Journal of Hazardous Materials 239240 (2012) 3239

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Journal of Hazardous Materials

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Monitoring the occurrence of emerging contaminants in treated wastewater and groundwater between 2008 and 2010. The Baix Llobregat (Barcelona, Spain)
Y. Cabeza a , L. Candela a, , D. Ronen b , G. Teijon a
Department of Geotechnical Engineering and Geoscience, Technical University of Catalonia-UPC, Gran Capitn s.n., 08034 Barcelona, Spain Ben-Gurion University of the Negev, J. Blaustein Institutes for Desert Research, Zuckerberg Institute for Water Research, Environmental Hydrology & Microbiology, Midreshet Ben-Gurion 84990, Israel
b a

a r t i c l e

i n f o

a b s t r a c t
The occurrence of 166 emerging compounds and four heavy metals (Cd, Ni, Hg and Pb) in treated wastewater and groundwater has been monitored at the Llobregat delta (Barcelona, Spain) over a period of 3 years. Selected compounds were pharmaceuticals, personal care products (PCPs), dioxins, polycyclic aromatic hydrocarbons (PAHs) and priority substances included in the 2008/105/CE Directive. Analysis was performed in tertiary treated wastewater (TWW), after an additional treatment of ultraltration reverse osmosis and UV disinfection, and groundwater from a deep conned aquifer. This aquifer is articially recharged with TWW through injection wells. After the advanced treatment, 38 pharmaceuticals, 9 PCPs, 9 pesticides and 7 PAHs still showed a frequency of detection higher than 25% in the TWW, although at low concentration levels (ng/l). Not all active compounds found in the TWW were present in groundwater, indicating possible degradation within the aquifer media after the injection. A number of chemicals, mainly 10 pesticides and 10 pharmaceuticals were only present in groundwater samples, conrming a different origin than the injected TWW, probably agricultural activities and/or inltration of poorly treated wastewater. 2012 Elsevier B.V. All rights reserved.

Article history: Available online 27 July 2012 Keywords: Emerging contaminants Groundwater Treated wastewater Monitoring

1. Introduction Since 1990 the chemical contamination of water resources by emerging contaminants is a matter of growing concern [15]. The pollutants considered as emerging contaminants between many others include drugs (e.g., antibiotics, painkillers), diagnosis products (e.g., X-ray contrast agents), steroids and hormones, antiseptics, personal care products (PCPs; e.g., sun screening agents and fragrances), petrol additives, surfactants, endocrine disruptors and pharmaceuticals. Although they are not routinely monitored due to lack of regulatory requirements, and high analytical costs, their presence has been reported in surface waters [[68], www.epa.gov/ppcp/lit.html] and to a lesser extent in groundwater [[912], http://ca.water.usgs.gov/gama/]. Pharmaceuticals are one of the most widely studied pollutants; less information has been obtained on the presence of other emerging contaminants. The largest contributing sources of emerging contaminants to aquatic environments are sewage efuents from wastewater treatment plants, as some of the contaminants are known to persist through the wastewater treatment process in an almost unaltered form [13,14]. Additionally, surface and groundwater

contamination may result from untreated urban water discharges and leakage from sanitary sewers and septic systems [15]. Recent studies have shown a decrease in the concentration of emerging contaminants when sewage efuents inltrate through surface spreading basins or river banks [10,16]. The objective of this study was to disclose during 20082010 the presence of 166 emerging contaminants (PCPs, pesticides, pharmaceuticals, polycyclic aromatic hydrocarbons-PAH and dioxins), priority substances in the 2008/105/EC Directive, and four heavy metals, in: (a) municipal treated wastewater (TWW) of the Depurbaix wastewater facility (tertiary treatment followed by ultraltration, reverse osmosis and UV disinfection), and (b) groundwater of the conned aquifer of the Llobregat river delta (Barcelona, Spain), articially recharged with the TWW. 2. Wastewater facility and study site The Depurbaix wastewater facility and recharge works are located in the Llobregat delta, approximately 10 km southwest of Barcelona, Spain (Fig. 1). The wastewater reclamation plant was placed in operation in October 2006 and serves a population of approximately 1,000,000 people. After primary elimination of sand and grease, and activated biological sludge treatment with nutrient removal, the tertiary treatment consists of occulationcoagulation and lamellar clarication followed by

Corresponding author. E-mail address: lucila.candela@upc.edu (L. Candela). 0304-3894/$ see front matter 2012 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.jhazmat.2012.07.032

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Fig. 1. The Llobregat delta study area location and schematic cross-section. Sampling and monitoring network: P1P4, TWW injection wells; Mp-47 and B-7-b piezometers; RL1RL6 monitoring wells.

ltration and UV disinfection. The additional treatment consists of ultraltration, reverse osmosis and UV disinfection [17]. The Llobregat delta, an unconsolidated geologic formation of quaternary age, is underlined by two superimposed aquifers composed of detritic sediments varying from clay to gravel and covering an area of 97 km2 . From the geologic point of view deposits are characterized by their complex heterogeneity and complex relationships among the different sedimentary units. A silt wedge of low permeability, which extends from the central part of the delta, and thickens in the seaward direction, separates the aquifers and connes the lower one, being the bedrock impervious blue clay of Pliocene age (Fig. 1). At the inland boundary of the delta the silt wedge pinches out and the two aquifers are hydraulically connected by ne sand layers. Both aquifers constitute a strategic water supply source and have been monitored since the 1960s [1820]; however, water quality of the surcial aquifer in many areas shows unsuitable levels of contaminants for any purpose. The lower conned aquifer, where TWW-recharge takes place, is composed of gravels and ne sands, has a thickness of 1030 m and extends below the delta surface and under the sea below the silt wedge. The deepest part for the top of the aquifer is 60 m below the sea level. Regional groundwater ow is to the Mediterranean Sea. Aquifer recharge is by rain and river inltration in the river valley. However, leakage from sewer systems, supply networks and damaged or deteriorated wells connecting the upper-polluted and deep aquifer can be signicant [18]. Since 1970 seawater intrusion was detected in several areas of this aquifer, as a consequence of intensive groundwater exploitation, and in 1977 the groundwater piezometric surface was up to 30 m below sea level. In an attempt to control seawater intrusion, a positive hydraulic barrier (a pressure ridge along the coast) was developed in 2007 injecting TWW from the Depurbaix facility [17,21]. During this rst

phase four 70 m deep injection wells (P1P4, Fig. 1) were drilled in the conned aquifer. The wells were located at 300 m intervals and at a distance of 1500 m from the seashore. TWW was injected through the wells at a depth of approximately 60 m. The initial injected amount increased from 620 to 2500 m3 /day (March 2008) in wells P1P3. Well P4 was discarded due to technical reasons. Groundwater was sampled from wells and piezometers pertaining to the Agencia Catalana de lAigua-ACA deep aquifer monitoring network. For this specic study, selected observation wells were those located between 4 and 800 m from the injection wells, namely two piezometers (B-7-b and Mp-47) and six monitoring wells (RL1RL6; Fig. 1). Fig. 1 depicts a schematic section of the hydraulic barrier, where injection and monitoring wells are shown. See reference [15] for more detailed information on the sampling network and the Depurbaix sewage treatment plant. 3. Materials and methods 3.1. Sample collection and preparation From January 2008 to May 2010 water samples were taken from the four TWW injection wells, the two piezometers and the 6 monitoring wells for physico-chemical (147 samples) and microbiological (17 samples) characterization and the analysis of emerging contaminants (121 samples). For the analysis of major ions, physico-chemical parameters (pH, temperature, electric conductivity (EC), total dissolved solids (TDS) and total organic carbon content (TOC)) and microbiological determinations (Escherichia coli and total coliforms), monthly water samples were collected in 500 ml low density polyethylene (PE-LD) bottles. For the analysis of emerging contaminants, samples were collected on a bimonthly basis in 1 l amber glass bottles with Teon

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coated taps. For the analysis of heavy metals, water samples were acidied in situ with 3% HNO3 , ltered with 0.45 m (Millipore ) and stored in PE-LD bottles. All samples were immediately stored in an insulated ice container and sent to the laboratory for analysis. Transit time for sample shipment was less than 24 h. 3.2. Analysis of emerging contaminants and heavy metals A total of 166 emerging contaminants were analyzed: 82 pharmaceuticals (e.g., analgesic/anti-inammatory drugs, antibiotics, lipid regulating agents), 18 personal care products (sunscreen agents, fragrances, disinfectant/antiseptics), 18 polyaromatic hydrocarbons and dioxins, 42 pesticides with different chemical active compounds, 19 of them considered as priority pollutants,

and 6 volatile priority pollutants. Heavy metals included Cd, Ni, Pb and Hg that are priority metals according to the 2008/105/EC Directive. The emerging contaminants and heavy metals were selected based on: (a) their metabolic routes; (b) their wide use as household products; (c) their inclusion as priority substances in the 2008/105/EC Directive on environmental quality, and (d) literature results from previous studies. All contaminants monitored during the study period are presented in Table 1. Due to technical reasons, PCPs and heavy metals are reported for 2008 only. Heavy metals were analyzed by inductive coupled plasma-mass spectrometry (ICP-MS). Emerging contaminants were analyzed by liquid chromatography, MS and gas chromatography, according to the compounds chemical properties as reported in Table 1.

Table 1 List of analyzed compounds and analytical methods applied. Group 1: liquid chromatography Q-TRAP-mass spectrometry (1) Pharmaceuticals Personal care products Pesticides Atrazinea , chlorfenvinfosa , chlorpyriphos-methyl, chlorpyriphos-ethyla , diurona , isoproturona , simazinea .

Biphenylol, chlorophene. 4-Amino-antipyrine (4-AA), 4-dimethyl aminoantipyrine (4-DAA), 4-MAA, acetaminophen, amitriptyline, amoxicillin, antipyrine, atenolol, azithromycin, bezabrate, caffeine, caffeine c13, carb. epoxide, carbamazepine, cefotaxime, ciprooxacin, citalopram, clarithromycin, clobric acid, clomipramine, clotrimazole, codeine, cotinine, cyclophosphamide, diatrizoate, diazepan, diclofenac, erythromycin, famotidine, fenobrate, fenobric acid, fenoprofen, uoxethine, furosemide, gembrozil, hydrochlorothiazide, ibuprofen, ifosfamide, indomethacine, iopamidol, iopromide, ketoprofen, ketorolac, lansoprazole, lincomycin, loratadine, mefenamic acid, mepivacaine, methylprednisolone 6-alpha sodium succinate (urbason), metoprolol, metronidazole, mevastatin, N-acetyl-4-amino-antipyrine (4-AAA), nadolol, naproxen, N-formyl-4-amino-antipyrine (4-FAA), nicotine, noroxacin, ooxacin, omeprazole, paraxanthine, paroxethine, phenacethin, pravastatin, primidone, propanolol hydrochloride, propyphenazone, ranitidine, salbutamol, salicylic acid, simvastatin, sotalol sulfadiazine, sulfamethazine, sulfamethoxazole, sulfapyridine, sulfathiazole, tamoxifen, terbutaline, tetracycline, trimethoprim, venlafaxine. Group II: gas chromatographymass spectrometry/mass spectrometry (2) Personal care products (PPCs) 2,7/2,8-Dichloro-dibenzo-p-dioxin, 3-(4-methylbenzylidene)camphor, benzophenone-3, BHT, celestolide, ethylhexyl methoxycinnamate, galaxolide, musk ketone, musk xylene, octocrylene, octyl-triazone, phantolide, TCPP, tonalide, traseolide, triclosan. PAHs and dioxins

Pesticides 4,4-DDE, 4,4-DDT, aldrin, alpha-endosulfana , ametryn, atrazin desethyl, beta-endosulfana , deltametrin, diazinon, dieldrin, endosulfan sulphatea , endrin, ethion, heptachlor, iprodion, isodrin, metoxychlor, oxyuorfen, parathion ethyl, parathion methyl, procymidone, propazine, terbutrin, terbutylazine.

2.3,7,8-Tetrachloro-dibenzo-p-dioxin, acenafthene, acenaphtylene, anthracenea , benzo(b)uoranthenea , benzo(a)anthracene, benzo(a)uoranthene, benzo(a)pyrenea , benzo(k)uoranthenea , benzo(ghi)perylene, chrysene, dibenzo(a,h)anthracene, uoranthene, uorene, naphthalenea , phenanthrenea pyrene. Group III: gas chromatographyhigh resolution-mass spectrometry (3) Pesticides priority pollutants Hexachloro-1,3-butadieneb , hexachlorobenzeneb , pentachlorobenzeneb , alfa-hexachlorocyclohexaneb , beta-hexachlorocyclohexaneb , gamma-hexachlorocyclohexane (lindane)b , delta-hexachlorohexaneb , alachlorb . Group IV: Inductively Coupled Plasma Mass Spectrometry (ICP-MS) (4) Heavy metals Cadmiumb , leadb , nickelb , mercuryb . Volatile priority pollutants

1,2,3-Trichlorobenzeneb , 1,2,4-trichlorobenzeneb , 1,3,5-trichlorobenzeneb , tetra-brominated diphenyl etherb , penta-brominated diphenyl etherb , hepta-brominated diphenyl etherb .

a Priority pollutants: (1) column: C-18 (3 mm 250 mm, 5m particle size); interface polarity: ESI (+) and ESI (); mobile phase: ESI (+), water (formic acid 0.1%)/ACN ESI (), water (0.05% ammonium formate)/ACN; operation mode MRM and (2) column: HP-5ms (5% diphenyl 95% dimethylsiloxane); operation mode: MS or MS/MS. b Priority pollutants: (3) column: ZB-5ms; operation mode: high-resolution selected ion recording (HR/SIR) and (4) RF power: 1500 W; plasma gas ow: 15 l/min; Nebulizer gas ow: 1 l/min; auxiliary gas ow: 0.9 l/min; sample uptake rate: 0.25 ml/min.

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3.3. Regulated chemicals and in situ chemical analysis In situ analysis included pH, EC, redox potential (Eh), dissolved oxygen and temperature. These determinations were performed using an Eijelkamp 18.28. The analysis of regulated chemicals, major ions and physico-chemical characteristics were performed following standard techniques [22].

4. Results and discussion 4.1. General All sampled waters were of sodium chloride type, with Cl concentration between 131 and 617 mg/l and Na+ concentration between 74 and 374 mg/l. From a microbiological perspective, E. coli presence was always below the detection level and total coliforms were only sporadically found in three wells (between <1 and 102 cfu/l), indicating low levels of microbial contamination. For the TWW samples, pH values ranged between 6.9 and 7.8 and TOC between <1 and 8.9 mg/l. In the deep conned aquifer the pH of groundwater is between 6.4 and 8.2. TOC reduction was observed in samples from wells RL-1RL-4 (Fig. 1). Results of all sampling campaigns show that 117 out of the 170 target compounds were detected in any type of sampled water, always at concentrations levels in the nanogram per liter range; 61 pharmaceuticals, 12 PCPs, 3 metals, 27 pesticides (16 of them priority pollutants) and 11 PAHs and dioxins (5 of them priority pollutants) were present at least in one water sample (TWW or groundwater) at their level of detection (LOD). Previous results of TWW analysis at the study site showed that (a) the tertiary treatment removed contaminants from 2.5% (e.g., galaxolide) to 100% (e.g., ibuprofen) and (b) after additional treatment, the majority of the analytes showed a concentration reduction below 0.1 g/l, and some of them were totally removed [15]. Similar reductive patterns have also been conrmed by other studies [2326]. It is important to stress that (a) 96 compounds were detected at least once in samples of TWW, and (b) one PCP (3-(4-methylbenzylidene)camphor); 10 pesticides (isoproturon, chlorotoluron, triuralin, atrazine, delta-HCH, alachlor, heptachlor, parathion ethyl, chlorfenvinfos A and metoxychlor); one volatile pollutant (1,2,3-TCB) and one PAH (benzo(ghi)perylene) were only detected in groundwater samples. Seven of them are included in the EC Directive list (Table 1). With regard to compounds found in both TWW and groundwater, they account for 91 chemicals, classied as 49 pharmaceuticals, 9 PCPs, 17 pesticides (10 included in the 2008/105/EC Directive), 10 PAHs, dioxins (5 included in the 2008/105/EC list) and 3 metals. The concentration of all compounds was always higher in TWW. The frequency of detection ranged between 3% and 90%, and even higher for nicotine, galaxolide (musk fragrance), ethylhexyl methoxycinnamate and octocrylene (ingredients of sunscreens), tonalide (synthetic fragrance), pentachlorobenzene (intermediate in the manufacture of pesticides), uorene (precursor of uorene compounds), hexachlorobenzene (fungicide), phenanthrene (dyestuffs and synthesis of drugs), chloropyrifos ethyl and pyrene (pesticides). Fig. 2 presents a summary of the compounds with a frequency of detection greater than 25%. Pharmaceuticals, the largest group being analyzed, are the most detected with 18 compounds, while PCPs present the highest frequency of detection (greater than 70%). In general terms their presence in water samples may be related to high consumption, as caffeine; persistence in the aquatic media (e.g., chlorpyrifos, pesticide), and percentage of unchanged compound (e.g., hydrochlorotiazide, diuretic; www.ema.europa.eu/docs/en GB/document../WC500033644.pdf)

Fig. 2. Compounds with a frequency of detection higher than 25% in both TWW and groundwater.

Fig. 3 presents the 34 compounds detected at concentration greater than 0.1 g/l in TWW and groundwater. Due to the absence of regulated limits for this type of compounds, the concentration of 0.1 g/l has been considered as a threshold value in this study. Table 2 presents CAS (Chemical Abstract Service) number and use of compounds of Fig. 3. 4.2. Results according to group of classes 4.2.1. Pharmaceuticals Pharmaceuticals were the most frequently detected group in both TWW and groundwater (Fig. 2), having the highest concentrations among all microcontaminants. For the 20082010 period, 24 compounds show concentration greater than 0.1 g/l in at least one sample in any type of water (Fig. 3). The most commonly detected compounds of this group (frequency of detection >25% in groundwater and TWW) are stimulants, anesthetics, diuretics, antibiotics, and analgesics probably associated to their widespread and frequent use. Note that many of them are non-prescription drugs. Pharmaceuticals presenting the highest concentrations in TWW are gembrozil (lipid-regulating agent, 716 ng/l), and diclofenac (anti-inammatory, 678 ng/l). For groundwater, iopromide (contrast agent) and gembrozil are the compounds with the highest detected concentration (687 and 852 ng/l, respectively). Four pharmaceuticals that were detected in the injected TWW, acetaminophen (paracetamol, analgesic and antipyretic), ranitidine (stomach protector), amitriptyline (antidepressant) and

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Fig. 3. Detected compounds at concentration higher than 0.1 g/l in at least one sample (20082010 period).

azithromycin (antibiotic) were not found in groundwater over the three years monitoring period. Ten pharmaceuticals: 4-AA, 4-MAA (metabolite of dipyrone), codeine (analgesic), ibuprofen (anti-inammatory), iopamidol and iopromide (X-ray contrast agents), ketorolac (nonsteroidal

anti-inammatory), loratadine (long-acting antihistamine), paraxanthine (metabolite of caffeine) and pravastatin (lipid-regulating agent), were only present in groundwater and not in the TWW samples. This observation suggests that the presence of these chemicals in groundwater is related to other sources of contamination rather

Table 2 CAS number and type of use for detected compounds shown in Fig. 3. Compound (ng/l) Atenolol Caffeine Carbamazepine Ciprooxacin Codeine Diazepam Diclofenac Erythromycin Furosemide Gembrozil Hydrochlorothiazide Ibuprofen Iopamidol Iopromide Mepivacaine N-acetyl-4-amino-antipyrine (4-AAA) Naproxen N-formyl-4-amino-antipyrine (4-FAA) Nicotine Ooxacin Paraxanthine Sulfamethazine Sulfamethoxazole Sulfapyridine Velafaxime BHT Ethylhexyl methoxycinnamate Galaxolide TCPP Atrazinea Diurona Chlorfenvinfos Ba
a

CAS number 29122-68-7 58-08-2 298-46-4 85721-33-1 76-57-3 439-14-5 15307-86-5 114-07-8 54-31-9 25812-30-0 58-93-5 15687-27-1 62883-00-5 73334-07-3 96-88-8 83-15-8 22204-53-1 1672-58-8 54-555-5 82419-36-1 611-59-6 57-68-1 723-46-6 144-83-2 93413-69-5 128-37-0 5466-77-3 1222-05-5 14609-54-2 93616-39-8 330-54-1 470-90-6

Use Cardioselective beta-adrenergic blocker Central nervous system stimulant Anticonvulsant Antibacterial agent Analgesic agent Sedative, anxiety-relieving and muscle-relaxing (Valium) Anti-inammatory agent Antibacterial agent Diuretic Lipid-regulating agent Diuretic Anti-inammatory agent with analgesic properties Contrast agent Contrast agent Local anesthetic Metabolite of metamizol Anti-inammatory agent with analgesic and antipyretic properties Metabolite of metamizol Insecticide, tobacco ingredient Antibacterial agent Psychoactive central nervous system stimulant. Metabolite of caffeine Antibacterial agent Antibacterial agent Antibacterial agent used to treat certain skin diseases Antidepressant Antioxidant Sunscreening agent Musk fragrance Flame retardant Herbicide Herbicide Pesticide

Priority pollutants (2008/105/EC)

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than injected TWW. Only codeine, ibuprofen, iopamidol, iopromide and paranxanthine were found at concentration greater than 0.1 g/l, the selected threshold concentration in this study. Compounds only detected in groundwater may be the result of poorly treated wastewater that inltrated into the aquifer through its inland lateral boundaries where the deep aquifer outcrops, through river banks or through wells interconnecting the upper polluted aquifer with the lower one. Isotopic data for tracing aquifer recharge has revealed absence of Tritium in some groundwater samples, which indicates water recharge prior to 1952, when thermonuclear testing took place. 4.2.2. PCPs, PAHs, dioxins and pesticides Analytical results of personal care products (PCPs) were only available for 2008. Out of the 18 analyzed compounds (Table 1), 10 were present in TWW at least once: benzophenone3 (anti-aging), BHT (antioxidant), ethylhexyl methoxycinnamate (sunscreen), galaxolide (fragrance), musks phantolide and musk ketone, octocrylene (sunscreen), tonalide (musk) and TCPP (ame retardant). With regard to groundwater, 3-(4-methylbenzylidene) camphor and all components detected in TWW except musk phantolide and ketone were detected at least once. Considering a frequency of detection between 70% and 100% (Fig. 2), benzophenone-3, BHT, ethylhexyl methoxycinnamate, galaxolide, octocrylene, tonalide and TCPP are the most detected compounds in all sampled waters. Regarding concentration levels, four PCPs: BHT, ethylhexyl methoxycinnamate, galaxolide and TCPP, with a concentration higher than 0.1 g/l, were detected in at least one sample of water. Mean concentration values ranged from 9.5 ng/l (ethylhexyl methoxycinnamate) to 213 ng/l (BHT) in TWW and from 29.38 ng/l (TCPP) to 133.41 ng/l (BHT) in groundwater. These results suggest that the detected compounds are persistent and ubiquitous in groundwater and TWW. Because some of them show strogenic action [27] additional research and monitoring is needed. With regard to pesticides 17 were detected in TWW, and 27 compounds of different group of classes (mainly insecticides and herbicides) in groundwater. It is suggested that the pesticides detected in groundwater only, are the result of intensive agriculture activity in the area [18]. The most detected (>25%) active compounds in both water types were diuron (a non-selective urea derivative pesticide), hexachlorobenzene (fungicide), terbutylazine (herbicide), chloropyrifos ethyl (insecticide, acaricide) and oxiuorfen (herbicide), as shown in Fig. 2. Only 3 priority pollutants have been found at concentrations higher than the dened threshold value: atrazine (2105.68 ng/l only in groundwater), diuron (0.27155 ng/l) and chlorfenvinfos B (0145 ng/l, only in groundwater). The only PAHs being found in more than 25% of the analyzed samples were uorene, phenanthrene, pyrene and benzo(k) uoranthene, always at concentrations of nanogram per liter. Dioxins have not been detected in any sample. 4.2.3. Metals Only Ni and Pb were found at concentration levels of g/l in both types of water with a frequency higher than 25%. Mean values ranged between 0.36 and 0.45 g/l for Cd and 28.2 and 12.1 g/l for Ni in TWW and groundwater, respectively. Both Ni and Pb were found at concentrations above the maximum allowable concentration according to the 2008/105/EC Directive of priority substances. 4.3. Time evolution of microcontaminants in groundwater The evolution of the total concentration of pharmaceuticals and pesticides in groundwater and TWW versus time (from June 2008 to July 2010) has been plotted in Fig. 4 in an attempt to assess the effect of TWW injection into the aquifer. As could be expected,

Fig. 4. Evolution of pharmaceuticals (a) and pesticides (b) along the 3 years study period in injected TWW and groundwater.

the concentrations in monitoring well Mp47 and injection well P1 (located 4 m one from the other; Fig. 1), present a similar trend that clearly shows the injected water contribution for both, pesticides and pharmaceuticals for the available sampling period (till July 2009). For the rest of the monitoring wells the increase in the concentration of compounds is related to the distance from the injection source and the physico-chemical and transport characteristics of the aquifer media. The mean values for individual compounds in groundwater (average for wells R1R6) and TWW during the monitoring period are summarized in Table 3. Only one sampling campaign was available for TWW in 2010. Selected chemicals are those presenting concentration values higher than the threshold value (Fig. 3) and with a frequency of detection higher than 25% in both types of waters (Fig. 2). The concentration trend of compounds in TWW varies widely over the monitoring period of 2 years, ranging between a maximum value for gembrozil, and a minimum one for sulfamethoxazole. The presence of the compounds and their concentrations maybe related to their pattern of consumption; the existence of seasonal variations has not been observed. With regard to the concentration of pharmaceuticals in groundwater, and taking as background values the concentrations observed in 2008, an increase is observed for bezabrate, carbamazepine, cotinine, diclofenac, furosemide, 4-AAA, 4-FAA, sulfamethazine and sulfamethoxazole. No signicant changes are observed for antipyrine, hydrochlorothiazide, mepivacaine, nicotine, primidone, propyphenazone and venlafaxime while

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Table 3 Time evolution of detected compounds in TWW and groundwater over the study period (mean concentration). 2008 Compounds Antipyrine Atenolol Bezabrate Caffeine Carb. epoxide Carbamazepine Ciprooxacin Cotinine Diazepam Diclofenac Erythromycin Furosemide Gembrozil Hydrochlorothiazide Iopamidol Mepivacaine N-acetyl-4-amino-antipyrine (4-AAA) Naproxen N-formyl-4-amino-antipyrine (4-FAA) Nicotine Ooxacin Primidone Propyphenazone Salicylic acid Sulfamethazine Sulfamethoxazole Sulfapyridine Venlafaxine Benzophenone-3 BHT Ethylhexyl methoxycinnamate Galaxolide Octocrylene TCPP Tonalide Fluorene Pyrene Benzo(k)uoranthenea 1,2,4-TCBa Atrazinea Chlorfenvinfos Ba Chloropyrifos-ethyl Diurona Hexachlorobenzenea Oxyuorfen Phenantrene Terbutylazine Nia Cda Pba
a b

2009 Groundwater 7 17 1.42 55.5 7.25 23.88 323.75 6.66 8 15 154.33 15.5 46.57 6 4.5 62.33 145 63.2 55.4 6 26 5.66 6.55 23.16 9 21.33 7.23 134.78 35.31 42.9 8.42 23.95 7.5 3.16 11.21 1.34 1.62 5.29 5 1.6 1.93 5.19 11.51 11.48 0.46 2.44 TWW 14 90.33 35 56.66 10 74.25 37.5 44.25 263.5 24 88.33 368 158.5 152.5 400.75 118 312.25 83 169 44.5 10.75 4 74.33 65.25 36.5 147.25 UD UD UD UD UD UD UD 3.58 23.52 0.85 1.79 2 1.71 18.69 58.33 1.04 5.5 16.56 37.06 UD UD UD Groundwater 4.33 5 3.44 16.83 62.4 64.5 10.11 8.28 55 8 63 8.42 113.25 88.88 18.42 27.62 3.33 83.9 37.8 19 2 UD UD UD UD UD UD UD 2.36 15.01 0.37 1.37 61.11 145 8.54 16.75 1.22 2.89 11.16 5.66 UD UD UD

2010 TWWb 8 218 32 12 10 10 34 11 100 39 88 266 49 402 265 25 158 53 7 3 65 21 176 UD UD UD UD UD UD UD 0.83 5.53 4.29 4.27 2.78 2.83 1.6 UD UD UD Groundwater 6.88 5 4.22 10 33.66 34.66 14 18.33 3.88 44.3 17 20.75 4.83 119.6 98.75 50 20.37 6 9.3 68.5 46 16.5 UD UD UD UD UD UD UD 0.77 3.98 4.44 0.67 3.31 0.31 3.68 1.82 UD UD UD

TWW 9 86.5 22.5 40.5 11.75 107 52 31.75 41.5 60.5 32.5 61.66 79.5 186.25 30.5 172 261.75 137.25 18.66 341 62.5 16 6 38 102.25 54 119 8 213 9.5 61 2.5 76.5 37.5 1.93 9 0.43 1.25 7.11 28.69 1.46 3.64 5.39 53.75 28.2 0.36 2.73

Priority pollutants (2008/105/EC). Only one sample; , under detection limit; UD, unavailable data. All values in ng/l except metals in g/l. Samples from Mp-47 and RL6 not considered.

a decreasing trend in concentration is observed for the rest (20 chemicals). Only two pesticides, hexachlorobenzene and pentachlorobenzene, present an increasing concentration trend while the concentration of the other pesticides decreases along time. 5. Conclusions The results of this study suggest that regardless of the advanced wastewater treatment not all contaminants are totally removed from TWW. 98 out of the 170 analyzed are still detected although at low concentrations (generally below 0.1 g/l) and for pharmaceuticals, values are below concentrations considered to be a therapeutic dose. Not all active compounds found in TWW are also detected in groundwater, indicating possible degradation and dilution processes in the aquifer media. On the other hand, presence of

compounds only detected in groundwater, as for example ibuprofen, totally removed after the tertiary treatment, or codeine, is probably related to the inltration of insufciently treated wastewater or leakages of urban origin in the recharge area of the aquifer. The simultaneous occurrence of pharmaceuticals and pesticides only in groundwater strengthens this hypothesis. Pharmaceuticals are the most detected group of contaminants (considering both frequency and concentration) in TWW and groundwater, since they are excreted by the human body (between 90% and 10% of the intake dose), because of their persistence, high consumption inefcient removal and rate of transformation, like caffeine, nicotine, carbamazepine (anti-epileptic drug), diazepan (sedative), bezabrate or 4-AAA and 4-FAA (metabolites of metamizol, a known analgesic). Since these types of compounds are used intensively and without prescription, quantitative data on consumption amounts is not available.

Y. Cabeza et al. / Journal of Hazardous Materials 239240 (2012) 3239

39

PCPs constitute an important group of chemicals with a frequency of detection greater than 75% over the studied period. They are persistent and they show a small removal rate. Obtained results reect a monitoring period of 1 year only and further studies on their occurrence and fate are needed. As for the pesticides, seven of the analyzed compounds show a high frequency of detection in TWW and groundwater due to low removal and high persistence in the aquifer media. Their origin is linked to their wide use in the agricultural area of the delta, highly developed until the 70s, prior to the control and protection measures implementation provided in the corresponding legal decree. According to the existing regulations, groundwater at the study site met drinking water standards albeit TWW recharge. However, as the risk of pollution by chemicals are of critical importance for the future safety of the aquifer, it is important to continue the monitoring of groundwater quality. The results of this study can help to identify the chemicals for future follow-up based on their frequency of detection or concentration level in both TWW and groundwater. Acknowledgments We acknowledge the Spanish Ministry of Science and Innovation (Projects CONSOLIDER-TRAGUA and CGL2010-22168-C03) for its nancial support. Furthermore, we thank the Comunitat dUsuaris dAiges del Delta del Llobregat, the Agencia Catalana del lAigua and the Universitat Autnoma de Barcelona for the sampling campaigns cooperation. Heavy metals and emerging contaminants were analyzed by the Pesticide Residue Research Group of the University of Almera and the Department of Physical and Analytical Chemistry of the University of Jan. Microbiological determinations were performed by the Universitat Autnoma de Barcelona. References
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