An environmental forensic procedure to analyse anthropogenic pressures of urban origin on surface water of protected coastal agro-environmental wetlands (L’Albufera de Valencia Natural Park, Spain)

Journal of Hazardous Materials 263P (2013) 214–223

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An environmental forensic procedure to analyse anthropogenic pressures of urban origin on surface water of protected coastal agro-environmental wetlands (L’Albufera de Valencia Natural Park, Spain) Juan Pascual-Aguilar a,∗ , Vicente Andreu a , Yolanda Picó b a Centro de Investigaciones sobre Desertificación-CSIC-UV-GV, Departamento de Degradación y Conservación de Suelos, Carretera de Moncada-Náquera km 4.5, 46115 Moncada, Valencia, Spain b Laboratori de Nutrició i Bromatologia, Facultat de Farmàcia, Universitar de València, Av. Vicent Andrés Estell´es s/n, 46100 Burjassot, València, Spain

h i g h l i g h t s • Carbamazepine was the pharmaceutical substance most detected with concentrations up to 31.0 ng/L. • Cocainics were found in higher concentrations (maximum of 67.8 ng/L in sample PM6) and in more sites. • Connectivity is strong between municipalities with high population, SWTPs and irrigation areas.

a r t i c l e

i n f o

Article history: Received 18 May 2013 Received in revised form 24 July 2013 Accepted 25 July 2013 Available online 2 August 2013 Keywords: Emerging contaminants Geographical information systems Environmental mass spectrometry Water quality Mediterranean marshlands

a b s t r a c t Detection and spatial distribution of 14 drugs of abuse and 17 pharmaceuticals in surface waters was investigated to determine transport hydrological connectivity between urban, agriculture and natural environments. Solid-phase extraction and liquid chromatography tandem mass spectrometry was applied to all samples. To determine spatial incidence of contaminants, analytical results of target compounds were georeferenced and integrated into a geographical information systems structure together with layers of municipal population, location of sewage water treatment plants and irrigation channels and sectors. The methodology was applied to L’Albufera Natural Park in Valencia (Spain). A total of 9 drugs of abuse were detected at 16 points (76% of the sample sites). Cocaine and its metabolite, benzoylecgonine, were the most detected substances, being found in 12 and 16 samples, respectively. Maximum concentrations were found in benzoylecgonine (78.71 ng/L) and codeine (51.60 ng/L). Thirteen pharmaceuticals were found at 16 points. The most detected compounds were carbamazepine (15 samples) and ibuprofen (11 samples). Maximum concentrations were detected in acetaminophen (17,699.4 ng/L), ibuprofen (3913.7 ng/L) and codeine (434.0 ng/L). Spatial distribution of pharmaceuticals showed a clear relationship between irrigation areas, high population densities municipalities (above 1000 h/km2 ) and sewage water treatment plants. © 2013 Elsevier B.V. All rights reserved.

1. Introduction Emerging contaminants are any synthetic or naturally occurring chemicals or microorganisms not commonly monitored in the environment. Due to persistency and potential for harming the environment, biota and humans, their identification and quantification in environmental compartments is of research concern. Of the many emerging contaminants that might be detected [1],

∗ Corresponding author. Tel.: +34 963 42 41 62; fax: +34 963 42 41 60. E-mail addresses: [email protected], [email protected] (J. Pascual-Aguilar), [email protected] (V. Andreu), [email protected] (Y. Picó). 0304-3894/$ – see front matter © 2013 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.jhazmat.2013.07.052

pharmaceuticals and drugs of abuse can be seen as mainly originated in urban environments. Many of them are also identified in aquatic environments after treatment in sewage water treatment plants (SWPTs) [2,3], which in turn pose major threats to other environments through hydrological connectivity of landscapes. Research has addressed the development of methods to determine the occurrence of illicit drugs and their metabolites in either inflow or treated wastewaters. Most recent works focused on the use of liquid chromatography separation (LC) coupled with mass spectrometry (MS) detection [4]. Gas chromatography (GC) separation coupled with MS has also been used [5]. The environmental implications of emerging contaminants might also be considered. After treatment, sewage water will enter the water system again and subsequently be used for human

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Fig. 1. Location of the study area and sampling points setting. The study area, line in green, is located between two coastal alluvial plains (Rivers Turia and Júcar) on which a traditional irrigation system was constructed (larger area with land use-cover background map). Municipalities are depicted in dark grey, with numbers for name identification in the map legend. Black dots with their respective codes (PM14, P3, etc.) refer to sampling points for surface water collection and analysis. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

consumption or in productive activities including farming, before finally circulating as surface water and even continuing the water cycle underground. Although some works have studied the presence of both pharmaceuticals and illicit substances in rivers and open water systems after passing through urban agglomerations and sewage treatment plants [6], little research has analysed flow paths and water incorporation into permanent water bodies such as coastal lagoons. Despite the successful development of analytical methods to detect emerging contaminants and their identification in different environmental compartments such as surface waters [7], soils [8] and underground waters [9], little progress has been made in identifying transmission mechanisms between environments, particularly between those landscapes and water deposits connected

by hydrological flows, either natural (rivers) or artificial (irrigation canals and ditches). The aim of this work is the development of an integral methodology to evaluate the presence and spatial distribution of illicit drugs in surface waters. Mediterranean coastal wetlands are of great interest for their rich biodiversity, but they are also fragile and exposed to various human pressures such as farming systems [10] and urban sprawl [11] that alter their ecological and environmental conditions. The methodology was thus applied in the Natural Park of L’Albufera de Valencia to obtain background on how these substances travel from urban and agricultural systems to the protected area. The working hypothesis considers that there is continuity of water flows. Therefore, connectivity between different

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environmental compartments is established regardless their dominant land use. Connectivity mechanisms also affect to the transport of dissolved emerging contaminants, appearing in places where their presence is not expected. To this end, the objectives were: (1) to determine water paths from different environments (urban and agriculture); (2) to identify the mechanism that allows hydrological connectivity among distinct, apparently unrelated environments; and (3) to differentiate between areas according to rates of contaminants presence and concentration.

2. Materials and methods 2.1. Study area L’Albufera de Valencia Natural Park is located in the eastern Iberian peninsula (Fig. 1). The original wetland area was constructed in the large alluvial plain formed by the river Turia to the north and the Júcar to the south. The area presents a complex relationship between its intrinsic natural importance (endemic species and biodiversity) and human activities (traditional agriculture and hinterland industrial and settlement development). The current Natural Park covers 274.4 km2 , including its marine area. Due to secular alterations within its limits, a large proportion of the land is covered by rice fields, which occupy the primitive marshland, with only a few hectares still in their natural state [12]. In the continental margins of the Natural Park, intensive irrigated farming operations are also found. A shallow lagoon (23.7 km2 ) is located in the centre of the Natural Park. The hydrology combines a complex human management system and natural contributions, with water coming from the historic irrigation system as the main source of water inflows to the Natural Park. There is a very dense structure of overland artificial channels for irrigation, 59.7 km in length with a density of 323 m/km2 , with waters mainly coming from the rivers Jucar and Turia, which finally drains into the lake or directly to the sea. These water contributions, particularly those from rice fields, are considered to be almost 70% of the total waters circulating the Natural Park and draining into the lake [13], and crucial in the function of ecosystems and in the recharge and chemistry of underground waters. Water inflows also arrive from the lake’s own hydrographic basin, with an area of 917.1 km2 in both directions as groundwater sources within the limits of the Natural Park and from several ravines, the main ones being La Rambla de Poyo and La Rambla de Beniparrell. Other gullies end in ditches in the orchards and rice fields that flow into the L’Albufera. The Natural Park is surrounded by a densely populated hinterland, due to the influence of the City of Valencia and its metropolitan area. Major pressures come from the activities of a population of more than 1,200,000 inhabitants.

2.2. Methodology To obtain insight into the presence of emerging contaminants of urban origin and their spatial distribution in the agro-natural protected wetlands, an integral methodology relating different information sources was developed, based on environmental forensics criteria [14]. The procedure followed three main steps (Fig. 2) that allowed the integration of different information sources: existing tabular data (population census and sewage water treatment plants), existing geographical digital layers (municipal boundaries and irrigation networks) and fieldwork (water sampling at different points of the Natural Park). Some procedures were further processed to finally obtain spatial layers that were integrated into

Fig. 2. Methodological design to analyse presence of pharmaceuticals and illicit drugs in the protected natural park of L’Albufera wetlands. Organisation in three components is related to data collection and identification of information sources, conversion and integration into a spatial GIS environment and layers overlay analysis for the identification of sectors prone to presence of contaminants.

a common geographical information system (GIS) for subsequent analysis. 2.2.1. Emerging contaminants (drugs of abuse and pharmaceuticals) detection Sample points were selected to identify presence and concentrations of pharmaceutical and illicit drugs. Surface waters were collected at different points of the irrigation ditches in the traditional farming area to establish only spatial variations in their occurrence, without taking into account temporal ones. A total of 21 samples of water were collected, covering the most important channels that flow into the research area, following a monitoring pattern (Fig. 1 and Table 1): points PM14, P1, PP8, PP1W PM11, PM9, and A2M9 were located in the irrigation zone and network whose waters are originally harvested in the river Turia, and they are also connected to the major municipal areas to the north of the Natural Park, such as Valencia, Sedaví, Alfafar, Massanassa, and Catarroja. The other sampling points were located downstream of several populations, such as Albal, Beniparrell, Silla, Algemesí, Sollana, Sueca and Cullera, which also receive contributions from wastewater treatment plants and are connected to the irrigation system with waters harvested in the river Jucar. In this area some sampling sites are located outside the limits of the Natural Park. This is due to two main reasons: accessibility to the point (PP4 and PPW17) and representativeness of the larger irrigation system where ditches have a very dense connection structure (PM6, PM5 and P17). There were no rainfall events during the fortnight prior to the sampling, which took place on 3 and 4 March 2008. Water samples were taken in clean amber glass bottles (capacity 2.5 L) from the irrigation channels, typically at 30 cm depth, filled to the top to eliminate air bubbles and kept at 4 ◦ C until reaching the laboratory. For both types of substances a common method was developed, using solid-phase extraction (SPE) and liquid chromatography tandem mass spectrometry (LC–MS/MS). Water samples were then analysed for the simultaneous determination of 14 drugs of abuse [15] and 17 pharmaceuticals from different therapeutic classes [16]. For drugs, a Waters Sunfire C18 analytical column (150 mm × 4.6 mm, 3.5 ␮m) was used for SPE, with MeOH 0.1% formic acid (A) and water 30 mM ammonium formiate and formic acid at pH = 3.5 (B) as mobile phases. Illegal substances consisted of three cocainics (COC cocaine, BECG benzoylecgonine, ECGME ecgonine methyl ester), four amphetamine-like compounds (AMP amphetamine, MAMP methamphetamine,

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Table 1 Sampling point’s location (UTM coordinates) and land use. Point

Location (X–Y UTM coordinates: projection system ED50) X

PM14 P1 PP8 PP1W PW12 PM11 PM9 A2M9 PMW10 PPW17 PM6 P9 P10 P6 PM3 PM5 PP5 PM2 PP4 P17 P3

727,552 726,075 727,370 728,356 725,643 728,148 728,569 728,993 726,042 723,456 723,291 727,218 729,882 733,369 732,220 724,297 732,099 736,496 733,958 732,608 735,263

Land use (Crop type)

Y 4,365,696 4,363,858 4,363,732 4,364,084 4,362,901 4,362,713 4,361,851 4,361,054 4,361,228 4,358,129 4,351,431 4,352,961 4,354,048 4,349,981 4,349,031 4,348,945 4,347,868 4,342,582 4,342,024 4,341,610 4,341,561

MDA 3,4-methylenedioxy amphetamine, MDMA or ecstasy 3,4-methylenedioxy methamphetamine), two cannabinoids (THCCOOH 11-nor-9-carboxy-9-THC, THC 9-tetrahydrocannabinol) and five opiates (6ACMOR 6-acetylmorphine, COD codeine, HER heroine, MOR morphine, MET methadone). For the pharmaceuticals, Oasis HLB cartridges [poly (divinylbenzene-co-N-pyrrolidone)] preconditioned with 5 mL of methanol and 5 mL of Milli-Q water were used. The mobile phase was eluent A (formic acid 0.1% in methanol) and eluent B (formic acid 0.1% in water). Target pharmaceuticals for identification and quantification were oxytetracycline, tetracycline, ofloxacin, fenofibrate, ciprofloxacin, norfloxacin, codeine, trimethoprim, diazepam, metoprolol, propanolol, sulfamethoxazole, carbamazepine, acetaminophen, ibuprofen, clofibric acid and diclofenac. In both cases LC separation was performed using an Alliance 2695HPLC separation module from waters. A Sunfire C18 column (4.6 mm × 150 mm, 3.5 ␮m, from waters) and a Gemini C18 (4.0 mm × 2.0 mm) guard cartridge (Phenomenex, Torrance, CA,USA) were used. Tandem MS analyses were performed on a Micromass Quattro triple quadrupole mass spectrometer (Manchester, UK). Instrument control, data acquisition and evaluation were done with the Masslynx NT software (v. 3.4). 2.2.2. Spatial representation of anthropogenic pressures Spatial distribution of all information gathered was performed using GIS techniques with ARCGIS (V. 10.1). Information obtained by different means (socioeconomic census, fieldwork, new GIS layers) was integrated into a common framework that could explain the spatial representativeness of anthropogenic pressures on incoming surface waters of the Natural Park. Initial information consisted of: (1) tabular data with municipal statistical values on the number of inhabitants for the year 2008 provided by the Spanish Institute of Statistics; (2) a digitised map with municipal boundaries; (3) tabular descriptive information for SWTPs; (4) a digital layer of the traditional irrigation systems (drainage networks) as stated by Hermosilla Pla [17,18]; and (5) data from the analysis of the above mentioned 21 water samples. Population and derived population density records were incorporated as part of the associated database of the municipal boundaries layer. Tabular information describing SWTPs was

Rice Rice Rice Rice Rice Rice Rice Rice Rice Citrus Citrus Rice Rice Rice Rice Orchard Orchard Rice Rice Citrus Rice

geo-referenced as a point theme. Irrigation systems were generalised into a polygon theme of irrigated areas according to the water origins and another line layer with major irrigation channel distribution influent to the park. Water analysis results were georeferenced to be incorporated as a point layer in the GIS structure. Finally, to identify the presence of both emerging contaminant groups, both GIS layers and results from the illicit drugs determination were compared in the GIS environment and their spatial structure related to socio-environmental components. 3. Results and discussion 3.1. Emerging contaminants identification and presence Among the 17 pharmaceuticals screened in surface waters from the L’Albufera Natural Park, 13 (acetaminophen, carbamazepine, ciprofloxacin, codeine, diazepam, diclofenac, metoprolol, ofloxacin, propanolol, sulfamethoxazole, ibuprofen, clofibric acid and trimethoprim) were detected (Table 2); one of them (ciprofloxacin) was identified in very small concentrations, below the limits of determination (LOD). Tetracycline, oxytetracycline, norfloxacin and fenofibrate were not present in water samples. 16 (76%) water samples analysed were contaminated by pharmaceuticals. In these, carbamazepine was the substance most frequently detected (15 samples) with concentrations ranging up to 31.0 ng/L. The mean concentration was calculated by considering the non detected values as zero and those of samples less than the MQL as the MQL was 7.3 ng/L. A high presence of this drug was also reported by other researchers, with mean concentrations between 1 and 794 ng/L [19,20]. Acetaminophen and ibuprofen were detected with frequency closed to 50%, but at much higher mean concentrations of 860.3 ng/L and 207.7 ng/L, respectively. For ibuprofen, a significant removal in SWTPs is reported in the literature [21], and as a result of its low distribution constant value, the removal should be based on biodegradation. Sulfamethoxazole was detected in 43% of the samples at lower mean concentration than the previous ones of 19.5 ng/L. This frequency of positive samples and mean concentration is similar to those reported by other authors [19], but differs from a few studies that only found some traces below the MLQ [22,23]. Of the other pharmaceuticals, diclofenac and ofloxacin were found in 6 samples (29%), codeine, and propanolol in 5 (24%), ciprofloxacin, diazepam

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Table 2 Values obtained for pharmaceuticals in ng/L. Point

Oxytetracycline

Tetracycline

Ofloxacin

Fenofibrate

Ciprofloxacin

Norfloxacin

Codeine

Trimethoprim

Diazepam

PM14 P1 PP8 PP1W PW12 PM11 PM9 A2M9 PMW10 PPW17 PM6 P9 P10 P6 PM3 PM5 PP5 PM2 PP4 P17 P3

ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND

ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND

ND 49.3 34.3 ND ND ND
ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND

ND
ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND

ND 68.1 27.1 ND ND ND ND 34.7 ND
ND 53.6 ND ND ND ND ND 40.5 ND ND 32.5 ND ND ND ND ND ND ND ND ND ND

ND 5.6 4.6 ND ND ND ND 6.0 ND ND 6.3 ND ND ND ND ND ND ND ND ND ND

1.8 5.4

12 36

9.6 28.8

1.2 3.6

0.9 2.7

0.3 0.9

Limits of determination (LOD) and limits of quantification (LOQ) 9.4 10 8.1 LOD 28.2 30 24.3 LOQ Point

Metoprolol

Propanolol

Sulfamethoxazole

Carbamazepine

Acetaminophen

Ibuprofen

Clofibric acid

Diclofenac

PM14 P1 PP8 PP1W PW12 PM11 PM9 A2M9 PMW10 PPW17 PM6 P9 P10 P6 PM3 PM5 PP5 PM2 PP4 P17 P3

ND 5.8 ND ND ND ND ND 5.6 ND ND ND ND ND ND ND ND ND ND ND ND ND

ND 6.8 3.3 ND ND
10.7 139.0 18.9 ND 4.1 ND ND 144.0 ND ND 44.8 ND ND ND ND ND ND 17.4 24.1 6.3 ND

6.8 24.1 16.0 ND 2.2 15.3 10.3 31.0 ND
26.2 ND ND ND 14.9 ND ND 23.1

ND ND ND ND ND ND ND ND ND ND 71.4 ND ND ND 21.7 ND ND
ND 125.6 25.3 ND ND ND ND 57.6 ND ND 260.9 ND ND ND 42.6 ND ND ND ND 73.2 ND

0.6 1.8

0.9 2.7

4.8 14.4

1.5 4.5

2.5 7.5

Limits of determination (LOD) and limits of quantification (LOQ) 1.2 0.6 0.9 LOD 3.6 1.8 2.7 LOQ

and clofibric acid in 4 (19%), trimethoprim in 3 (14%) and metoprolol in 2 (9.5%) with lower mean concentrations. Out of the 14 illegal drug compounds, only five were not detected (MAMP, MDA, THC, 6-ACMOR and HER). Substance detection was also effective in 16 points (Table 3). This is the same number of total points as those found with pharmaceuticals. Of these, 14 points present both types of contaminants, pharmaceuticals and drugs of abuse (PM14, P1, PP8, PP1W, PW12, PM11, PM9, A2M9, PMW10, PPW17, PM6, P9, P10, P6, PM3, PM5, PP5, PM2 and PP4). In point P17, different concentrations of 6 pharmaceuticals were found and in point PP1W only presence of one drug of abuse was identified (BEGG). Average values of the 21 water samples were 0.28, 4.28, 0.07, 0.16, 0.22, 0.24, 8.46, 0.57 and 0.10 ng/L for COC, BECG, ECGME, AMP, MDMA, THC-COOHM, COD, MOR, and MET, respectively. As for pharmaceuticals, these values were obtained considering that samples with drug concentrations below LOQ were at the LOQ level, and that non detected (ND) concentration of a drug was zero.

The highest total concentrations of drugs of abuse and metabolites, above 78 ng/L, were found in PM 6. This sample also presented the largest number of drugs of abuse (COC, BECG, ECGME, AMP, MDMA, COD, MOR and MET). This could be due to the direct spillage of sewage water from different night clubs and discotheques of the zone into the channel where the sample was taken. The rest of the surface waters from agricultural fields around L’Albufera Natural Park presented total levels of the target analytes below 60 ng/L (most of them below 20 ng/L), showing a fairly constant occurrence of these contaminants in the area’s surface waters. In addition to PM6, six samples PM14 (COC, BEGG, THC-COOH and COD), P1, PM11 and A2M9 (COC, BEGG, MDMA, COD, and MET), PP8 (COC, BEGG, COD, and MET), and PPW17 (COC, BEGG, MDMA, MOR and MET) are markedly more contaminated by drugs than the rest. Of the total number of possible occurrence (294: 21 sample points by 14 compounds), in 51 cases (21%) drugs of abuse were detected. Cocainics (mainly COC and BEGG with concentrations ranging from 0.02 to 4.43 ng/L and 0.05 to 78.71 ng/L, respectively)

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Table 3 Values obtained for drugs of abuse in ng/L. Point

PM14 P1 PP8 PP1W PW12 PM11 PM9 A2M9 PMW10 PPW17 PM6 P9 P10 P6 PM3 PM5 PP5 PM2 PP4 P17 P3

Cocainics

Amphetamine-like compounds

Cannabinoids

Opiates

COC

BEGG

ECGME

AMP

MAMP

MDA

MDMA

THC-COOH

THC

6-ACMOR

COD

HER

MOR

MET

0.08 0.34 0.18 ND ND 0.16 ND
0.53 3.01 1.22
ND ND ND ND ND ND ND ND ND ND
ND ND ND ND ND ND ND ND ND ND 3.38 ND ND ND ND ND ND ND ND ND ND

ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND

ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND

ND

ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND

ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND

20.80 51.60 31.30 ND ND 20.10 ND 35.10 ND ND 18.69 ND ND ND ND ND ND ND ND ND ND

ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND

ND ND ND ND ND ND ND ND ND 0.30 11.70 ND ND ND ND ND ND ND ND ND ND

ND 0.69 0.14 ND ND
0.41 1.37

0.1 0.35

1.54 5.13

1.22 4.07

0.09 0.3

0.01 0.03

0.05 0.17

0.04 0.13

0.01 0.03

Limits of determination (LOD) and limits of quantification (LOQ) 0.02 0.05 0.41 0.12 0.22 LOD 0.06 0.15 1.37 0.4 0.75 LOQ

were detected in larger proportions than the rest of illicit substances in 29 cases (57%), followed by opiates COD, MOR and MET (14 cases, 27%). Amphetamine-like compounds were found on 7 occasions, while cannabinoids where only found in point PM14 as THC-COOH. The contamination pattern and concentration of illicit drugs observed in surface water is comparable to those reported in similar monitoring studies carried out in surface waters from other European Countries, such as Belgium [24,25], Italy ([26], Ireland ([27], United Kingdom [6], France ([28], Spain: in the Llobregat and Ebro river Basins, both located in Catalonia at the North of the study area; [29–31], Poland [32] and USA [7].

3.2. Spatial incidence of emerging contaminants Five irrigation sectors are found within the limits of the Natural Park (Figs. 3 and 4). Each of them had different water harvesting sources. From north to south, two sectors collect waters and build their irrigation structures from the river Turia, where two water dams are constructed (both are found inside municipalities with population densities between 1000 and 6000 h/km2 ). One sector takes waters from a higher section of the river and builds its irrigation area through two major ditches that flow from the right river side. Each one has an SWTP (TP1 and TP2) immediately close to their path. A second irrigation sector is constructed from the dam located at the lower river Turia section, driving two main canals from the left river bank. SWTPs TP4 and TP5 are located along their courses. A greater sector is built with waters harvested from river Júcar that contribute to the construction of most of the irrigated landscape of the study area, within which several SWTPs are scattered (TP9, TP10, TP11, TP12 and TP13). This is an area with much lower population densities, below 1000 h/km2 in most municipalities. The river Jucar irrigation sector also receives left over waters from the river Magro external system. The agricultural system is completed with a small sector whose main source of water is the lake, although underground waters are also supplied to the irrigation network. As only incoming waters from rivers were

examined in this study, samples from this small irrigation sector were not analysed. Pharmaceutical and drugs of abuse target compounds varied spatially. Pharmaceuticals were detected at higher concentrations at P1, PP8, PP4, PM6, A2M2 and PM11 (Table 2 and Fig. 3). The highest concentrations for 7 out of the 13 detected compounds in surface water were found at site PM6, not considering below LOQ values. This sample point is located near of the L’Albufera South SWTP TP10. However, the high presence of pollutants and values cannot be explained by the presence in the neighbourhood of the treatment plant, as it is not connected to the irrigation channels that collect the wastewater coming from the SWTP. This point is near an industrial area with different nightclubs, and the high level of pharmaceuticals could be due to the direct spillage of sewage water in the small irrigation channels. In contrast, samples from PM5, which is close to the system that drives the wastewater to the lake to maintain the ecological flow, do not show high concentrations of pharmaceuticals. The second group of points with high concentrations and frequency of pharmaceuticals were sites P1, PP8, PM11 and A2M2, this is a sector with very high population densities. In contrast, fewer substances and lower values were detected in the irrigation sector of points PM14 and PP1W. The influence of SWTPs TP2 and TP3 is evident for the sector, with water harvested from the higher section of the Turia River supporting a true interconnection between SWTP and the irrigation network by water poured into the ditch from sewage treatment plants. For the second sector, interconnection is less evident, suggesting that water is mainly driven to the sea rather than directed to the irrigation system, although treated water is poured into the ditch, as supported by site PM14. The river Júcar area has, in general, both a lesser number of compounds detected and lower concentrations, except for point PM6. Within the sector, higher values are found at sites PM3 and PP5, which have their irrigation network connected to SWTP TP13. Point PP17 presents a remarkable concentration of pharmaceuticals and, to a lesser degree, so does point PP4, although both sites are located near TP13 SWTP. However, it is not clear why these points show this distribution pattern. As they are located close to the city of Sueca, direct spill into irrigation canals might

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Fig. 3. Spatial significance of pharmaceuticals. The map is a graphic overlay of different layers of information: irrigation networks and their related sectors, including the original water harvesting point (arrow in grey colour); Ranges of the number of pharmaceutical compounds (circles in grey colour) and ranges of mean concentrations (circles in black) found at each sampling site, and location of SWTPs (triangles in black) with their respective identification codes (TP1, TP2, etc.).

be possible. Points P9, P10 and P6, in the north of the Júcar sector, and point P3, in the south, do not present any pharmaceutical as they are not inside irrigation networks connected to SWTPs. Spatial distribution of drugs of abuse follows a similar pattern to that of pharmaceuticals. Point PM6 was found to have the greatest number of substances (8 out of 14) and a higher concentration mean (8.68 ng/L). It is the only site where EGME and AMP were found, supporting the idea of uncontrolled direct spilling into the irrigation ditch. Links between the irrigation system and SWTPs are also corroborated in the two northern sectors whose waters are harvested from the river Turia. The presence and detection of illicit

compounds in the western irrigation area was more notable in sites P1, PP8, PW12, PM11, PM9 and A2M9 than in those located in the eastern part (sites PM14 and PP1W). Apart from point PM6, the remaining sites inside the agricultural zone irrigated with waters collected in the river Júcar show the same spatial pattern as for pharmaceuticals, with fewer compounds identified and in lower concentrations. Summarising, higher concentrations of the pharmaceuticals and drugs of abuse detected were mainly found in the sites located in ditches whose irrigation networks are connected to SWTP outflows. This distribution is reasonable because the main sources of these substances are effluents from sewage treatment plants.

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Fig. 4. Spatial significance of illicit drugs. The map is a graphic overlay of different information layers: irrigation networks and their related sectors, including the original water harvesting point (arrow in grey); Ranges of the number of illicit substances (circles in grey) and ranges of mean concentrations (circles in black) found at each sampling site, and location of SWTPs (triangles in black) with their respective identification codes (TP1, TP2, etc.).

This connection suggests a larger landscape and environmental compartments structure in which hydrological connectivity allows transport of non desirable substances. In a connectivity framework like this, contaminants will be released into the agricultural environment though the irrigation network (it could also be done by application of biosolids or other solid waste materials obtained from SWTPs) to soil, as stated by Saccà [33]. Contaminants may degrade and disappear with time, or else infiltrate and percolate into deep water layers [34]. The presence of emerging contaminants highlight the need to implement different treatments other than those conventionally

used in SWTPs, as the one reported by Cabeza et al. [34], with treatment of ultrafiltration reverse osmosis and UV disinfection. Once contaminated water enters the agricultural system, some dissemination mechanisms should be considered related to both human health and environmental risk. Persistence and accumulation on agricultural soils of the study area should be of major concern, because soils may have a storage capacity that would allow residence time and accumulation of contaminants when irrigated with waste waters [35]. Some compounds persist for months after irrigation, and accumulate in soil which, together with new supplies by incoming

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irrigation waters, will establish potential human exposure pathways through ingestion of food plants cultivated on land irrigated with waste waters [36]. Although it has been established values of plant uptakes of emerging contaminants, this kind of studies is very scarce and based on experimental trials [37] and/or indirect estimations [38]. One of the major concerns in the study area is the environmental impact produced in the Natural Park. So far very little is known on the ecotoxicology of emerging contaminants to wild species. Effects on biota may be related to the chemical properties of the contaminants. Exposure of Pimephales promelas results in reproductive disruption due to endocrine-active chemicals in the SWTP effluent [39]. Summarising, the health problems caused by the consumption of these compounds and the fact that most of these residues still have potent activities constitute a justifiable motive to presuppose that their regular presence in distinct hydrological and environmental compartments will have potential implications for human health and wildlife [26,40]. The regular presence of these substances in water samples could entail consequences for aquatic and terrestrial organisms, particularly in ecosystems (such as the study area) that are the last reservoirs of several autochthonous species and a key stopover point for migratory birds.

The spatial incidence and trend of contaminants refers to four patterns: (1) larger number of contaminants and higher concentrations detected, which will be in sectors with very high population densities and urban water from SWTPs linked to irrigation networks (P1, PP8, PM11, PM9 and A2M9); (2) sites with some contaminants in smaller concentrations detected that are linked to SWTPs in municipalities with lower population density (less than 500 h/km2 ); (3) sites that by their higher concentration and number of compounds detected may suggest direct spill into the irrigation network as suggested by PM6; and (4) sites without any compound detected and located in areas without connection between urban waters and the Natural Park (P9, P10 and P6). Effects on human health may be related to the accumulation and residence of contaminants on soils and waters. Human exposure should be produced by the creation of pathways [37] between irrigated soils with SWTPs effluents, food plants uptakes [38,39] and human consume. Despite the potential environmental impact, very little is known about the effects on aquatic organisms. The study constitutes and improvement of existing procedures mainly devoted to the detection of emerging. The connectivity analysis suggests the need of further monitoring to determine spatial and temporal patterns of contaminants, and to establish the consequences of persistent contaminants on human and environmental health.

4. Conclusions

Acknowledgements

Detection of emerging contaminants of urban origin in surface water applying multi-residue analytical methodology based on liquid chromatography–tandem mass spectrometry was effective for the identification of substances not commonly monitored in the environment, particularly in SWTPs where treatment of these chemicals is not considered. The application of a spatial analysis using environmental forensic procedures helps the identification of sectors with different presence of contaminants and the understanding of connectivity patterns between environments. Drugs of abuse were identified in a large proportion of the samples, up to 16 out of 21 sites. Concentrations were different between compounds and samples. They ranged from quantification limits to values above 50.00 ng/L (78.71 ng/L in sample PM6, and 51.60 ng/L in sample P1). Of the 14 compounds analysed, several were identified (cocainics COC, BEGG and ECGME, amphetaminelike compounds AMP and MDMA, cannabinoids THC-COOH, and opiates COD, MOR and MET). There is a marked trend in the use of substances, with cocainics the most detected (particularly BEGG and COC), followed by opiates. Substance concentrations obtained do not differ significantly from those found elsewhere [7,26,31]. A large number of pharmaceuticals (13 out of 17) were detected in surface waters. Of the 21 monitored sites, they were quantified in 16 points. Number of compounds and concentrations varies among sites. Higher amounts of analytes were found in PM6 (with a total of 12 compound), P1 and A2M9 (11 compounds) and PP8 (9 compounds). Trends in detected substances are also found, with carbamazepine, ibuprofen, acetaminophen and sulfamethoxazole the compounds most frequently detected (found in 15, 11, 10 and 9 samples, respectively). Results showed a wide range of concentrations with maximums of 17,699.4 ng/L for acetaminophen, 3913.7 ng/L for ibuprofen and 434.0 ng/L for codeine (all three in site PM6). Substances concentrations obtained do not differ significantly from those reported by other authors [19], although differences are found if compared to some studies [22,23]. As none of the samples were collected at the direct outflows of SWTPs, the presence of either drugs of abuse or pharmaceuticals indicates connections between hydrological compartments or water flow paths between environments.

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