sci Total Environ 2011;409:3894–901.

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Emerging organic contaminants in surface water and groundwater: a first overview of the situation in Italy.

This paper provides the first review of the occurrence of 161 emerging organic compounds (EOCs) in Italian surface water and groundwater. The reported...
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