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8 Páginas.-- 4 Figuras.-- 3 Tablas, The effect of graphene oxide on the anaerobic digestion of waste activated sludge was investigated at two graphene oxide concentrations (0.025 and 0.075 g graphene oxide per g volatile solids) using biochemical methane potential tests. The occurrence of 36 pharmaceuticals was monitored in the solid and liquid phases before and after the anaerobic treatment. The addition of graphene oxide improved the removal of most pharmaceuticals detected, even those that are considered persistent to biological degradation, such as azithromycin, carbamazepine, and diclofenac. No significant differences were observed in the final specific methane production without graphene oxide and with the lowest graphene oxide concentration, yet the highest graphene oxide concentration partially inhibited methane production. The relative abundance of antibiotic resistance genes was not affected by the graphene oxide addition. Finally, significant changes in the microbial community including bacteria and archaea were detected with graphene oxide addition., This research is funded by AEI (Agencia Estatal de Investigación, Spanish Government) through project ANTARES (PID 2019-110346RB-C22). O. Casabella acknowledges funding from the Secretariat of Universities and Research from Generalitat de Catalunya and the European Social Fund for his FI fellowship (2022 FI_B1 00122). M. Gros acknowledges her Ramon y Cajal contract (RYC 2020-030324-I) funded by the MCIN/AEI 10.13039/501100011033 and by “ESF Investing in your future”. The authors acknowledge the support from the Economy and Knowledge Department of the Catalan Government through a Consolidated Research Group (ICRA-TECH - 2021 SGR 01283) and (SGR ICRA-ENV 2021 01282).

In this study, a comprehensive suspect screening of organic micropollutants (MPs), and some of their transformation products (TPs) and metabolites, was performed in waste, river and coastal waters from the Ebro Delta region (Catalonia, Spain). For this purpose, an automated suspect screening workflow was developed using two analytical steps: (i) identification of suspected compounds using on-line databases; and (ii) semi-quantification of identified compounds by using isotopic labelled standards. Using this strategy, several pollutants were identified comprising pharmaceuticals, pesticides, abused substances, personal care products, industrial chemicals and surfactants of major relevance in Catalonia. Additionally, their occurrence was evaluated along the wastewater-recipient water chain until they reach estuaries and the Mediterranean Sea. The most ecologically relevant compounds detected, that could be considered as suitable markers of wastewater contamination in freshwater and coastal ecosystems, were highlighted. Results reveal that some suspected TPs and metabolites were more ubiquitous than their parent compound and found at similar concentration levels. These results evidence that suspect screening methodologies can be a useful tool for the identification of relevant markers of wastewater contamination.

This study investigates the occurrence, transport, and risks associated to antibiotic residues, antibiotic resistance genes (ARGs) and antibiotic resistant Escherichia coli (AR-E. coli) in eleven natural springs in an agroecosystem environment with intense livestock production, where groundwater nitrate concentration usually sets above 50 mg L

The fate and degradation of 28 multiple-class veterinary pharmaceuticals in an on-farm pig slurry treatment plant based on solid-liquid separation and a nitrification-denitrification (NDN) sequence batch reactor (SBR) were evaluated for the first time. The pharmaceuticals detected at the highest concentrations in raw pig slurries belonged to the group of tetracycline antibiotics. Fluoroquinolone, lincosamide and pleuromutilin antibiotics and other drugs such as flubendazole and flunixin were also frequently detected. After solid-liquid separation, target compounds were distributed in an average of 64% onto the liquid fraction. Pharmaceuticals distributed in this fraction were removed in an average of almost 50% after being treated in NDN-SBR. Lincomycin was the compound with the highest removal percentage, reaching 100% reduction, while tetracyclines and fluoroquinolones showed moderate removal percentages (50 and 40%, respectively). Regarding nitrogen removal, NDN-SBR reduced a 77% of the content of this nutrient in the liquid slurry fraction.

The occurrence of veterinary antibiotics and hydro-chemical parameters in eleven natural springs in a livestock production area is evaluated, jointly with the characterization of their DOM fingerprint by Orbitrap HRMS. Tetracycline and sulfonamide antibiotics were ubiquitous in all sites, and they were detected at low ng L−1 concentrations, except for doxycycline, that was present at μg L−1 in one location. DOM analysis revealed that most molecular formulas were CHO compounds (49 %–68 %), with a remarkable percentage containing nitrogen and sulphur (16 %–23 % and 11 %–24 %, respectively). Major DOM components were phenolic and highly unsaturated compounds (~90 %), typical for soil-derived organic matter, while approximately 11 % were unsaturated aliphatic, suggesting that springs may be susceptible to anthropogenic contamination sources. Comparing the DOM fingerprint among sites, the spring showing the most different profile was the one with surface water interaction and characterized by having lower CHO and higher CHOS formulas and aliphatic compounds. Correlations between antibiotics and DOM showed that tetracyclines positively correlate with unsaturated oxygen-rich substances, while sulfonamides relate with aliphatic and unsaturated oxygen-poor compounds. This indicates that the fate of different antibiotics will be controlled by the type of DOM present in groundwater This work was funded by the EU Marie Sklodowska Curie Actions through the project number 750104, and the Spanish Ministry of Science and Innovation through the project PACE-IMPACT (FEDER-MCIU-AEI/CGL 2017-87216-C4-4-R). The authors also acknowledge Generalitat de Catalunya through the Consolidated Research Group (SGR ICRA-ENV 2017 1124) and the funding from CERCA program. N. Catalán received funding from the EU Marie Sklodowska Curie Actions grant agreement Nº. 839709. M.J. Farré acknowledges her Ramón y Cajal fellowship (RyC-2015-17108) from the Spanish Ministry of Science, Innovation and Universities, AEI-MICIU

This study investigates the effect of psychrophilic, mesophilic and thermophilic temperatures on the anaerobic treatment of slaughterhouse wastewater, in terms of biogas production, occurrence of 30 pharmaceutical compounds of veterinary use, 4 antibiotic resistance genes (ARGs) which provide resistance to tetracyclines (tetW), fluoroquinolones (qnrS), macrolide-lincosamide-streptogramin (ermB) and sulfonamides (sul1) antibiotics, as well as class I integron-integrase gene (intI1), related to horizontal gene transfer. The highest methane yield was obtained at a mesophilic temperature (35 °C) (323 mL CH4/g TCOD) followed by the yield obtained at thermophilic temperature (53 °C) (242 mL CH4/g TCOD). Regarding pharmaceuticals, chlortetracycline, oxytetracycline, tilmicosin, and lincomycin were the most abundant in the slaughterhouse wastewater, being detected predominantly in the solid phase (with median concentrations >200 μg/kg dry weight). On the other hand, ciprofloxacin, ofloxacin, norfloxacin, lincomycin and ibuprofen were the most predominant in the anaerobic digestate regardless of the treatment temperature. Psychrophilic temperatures (21 °C) exhibited moderate to low pharmaceuticals removal, while a large fraction of them were removed at a thermophilic temperature reaching 70–90% removals for tetracycline, macrolides and one sulfonamide (sulfapyridine) S. Zahedi acknowledges the funding received from the Spanish Ministry of Science and Innovation (MICINN) (IJCI-2017-33248). This study was supported by the Spanish Government (Ministerio de Ciencia e Innovación, project PID2019-110346RB-C22). The authors acknowledge the support from the Economy and Knowledge Department of the Catalan Government through a Consolidated Research Group (ICRA-TECH - 2017 SGR 1318) and (SGR ICRA-ENV 2017 1124).

In the present paper, the mesophilic (35 °C) and thermophilic (55 °C) biomethanization of poultry and cattle manures were investigated using biochemical methane potential (BMP) tests. Specific methane production (SMP), 24 pharmaceutical compounds (PhACs), and five antibiotic resistance genes (ARGs) (bla

The effect of anaerobic treatment of swine manure at 35 °C (mesophilic) and 55 °C (thermophilic) on methane production, microbial community and contaminants of emerging concern was investigated. Pasteurization pretreatment and post treatment was also investigated in combination with anaerobic treatment at 35 °C. Specific methane production (SMP), 26 pharmaceutical compounds (PhACs) and five antibiotic resistance genes (ARGs) (qnrS, tetW, ermB, sul1 and blaTEM) were evaluated. Mesophilic treatment resulted in the highest SMP regardless of whether pasteurization was applied. Marbofloxacin was the most abundant antibiotic in swine manure. In general, all groups of PhACs showed higher removals under thermophilic temperatures as compared to mesophilic. In general, pasteurization pretreatment followed by mesophilic anaerobic digestion provided the highest removals of ARGs. Finally, the genera Streptococcus, Clostridium and Pseudomonas which contain pathogenic species, were present in the swine manure. Streptococcus, which was the most abundant, was decreased during all the treatments, while the others only decreased under certain treatments S. Zahedi acknowledges the funding received from the Spanish Ministry of Science and Innovation (MICINN) (IJCI-2017-33248). This study was supported by the Spanish Government (Ministerio de Ciencia e Innovación, project PID2019- 110346RB-C22). The authors acknowledge the support from the Economy and Knowledge Department of the Catalan Government through a Consolidated Research Group (ICRA-TECH - 2017 SGR 1318) and (SGR ICRA-ENV 2017 1124). ICRA researchers also acknowledge the funding from CERCA program

A suspect screening methodology was developed for the fast and reliable identification of 360 contaminants of emerging concern (CECs) of anthropogenic origin in the vulnerable area of the Ebro Delta (Catalonia, Spain) and to track for potential contamination sources. The suspect screening methodology was combined with a risk assessment approach to prioritize the most ecologically relevant CECs. Out of the 360 suspects, 37 compounds were tentatively identified, 22 of which were fully confirmed using isotopically labelled standards. The detected suspect compounds included pesticides, pharmaceuticals, personal care products, stimulants and their metabolites. Pesticides were more ubiquitous in irrigation and drainage channels, while pharmaceuticals, stimulants, and personal care products were the most common in effluent wastewaters, in the receiving freshwater systems as well as in the marine environment. Ten compounds were found to be of high ecological concern, including the pharmaceuticals telmisartan, venlafaxine, and carbamazepine, the herbicides terbuthylazine, desethylterbuthylazine, and terbutryn, the fungicides azoxystrobin, tebuconazole and prochloraz and the insecticide tebufenozide. These compounds could be used as markers of anthropogenic contamination in riverine and coastal ecosystems. UCR::Vicerrectoría de Investigación::Unidades de Investigación::Ciencias Básicas::Centro en Investigación en Contaminación Ambiental (CICA)

The fate and transport of 34 veterinary pharmaceuticals (PhACs) is investigated in swine slurry and dairy cattle manure-amended agricultural soils, from an experimental field site, by using both analytical and modelled data. Potential differences on PhACs fate, attributed to the application of distinct swine slurry fractions (total, solid, and liquid), are herein assessed for the first time. Surface and deep soil layers, up to a depth of 120 cm, were analyzed at different periods after an annual fertilization event. Using input data representing typical agricultural soil conditions and the PhACs concentration measured in organic fertilizers the transport of these pollutants was modelled for a period of 10 years, including the monitored annual fertilization event. Fluoroquinolone, tetracycline and pleuromutilin antibiotics, together with anti-helmintics and analgesic and anti-inflammatories, were detected in manure-amended soils, at average concentrations ranging from 0.078 to 150 μg/kg dw in surface layers, with the highest levels found in the fields fertilized with the swine slurry solid fraction. Even though severe disagreements were observed between experimental and simulated PhACs concentrations along the soil column, both approaches pointed out that target compounds strongly adsorb onto surface layers, showing limited mobility along the soil profile. Thus, repeated manure and slurry fertilizations will contribute in building up persistent PhACs residues in the uppermost layers of the soil, while leaching will be a minor process governing their fate towards the subsurface. The ecotoxicological risks posed by the occurrence of PhACs in soils were estimated to be low for terrestrial organisms. Nevertheless the antibiotic enrofloxacin showed some potential to induce negative effects to crops This work has been supported by the Secretary of Universities and Research of the Counsel of Economy and Knowledge of the Catalan Government (AGAUR) and the COFUND Program of the Marie Curie Actions of the 7th R&D EU Program. It has also been supported by the projects PERSIST (EU Water Joint Programming Initiative, JPIW2013-118) and REMEDIATION (CGL2014-57215-C4-2-R), and the University of Girona funds MPCUdG2016/061. Authors also acknowledge the support from the Economy and Knowledge Department of the Catalan Government through Consolidated Research Group (ICRA-ENV 2017 SGR 1124)

Sewage sludge reuse will become crucial for the sustainability of agriculture, given the increasing population and the lack of essential nutrients for crop growth. Nevertheless, this practice raises some concerns, due to the large amounts of contaminants of emerging concern (CECs) present in sewage sludge, including pharmaceuticals and personal care products (PPCPs), microplastics (MPs), engineered nanomaterials (ENMs), per- and polyfluoroalkyl substances (PFASs), flame retardants, plasticizers, metals, antibiotic resistance bacteria (ARB) and resistance genes (ARGs). These CECs may adversely affect the environment and, ultimately, human health through the consumption of crops grown under sludge-amended soils. This chapter reviews the potential environmental and human health risks associated with sewage sludge reuse in agriculture, by focusing on relevant classes of CECs, such as PPCPs, MPs, carbon-based ENMs and considering ARBs and ARGs, a topic so far poorly addressed. The risks discussed focus on the contamination of aquatic and terrestrial ecosystems and on CECs uptake by crops intended for human consumption. Finally, technological strategies to improve sludge treatment, and thus minimize such risks, are briefly discussed.

This study is the first attempt to quantify environmental fluxes per capita of organic contaminants discharged from on-site sewage treatment facilities (OSSFs) in affected recipients. Five sites were monitored around the River Fyris in Sweden: three mainly affected by OSSFs and two mainly affected by municipal sewage treatment plants (STPs). Gas chromatography-mass spectrometry was used to determine environmental concentrations of 30 anthropogenic contaminants, including organophosphorus compounds, rubber and plastic additives, UV stabilizers, fragrances, surfactant ingredients and polycyclic aromatic hydrocarbons. Uni- and multivariate statistical analysis of the most frequently detected contaminants showed that median fluxes per capita of tris(1,3-dichloro-2-propyl) phosphate, tris(1-chloro-2-propyl) phosphate, tris(2-chloroethyl) phosphate, and n-butylbenzene sulfonamide were similar at OSSF and STP sites, but the mass fluxes per capita of tris-(2-butoxyethyl) phosphate, 2-(methylthio)benzothiazole, and galaxolide, were significantly lower (∼2-3-fold) at OSSF sites than at STP sites (Mann-Whitney, α = 0.05). Differences between these sites were larger in samples collected in summer and autumn than in samples collected in winter. Deviations likely originated from differences in fate processes and distances between source and sampling sites. Further studies are needed to characterize mass fluxes per capita of contaminants in waters that directly receive discharges from OSSFs.

Antibiotics are an increasing focus of interest due to their high detection frequency in the environment. However, their presence in water bodies is not regulated by environmental policies. This field study investigates, for the first time, the occurrence, behavior and fate of a selection of 53 antibiotics, including up to 10 chemical groups, in an alluvial aquifer originated from manure application in an agricultural region using hydrogeological, hydrochemical and isotopic approaches. Up to 11 antibiotics were found in groundwater corresponding to 4 different chemical groups: fluoroquinolones, macrolides, quinolones and sulfonamides. In surface water, only 5 different antibiotics from 2 chemical groups: fluoroquinolones and sulfonamides, were quantified. The most frequent antibiotics were sulfamethoxazole and ciprofloxacin. Concentrations of antibiotics were in the order of ng/L, with maximum concentrations of 300 ng/L in groundwater. Hydrochemistry and isotopic data and geostatistics confirmed the spatial trend observed for nitrates, where nitrate concentrations tend to be higher in the margin areas of the study area, and lower concentrations are found nearby the river. On the other hand, no clear continuous spatial concentration trend of antibiotics was observed in the aquifer, supported by the short spatial correlation found in the variograms. This indicates that the physical-chemical properties and processes of each antibiotic (mainly, sorption and degradation), and other environmental issues, such as a patchy diffuse input and the manure antibiotic content itself, play an important role in their spatial distribution in groundwater. A discussion on the estimation of the antibiotic sorption parameter reveals the difficulties of describing such phenomena. Furthermore, retardation factors will extend over several orders of magnitude, which highly affects the movement of individual antibiotics within the aquifer. To summarize, this study points out the difficulties associated with antibiotic research in groundwater in order to define water resources quality management strategies and environmental regulations

This study investigated the potential of biochar filters as a replacement or complement for sand filters for removal of pharmaceutically active compounds (PhACs) from wastewater in onsite sewage facilities (OSSF). Specifically, the study investigated the effects of biodegradation, adsorption and a combination of these processes on removal of four model PhACs from wastewater in biochar filters operated under hydraulic loading conditions mimicking those found in onsite infiltration beds. Concentrations and removal of the four PhACs (i.e. carbamazepine, metoprolol, ranitidine and caffeine) were investigated over 22 weeks in four treatments: biochar (BC) with active or inactive biofilm (BC-active-biofilm, BC-inactive-biofilm), biochar without biofilm (BC-no-biofilm) and sand with active biofilm (Sand-active-biofilm). The adsorption of carbamazepine was high in BC-no-biofilm (99% removal after 22 weeks), while biodegradation was very low in Sand-active-biofilm (7% removal after 22 weeks). Removal of carbamazepine in BC-active-biofilm was high and stable over the 22 weeks (> 98%), showing a significant role of biofilm in filter biogeneration. However, carbamazepine removal declined over time in BC-inactive-biofilm, from 99% in week 13 to 73% in week 22. Metoprolol was poorly degraded in Sand-active-biofilm (37% after 22 weeks), while adsorption seemed to be the major pathway for removal of metoprolol in biochar. Ranitidine and caffeine were efficiently removed by either adsorption (97% and 98%, respectively, after 22 weeks) or biodegradation (99% and > 99%, respectively, after 22 weeks). In conclusion, biochar is a promising filter medium for OSSF, especially for persistent PhACs such as carbamazepine and metoprolol.

One of the main risks associated with effluents from both wastewater treatment plants (WWTPs) and on-site sewage treatment facilities (OSSFs) is the release of micropollutants (MPs) in receiving water bodies. However, the impact of MPs present in the effluents of OSSFs in the aquatic environment has not been studied so far. The current study evaluates the impact of the effluents of OSSFs and small-to-large scale WWTPs on natural waters. The discharge of 74 MPs was assessed including pharmaceuticals, personal care products, pesticides, artificial sweeteners and perfluoroalkyl substances (PFASs). The sampling was carried out within a Swedish catchment and included three sites that are exclusively affected by OSSFs and other sites that are mainly affected by WWTPs or a mixture of sources (7 sites, 28 samples). Results show that although OSSFs serve a much smaller total number of people, the MPs emitted from OSSFs reached the aquatic environment in significant quantities (concentrations of > 150 ng L − 1 of ∑ MPs). The composition profiles for sites affected by WWTPs were similar and were dominated by sucralose (27% of the ∑ MPs), caffeine (27% of the ∑ MPs), lamotrigine (10% of the ∑ MPs), desvenlafaxine (5% of the ∑ MPs), and diclofenac (4% of the ∑ MPs). In contrast, the sites affected by OSSFs showed high variability, exhibiting a different profile from those affected by WWTPs and also from each other, demonstrating that OSSFs are not homogeneous sources of MPs. Some specific compounds, such as diethyltoluamide (DEET) and caffeine, were proportionally much more important at sites affected by OSSFs than at sites affected by WWTPs (representing a much higher percentage of the ∑ MPs in the OSSFs). In contrast, PFASs did not show high concentration variation among the different sampling sites and the composition profiles were relatively similar, indicating that these substances follow different routes of entry into the aquatic environment.

This study evaluated the occurrence and distribution of 81 pharmaceutically active compounds (PhACs) in the vulnerable area of the Ebro Delta region (Catalonia, Spain), to assess the environmental impact of wastewater treatment plants discharge to coastal environments. The occurrence of PhACs was followed along the wastewater-recipient water-sediment chain until they reach estuaries and the Mediterranean Sea. Water and sediment samples were collected in an integrated way at different sampling points covering three different seasons in reaches of the Ebro River located upstream and downstream from wastewater treatment plants (WWTPs), surrounding channels, estuaries, and the associated receiving seawater. 28 out of the 57 compounds detected in effluent wastewater were positively identified in estuary and seawaters, revealing that WWTP discharges are an important source of contamination in coastal environments and that PhACs are suitable markers of urban contamination in these areas. The substances with the highest frequency of detection belonged to the groups of analgesics/anti-inflammatories (acetaminophen, salicylic acid), antihypertensives (valsartan), psychiatric drugs (carbamazepine), and antibiotics (clarithromycin, trimethoprim). In general, a decrease in concentration was observed from inland sampling points towards the Mediterranean Sea, resulting from a dilution in the recipient marine water bodies. A reduced number of PhACs, at concentrations ranging from 0.1 to 12.5 ng g−1 dry weight (d.w.) was detected in sediment samples, indicating that sorption is a minor natural attenuation pathway for these compounds. Finally, a prioritization strategy, based on the compounds concentration and frequency of detection in seawater, removal efficiency in WWTP, bioaccumulation potential, toxicity to marine organisms and persistency, was used to highlight the PhACs of major ecological concern and that could be used as relevant indicators of wastewater contamination in coastal environments., This work was supported by the Spanish Ministry of Economy and Competitiveness, Goverment of Spain, through the project TransformCoast (CGL-2014-56530-C4-4-R). Authors acknowledge the support from the Economy and Knowledge Department of the Catalan Government through Consolidated Research Group (ICRA-ENV 2017 SGR 1124) and Water and Soil Quality Unit (2017 SGR 1404). M. Celic acknowledges her grant received from the Spanish Ministry of Economy and Competitiveness (BES-2015-072297).

Much progress has been made in the past few decades in understanding the sources, transport, fate, and biological effects of contaminants of emerging concern (CECs) in aquatic ecosystems. Despite these advancements, significant obstacles still prevent comprehensive assessments of the environmental risks associated with the presence of CECs. Many of these obstacles center around the extrapolation of effects of single chemicals observed in the laboratory or effects found in individual organisms or species in the field to impacts of multiple stressors on aquatic food webs. In the present review, we identify 5 challenges that must be addressed to promote studies of CECs from singular exposure events to multispecies aquatic food web interactions. There needs to be: 1) more detailed information on the complexity of mixtures of CECs in the aquatic environment, 2) a greater understanding of the sublethal effects of CECs on a wide range of aquatic organisms, 3) an ascertaining of the biological consequences of variable duration CEC exposures within and across generations in aquatic species, 4) a linkage of multiple stressors with CEC exposure in aquatic systems, and 5) a documenting of the trophic consequences of CEC exposure across aquatic food webs. We examine the current literature to show how these challenges can be addressed to fill knowledge gaps. Environ Toxicol Chem 2019;38:46–60, Funding for the present review was provided by the US Geological Survey Oregon Water Science Center, and the US Geological Survey Toxic Substances Hydrology Program. H.L. Schoenfuss received support from the Great Lakes Restoration Initiative through the US Fish and Wildlife Service CEC team, as well as additional funding from a National Science Foundation grant (CBET 1336062).

Made available in DSpace on 2021-06-25T11:06:44Z (GMT). No. of bitstreams: 0 Previous issue date: 2021-03-20 Centres de Recerca de Catalunya Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) Generalitat de Catalunya This work evaluated for the first time the sustainability of vinasse reuse as a fertilizer in sugarcane crops by assessing the occurrence of organic contaminants and their potential for dissemination to soils and groundwater in fertigated areas. A comprehensive screening of organic contaminants was performed in vinasse, soil and groundwater using target analysis, to investigate the occurrence of multiple-class antibiotics, in combination with suspect screening using NORMAN Digital Sample Freezing Platform. Even though antibiotics are used in the ethanol production process and were expected to be ubiquitous contaminants, they were not detected in any of the samples. Nevertheless, the HRMS-based wide-scope suspect screening (including >7800 substances such as pharmaceuticals, agrochemicals, preservatives and industrial chemicals) allowed the tentative identification of 56 compounds, mostly pesticides, food additives, industrial and naturally occurring substances. Results showed no overlap between the compounds detected in vinasse and environmental samples, suggesting that the pollutants found in soil and groundwater might come from alternative sources other than vinasse reuse. São Paulo State University (Unesp) Institute of Chemistry São Paulo State University (Unesp) Bioenergy Research Institute (IPBEN) Catalan Institution for Research and Advanced Studies (ICREA) Catalan Institute for Water Research (ICRA), Emili Grahit 101 University of Girona São Paulo State University (Unesp) Institute of Chemistry São Paulo State University (Unesp) Bioenergy Research Institute (IPBEN) FAPESP: 2016/06352-4 FAPESP: 2018/15739-5 Generalitat de Catalunya: SGR ICRA-ENV 2017 1124

The present study is the first comprehensive monitoring of 13 selected endocrine disrupting compounds (EDCs) in untreated urban and industrial wastewater in Serbia to assess their impact on the Danube River basin and associated freshwaters used as sources for drinking water production in the area. Results showed that natural and synthetic estrogens were present in surface and wastewater at concentrations ranging from 0.1 to 64.8 ng L−1. Nevertheless, they were not detected in drinking water. For alkylphenols concentrations ranged from 1.1 to 78.3 ng L−1 in wastewater and from 0.1 to 37.2 ng L−1 in surface water, while in drinking water concentrations varied from 0.4 to 7.9 ng L−1. Bisphenol A (BPA) was the most abundant compound in all water types, with frequencies of detection ranging from 57% in drinking water, to 70% in surface and 84% in wastewater. Potential environmental risks were characterized by calculating the risk quotients (RQs) and the estrogenic activity of EDCs in waste, surface and drinking water samples, as an indicator of their potential detrimental effects. RQ values of estrone (E1) and estradiol (E2) were the highest, exceeding the threshold value of 1 in 60% of wastewater samples, while in surface water E1 displayed potential risks in only two samples. Total estrogenic activity (EEQt) surpassed the threshold of 1 ng E2 L−1 in about 67% of wastewater samples, and in 3 surface water samples. In drinking water, EEQt was below 1 ng L−1 in all samples.

This study investigated, for the first time, the occurrence and fate of 29 multiple-class pharmaceuticals (PhACs) in two source separated sanitation systems based on: (i) batch experiments for the anaerobic digestion (AD) of fecal sludge under mesophilic (37 °C) and thermophilic (52 °C) conditions, and (ii) a full-scale blackwater treatment plant using wet composting and sanitation with urea addition. Results revealed high concentrations of PhACs in raw fecal sludge and blackwater samples, with concentrations up to hundreds of μg L−1 and μg kg−1 dry weight (dw) in liquid and solid fractions, respectively. For mesophilic and thermophilic treatments in the batch experiments, average PhACs removal rates of 31% and 45%, respectively, were observed. The average removal efficiency was slightly better for the full-scale blackwater treatment, with 49% average removal, and few compounds, such as atenolol, valsartan and hydrochlorothiazide, showed almost complete degradation. In the AD treatments, no significant differences were observed between mesophilic and thermophilic conditions. For the full-scale blackwater treatment, the aerobic wet composting step proved to be the most efficient in PhACs reduction, while urea addition had an almost negligible effect for most PhACs, except for citalopram, venlafaxine, oxazepam, valsartan and atorvastatin, for which minor reductions (on average 25%) were observed. Even though both treatment systems reduced initial PhACs loads considerably, significant PhAC concentrations remained in the treated effluents, indicating that fecal sludge and blackwater fertilizations could be a relevant vector for dissemination of PhACs into agricultural fields and thus the environment.

This study evaluated the chronic impact and biodegradability of sulfamethoxazole under anaerobic conditions. For this purpose, a lab-scale anaerobic sequencing batch reactor was operated in a sequence of different phases with gradually increasing sulfamethoxazole doses of 1 to 45 mg/L. Conventional parameters, such as COD, VFA, and methane generation, were monitored with corresponding antimicrobial concentrations in the reactor and the methanogenic activity of the sludge. The results revealed that anaerobic treatment was suitable for pharmaceutical industry wastewater with concentrations of up to 40 mg/L of sulfamethoxazole. Higher levels exerted toxic effects on the microbial community under anaerobic conditions, causing the inhibition of substrate/COD utilization and biogas generation and leading to a total collapse of the reactor. The adverse long-term impact was quite variable for fermentative bacteria and methanogenic achaea fractions of the microbial community based on changes inflicted on the composition of the residual organic substrate and mRNA expression of the key enzymes.

This paper describes a stability study performed for 56 antibiotics belonging to 9 different groups - macrolides, tetracyclines, fluoroquinolones, quinolones, penicillins, cephalosporines, lincosamides, sulfonamides and nitroimidazole antibiotics - in purified water samples fortified with the selected compounds at 10. ng/ml. For this purpose, three different sample preservation modes were tested with the aim of avoiding biotic and abiotic degradation: (i) storage at -20. °C, (ii) storage at -20. °C with 0.1% of EDTA and (iii) pre-concentration in a solid phase extraction cartridge (SPE), which was afterwards stored at -20. °C. Concentrations of antibiotics in the samples preserved using the different protocols were monitored after 0, 1, 2 and 12 weeks. The results showed that, for the accurate determination of all compounds they should be analyzed right after sampling. However, if this is not possible, most of the antibiotics can be analyzed within the 1st week after sampling and preservation at -20. °C (with or without EDTA) or in a SPE cartridges at -20. °C. Nonetheless, some antibiotics found extensively in the environment, such as sulfamethoxazole, ciprofloxacin, ofloxacin, erythromycin, azithromycin and clarithromycin exhibited low stability after 1 week preservation and, therefore, they should be analyzed within this time

This paper describes the degradation of the X-ray contrast agent iopromide (IOP) and the antibiotic ofloxacin (OFLOX) by the white-rot-fungus Trametes versicolor. Batch studies in synthetic medium revealed that between 60 and 80% of IOP and OFLOX were removed when spiked at approximately 12 mg L−1 and 10 mg L−1, respectively. A significant number of transformation products (TPs) were identified for both pharmaceuticals, confirming their degradation. IOP TPs were attributed to two principal reactions: (i) sequential deiodination of the aromatic ring and (ii) N-dealkylation of the amide at the hydroxylated side chain of the molecule. On the other hand, OFLOX transformation products were attributed mainly to the oxidation, hydroxylation and cleavage of the piperazine ring. Experiments in 10 L-bioreactor with fungal biomass fluidized by air pulses operated in batch achieved high percentage of degradation of IOP and OFLOX when load with sterile (87% IOP, 98.5% OFLOX) and unsterile (65.4% IOP, 99% OFLOX) hospital wastewater (HWW) at their real concentration (μg L−1 level). Some of the most relevant IOP and OFLOX TPs identified in synthetic medium were also detected in bioreactor samples. Acute toxicity tests indicated a reduction of the toxicity in the final culture broth from both experiments in synthetic medium and in batch bioreactor.

This study investigated, for the first time, the distribution and fate of 28 multiple-class veterinary pharmaceuticals and antibiotics (PhACs), and their corresponding antibiotic resistance genes (ARGs), in a full-scale on-farm livestock waste treatment plant. The plant relies on several technologies, including: anaerobic digestion (AD), solid-liquid separation, and two stages reverse osmosis (RO) of the liquid digestate. Tetracycline, fluoroquinolone, lincosamide and pleuromutilin antibiotics, together with anti-helmintic (flubendazole) and anti-inflammatory (flunixin) drugs were the most frequently detected compounds in livestock waste and in slaughterhouse sludge. This last fraction is used as co-substrate in the AD process and showed to be an important input source of PhACs and ARGs. In terms of treatment performance, AD exhibited moderate to low PhACs and ARGs reduction, while a large fraction (50%) of the PhACs present in the digestate were distributed onto the solid fraction, after solid-liquid separation. Both solid and liquid digestates had relatively high copy numbers of ARGs. Finally, RO showed high rejection percentages for all PhACs (90%), with concentrations in the low ng L

The present work describes the development of a fast and robust analytical method for the determination of 53 antibiotic residues, covering various chemical groups and some of their metabolites, in environmental matrices that are considered important sources of antibiotic pollution, namely hospital and urban wastewaters, as well as in river waters. The method is based on automated off-line solid phase extraction (SPE) followed by ultra-high-performance liquid chromatography coupled to quadrupole linear ion trap tandem mass spectrometry (UHPLC-QqLIT). For unequivocal identification and confirmation, and in order to fulfill EU guidelines, two selected reaction monitoring (SRM) transitions per compound are monitored (the most intense one is used for quantification and the second one for confirmation). Quantification of target antibiotics is performed by the internal standard approach, using one isotopically labeled compound for each chemical group, in order to correct matrix effects. The main advantages of the method are automation and speed-up of sample preparation, by the reduction of extraction volumes for all matrices, the fast separation of a wide spectrum of antibiotics by using ultra-high-performance liquid chromatography, its sensitivity (limits of detection in the low ng/L range) and selectivity (due to the use of tandem mass spectrometry) The inclusion of β-lactam antibiotics (penicillins and cephalosporins), which are compounds difficult to analyze in multi-residue methods due to their instability in water matrices, and some antibiotics metabolites are other important benefits of the method developed. As part of the validation procedure, the method developed was applied to the analysis of antibiotics residues in hospital, urban influent and effluent wastewaters as well as in river water samples. © 2013 Elsevier B.V., This work has been supported by the Spanish Ministry of Economy and Competitiveness through the projects DEGRAPHARMAC (CTQ2010-21776-C02-2), the European Project ENDETECH (FP7-ENV-2011-ECO-INNOVATION) and by the European Regional Development Fund (ERDF). M. Villagrasa is acknowledged for her technical assistance with the UHPLC and 5500QTRAP™. Gabriela Poch from TRARGISA is acknowledged for the collection of wastewater samples at WWTP1. Sara Chamorro, Gianluigi Buttiglieri and Neus Collado from the Catalan Institute for Water Research (ICRA) are acknowledged for providing wastewater samples and Belinda Huerta is acknowledged for her help in the laboratory. Prof. Barceló acknowledges King Saud University for his visiting professorship.

A new sensitive method based on pressurized liquid extraction (PLE) and purification by gel permeation chromatography (GPC) prior to ultra-high-performance liquid chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS) was developed for the determination in fish homogenate, liver and muscle of twenty pharmaceuticals compounds and metabolites from seven commonly used therapeutic families. An extensive matrix effect evaluation was performed in order to select the best approach when analyzing such complex matrices. Limits of detection (MDLs) for the target compounds were in the range of 0.03-0.50ng/g for fish homogenate, 0.01-0.42ng/g for fish muscle, and 0.08-0.98ng/g for fish liver. The method was applied to fish tissues of eleven fish species from four heavily impacted Mediterranean rivers. Nine compounds from five therapeutic families were measured at concentrations higher than MDLs. Highest levels were found in trout liver, with a maximum concentration of 18ng/g for carbamazepine, whereas the most ubiquitous compound was diclofenac.

On-site sewage treatment facilities (OSSFs), which are used to reduce nutrient emissions in rural areas, were screened for anthropogenic compounds with two-dimensional gas chromatography–mass spectrometry (GC × GC–MS). The detected compounds were prioritized based on their persistence, bioaccumulation, ecotoxicity, removal efficiency, and concentrations. This comprehensive prioritization strategy, which was used for the first time on OSSF samples, ranked galaxolide, α-tocopheryl acetate, octocrylene, 2,4,7,9-tetramethyl-5-decyn-4,7-diol, several chlorinated organophosphorus flame retardants and linear alkyl benzenes as the most relevant compounds being emitted from OSSFs. Twenty-six target analytes were then selected for further removal efficiency analysis, including compounds from the priority list along with substances from the same chemical classes, and a few reference compounds. We found significantly better removal of two polar contaminants 2,4,7,9-tetramethyl-5-decyn-4,7-diol (p = 0.0003) and tris(2-butoxyethyl) phosphate (p = 0.005) in soil beds, a common type of OSSF in Sweden, compared with conventional sewage treatment plants. We also report median removal efficiencies in OSSFs for compounds not studied in this context before, viz. α-tocopheryl acetate (96%), benzophenone (83%), 2-(methylthio)benzothiazole (64%), 2,4,7,9-tetramethyl-5-decyn-4,7-diol (33%), and a range of organophosphorus flame retardants (19% to 98%). The environmental load of the top prioritized compounds in soil bed effluents were in the thousands of nanogram per liter range, viz. 2,4,7,9-tetramethyl-5-decyn-4,7-diol (3000 ng L− 1), galaxolide (1400 ng L− 1), octocrylene (1200 ng L− 1), and α-tocopheryl acetate (660 ng L− 1).

A comprehensive screening of micropollutants was performed in wastewaters from on-site sewage treatment facilities (OSSFs) and urban wastewater treatment plants (WWTPs) in Sweden. A suspect screening approach, using high resolution mass spectrometry, was developed and used in combination with target analysis. With this strategy, a total number of 79 micropollutants were successfully identified, which belong to the groups of per- and polyfluoroalkyl substances (PFASs), pesticides, phosphorus-containing flame retardants (PFRs) and pharmaceuticals and personal care products (PPCPs). Results from this screening indicate that concentrations of micropollutants are similar in influents and effluents of OSSFs and WWTPs, respectively. Removal efficiencies of micropollutants were assessed in the OSSFs and compared with those observed in WWTPs. In general, removal of PFASs and PFRs was higher in package treatment OSSFs, which are based on biological treatments, while removal of PPCPs was more efficient in soil bed OSSFs. A novel comprehensive prioritization strategy was then developed to identify OSSF specific chemicals of environmental relevance. The strategy was based on the compound concentrations in the wastewater, removal efficiency, frequency of detection in OSSFs and on in silico based data for toxicity, persistency and bioaccumulation potential.

The extensive and intensive use of chemicals in our developed, highly technological society includes more than 100,000 chemical substances. Significant scientific evidence has lead to the recognition that their improper use and release may result in undesirable and harmful side-effects on both the human and ecosystem health. To cope with them, appropriate risk assessment processes and related prioritization schemes have been developed in order to provide the necessary scientific support for regulatory procedures. In the present paper, two of the elements that constitute the core of risk assessment, namely occurrence and hazard effects, have been discussed. Recent advances in analytical chemistry (sample pre-treatment and instrumental equipment, etc.) have allowed for more comprehensive monitoring of environmental pollution reaching limits of detection up to sub ng L − 1 . Alternative to analytical measurements, occurrence models can provide risk managers with a very interesting approach for estimating environmental concentrations from real or hypothetical scenarios. The most representative prioritization schemes used for issuing lists of concerning chemicals have also been examined and put in the context of existing environmental policies for protection strategies and regulations. Finally, new challenges in the field of risk-assessment have been outlined, including those posed by new materials (i.e., nanomaterials), transformation products, multi-chemical exposure, or extension of the risk assessment process to the whole ecosystem.

Even though Ibuprofen is one of the most studied pharmaceutical in the aquatic environment, there is still a lack of information about its fate and the generation of different transformation products along wastewater treatment plants (WWTPs). Ibuprofen biotransformation products can be generated by human metabolism or by microorganisms present in WWTPs and in natural waters, soils, and sediments, which increase the probability to find them in environment. In this work, the presence of ibuprofen and its main metabolites: ibuprofen carboxylic acid (CBX IBU), 2-hydroxylated ibuprofen (2-OH IBU) and 1-hydroxylated ibuprofen (1-OH IBU), was monitored quantitatively along the biodegradation processes occurring in different batch activated sludge (BAS) experiments under different working conditions. Total ibuprofen removal, achieved in almost all the experiments, was related in part to the formation of the metabolites mentioned. Another ibuprofen metabolite, 1,2-dihydroxy ibuprofen, was detected in BAS experiments for the first time. The metabolites 2-OH IBU and 1-OH IBU remained in solution at the end of ibuprofen biodegradation experiments whereas CBX IBU disappeared faster than hydroxylated metabolites. In addition, also the biodegradation of 1-OH IBU, 2-OH IBU and CBX IBU was evaluated in batch experiments: CBX IBU removal occurred at the highest rate followed by IBU, 2-OH IBU, and 1-OH IBU, which exhibited the lowest removal rate. Finally, Ibuprofen and ibuprofen metabolites were monitored in sewage and natural water samples, where they were found at higher levels than expected: the maximum concentration in influent wastewater samples were 13.74, 5.8, 38.4, 94.0 μg/L for IBU, 1-OH IBU, CBX IBU and 2-OH IBU respectively; whereas maximum levels in effluent wastewater samples were 1.9, 1.4, 10.7, 5.9 μg/L for IBU, 1-OH IBU, CBX IBU and 2-OH IBU respectively. High levels of the compounds were also found in river samples, in particular for CBX IBU, which was detected up to 3.9 μg/L.

The present work describes the development of an analytical method, based on automated off-line solid phase extraction (SPE) followed by ultra-high-performance liquid chromatography coupled to quadrupole linear ion trap tandem mass spectrometry (UPLC-QqLIT) for the determination of 81 pharmaceutical residues, covering various therapeutic groups, and some of their main metabolites, in surface and treated waters (influent and effluent wastewaters, river, reservoir, sea and drinking water). For unequivocal identification and confirmation, two selected reaction monitoring (SRM) transitions per compound are monitored. Quantification is performed by the internal standard approach, indispensable to correct matrix effects. Moreover, to obtain an extra tool for confirmation of positive findings, an information dependent acquisition (IDA) experiment was performed, with SRM as survey scan and an enhanced product ion (EPI) scan as dependent scan. Compound identification was carried out by library search, matching the EPI spectra achieved at one fixed collision energy with those present in a library. The main advantages of the method are automation and speed-up of sample preparation by the reduction of extraction volumes for some matrices, the fast separation of a big number of pharmaceuticals, its high sensitivity (limits of detection in the low ng/L range), selectivity, due to the use of tandem mass spectrometry, reliability since a significant number of isotopically labeled compounds are used as internal standards for quantification and finally, the analysis of tap, reservoir and sea waters, since information about occurrence of pharmaceuticals in these matrices is still sparse. As part of the validation procedure, the method developed was applied to the analysis of pharmaceutical residues in waste and surface waters from different sites in Catalonia (North East of Spain).

During 8 sampling campaigns carried out over a period of two years, 72 samples, including influent and effluent wastewater, and sludge samples from three conventional wastewater treatment plants (WWTPs), were analyzed to assess the occurrence and fate of 43 pharmaceutical compounds. The selected pharmaceuticals belong to different therapeutic classes, i.e. non-steroidal anti-inflammatory drugs, lipid modifying agents (fibrates and statins), psychiatric drugs (benzodiazepine derivative drugs and antiepileptics), histamine H2-receptor antagonists, antibacterials for systemic use, beta blocking agents, beta-agonists, diuretics, angiotensin converting enzyme (ACE) inhibitors and anti-diabetics. The obtained results showed the presence of 32 target compounds in wastewater influent and 29 in effluent, in concentrations ranging from low ng/L to a few μg/L (e.g. NSAIDs). The analysis of sludge samples showed that 21 pharmaceuticals accumulated in sewage sludge from all three WWTPs in concentrations up to 100 ng/g. This indicates that even good removal rates obtained in aqueous phase (i.e. comparison of influent and effluent wastewater concentrations) do not imply degradation to the same extent. For this reason, the overall removal was estimated as a sum of all the losses of a parent compound produces by different mechanisms of chemical and physical transformation, biodegradation and sorption to solid matter. The target compounds showed very different removal rates and no logical pattern in behaviour even if they belong to the same therapeutic groups. What is clear is that the elimination of most of the substances is incomplete and improvements of the wastewater treatment and subsequent treatments of the produced sludge are required to prevent the introduction of these micro-pollutants in the environment.

In a long term study, which covered 4 sampling periods over three years, a total number of 84 samples, specifically 28 influent, effluent, from seven WWTP located in the main cities along the Ebro river Basin (North East of Spain), as well as receiving river waters, were analyzed to assess the occurrence of 73 pharmaceuticals covering several medicinal classes. Results indicated that pharmaceuticals are widespread pollutants in the aquatic environmental. Linking the calculation of removal rates with half-lives, assuming that compound degradation followed pseudo-first order kinetics, suggested that conventional wastewater treatments applied at the seven WWTP were unable to completely remove most of the pharmaceuticals under study. The evaluation of compound degradability, in terms of half-lives, is an important task to discuss integrated solutions for mitigation of pollutants entry into the water cycle. High half-lives observed for the majority of pharmaceuticals in WWTP suggest that, in order to enhance compound degradation, higher hydraulic retention times should be required. The wide spectrum of substances detected in receiving river waters indicates that WWTP outlets are major contributors of pharmaceuticals in the aquatic environment. However, municipal wastewater treatment represents an obligatory and final treatment step prior to their release into the aquatic media, since load of pharmaceuticals in outlets were considerably reduced after treatment. Finally, hazard posed by pharmaceuticals in both surface and effluent wastewaters was assessed toward different aquatic organisms, (algae, daphnids and fish). The overall relative order of susceptibility was estimated to be algae > daphnia > fish. Results indicate that no significant risks could be associated to the presence of pharmaceuticals in those matrices, indicating that reduction of compound concentration after wastewater treatment as well as dilution factor once pharmaceuticals are discharged in receiving river water efficiently mitigate possible environmental hazards., EU project AQUATERRA (GOCE 505428) and the Spanish Ministry of Science and Education Project CEMAGUA (CGL2007-64551)

26 pages, 3 tables, 3 figures., Pharmaceutically active compounds (PhACs) and drugs of abuse (DAs) are two important groups of emerging environmental contaminants that have raised an increasing interest in the scientific community. A number of studies revealed their presence in the environment. This is mainly due to the fact that some compounds are not efficiently removed during wastewater treatment processes, being able to reach surface and groundwater and subsequently, drinking waters. This paper reviews the data regarding the levels of pharmaceuticals and illicit drugs detected in wastewaters and gives an overview of their removal by conventional treatment technologies (applying activated sludge) as well as advanced treatments such as membrane bioreactor. The paper also gives an overview of bank filtration practices at managed aquifer recharge sites and discusses the potential of this approach to mitigate the contamination by PhACs and DAs., This work has been supported by the EU project INNOVA-MED (INCO-CT-2006-517728) and by the Spanish Ministry of Science and Innovation Projects CTM2007-30524-E and CEMAGUA (CGL2007-64551).

Comparability of monitoring data are essential for any meaningful assessment and for the management of environmental risks of emerging pollutants. The reliability and comparability of data at European level is often limited, because analytical methods for emerging pollutants are often not fully validated, not harmonized or not suitable for all relevant matrices. This paper describes a collaborative interlaboratory exercise for the analysis of non-steroidal anti-inflammatory drugs (NSAIDs) residues in freshwater and wastewater, held in the framework of the EU project "Network of reference laboratories for monitoring of emerging environmental pollutants" (NORMAN). The NSAID compounds selected in this study were ketoprofen, naproxen, ibuprofen and diclofenac. Thirteen laboratories distributed along nine European Countries (Austria, France, Germany, Greece, Italy, Slovak Republic, Slovenia, Spain, and Switzerland) took part in this exercise, 126 samples were analyzed and a total number of 473 values in duplicate were collected. Samples selected in this study include environmental water (river water and waste water) and artificial water (fortified environmental and distilled water) with different ranges of complexity. Two analytical methods were proposed by the organiser; one is based on the use of solid phase extraction (SPE) followed by liquid chromatography-tandem mass spectrometry (LC-MS/MS) and the second one is based on SPE followed by gas-chromatography-mass spectrometry (GC-MS), however, in the first round some different approaches were also admitted. The main goals of this interlaboratory comparison were to evaluate the available analytical schemes for NSAID analysis in natural waters, to evaluate the repeatability (r) and reproducibility (R) between participating laboratories, and to evaluate the influence of the analytical method and sample matrices on the results.

This paper reports on a comprehensive reconnaissance of over seventy individual wastewater contaminants in the region of Western Balkan (WB; Bosnia and Herzegovina, Croatia and Serbia), including some prominent classes of emerging contaminants such as pharmaceuticals and personal care products, surfactants and their degradation products, plasticizers, pesticides, insect repellents, and flame retardants. All determinations were carried out using a multiresidue analytical approach, based on the application of gas chromatographic and liquid chromatographic techniques coupled to mass spectrometric detection. The results confirmed a widespread occurrence of the emerging contaminants in municipal wastewaters of the region. The most prominent contaminant classes, determined in municipal wastewaters, were those derived from aromatic surfactants, including linear alkylbenzene sulphonates (LAS) and alkylphenol polyethoxylates (APEO), with the concentrations in raw wastewater reaching into the mg/l range. All other contaminants were present in much lower concentrations, rarely exceeding few microg/l. The most abundant individual compounds belonged to several classes of pharmaceuticals (antimicrobials, analgesics and antiinflammatories, beta-blockers and lipid regulators) and personal care products (fragrances). Due to the rather poor wastewater management practices in WB countries, with less than 5% of all wastewaters being biologically treated, most of the contaminants present in wastewaters reach ambient waters and may represent a significant environmental concern.

This paper describes the development of an analytical methodology to determine eight β-blockers in waste waters using molecularly imprinted polymers (MIPs) as extraction and pre-concentration material, followed by liquid chromatography–quadrupole-linear ion trap mass spectrometry (LC–QqLIT MS). The advantages offered by MIPs, in terms of selectivity and specificity, were compared with the most commonly polymeric materials used (the lipophilic–hydrophilic balanced Oasis® HLB cartridges). Even though recoveries achieved with both sorbents were similar, ranging from 50 to 110% for sewage treatment plant (STP) effluent and 40–110 for STP influent, respectively, MIPs provided lower method detection limits than Oasis® HLB, due to their specificity for target analytes and closely related analogues. Method detection limits (MDL) achieved using MIPs ranged from 0.2 to 6.4 ng/L for STP effluent and from 0.4 to 6.5 ng/L for STP influent. To highlight the advantages of MIPs against conventional polymeric cartridges, a detailed matrix effects study as well as cross reactivity tests were performed. For the latter purpose, the extraction efficiency of some pharmaceuticals and pesticides belonging to different therapeutic classes was assessed. LC–QqLIT MS, used for quantification and confirmation, proved to be a powerful analytical tool, as instrumental detection limits (IDL) achieved ranged from 0.2 to 2.7 pg injected (in multiple reaction monitoring mode (MRM)). In addition the inclusion of high sensitive MS/MS scans for each compound when working in Information Dependent Acquisition mode (IDA) provided extra confirmation for unequivocal identification of target compounds in complex environmental matrices.

Attenuation of pharmaceuticals due to natural sunlight is expected to be an important removal pathway in wastewater treatment plants using treatment lagoon systems. In this work, the photolysis of two antidepressants, amisulpride and desipramine, has been investigated in both ultrapure water and wastewater under simulated solar irradiation. Results showed that for amisulpride short irradiation times (t1/2 approximately 3h in pure water and 4h in wastewater) were adequate to degrade the parent compound while a longer exposure period was required for desipramine (t1/2 of approximately 36 h in pure water), although its degradation is enhanced almost three times by indirect photolysis in wastewaters. A significant number of transformation products (TPs) were identified for both pharmaceuticals by high-resolution mass spectrometry. In general, TPs formed are not persistent although acute toxicity tests for desipramine and its TPs showed an increase of the mixture toxicity after solar irradiation, suggesting that some TPs may be more toxic than the parent compound. In wastewaters collected from treatment lagoons, only amisulpride and one of its major TPs, TP 357, were detected. This indicates that long solar exposure times may be necessary for an effective elimination of these substances in lagoon systems or that photolysis may not be the main removal pathway for these particular compounds.

The seasonal variations in the occurrence and distribution of pharmaceuticals were evaluated in seawater and sediment of Mar Menor lagoon from spring 2010 to winter 2011. A total of 20 pharmaceuticals in seawater and 14 in sediments were found at concentrations from low ngL(-)(1) up to 168ngL(-)(1) (azithromycin) in seawater and from low ngg(-1) up to 50.3ngg(-1) (xylazine) in sediments. Azithromycin, xylazine and metoprolol were the most ubiquitous compounds in seawater since they were found in all seawater samples collected. Seven compounds were quantified in both matrices: clarithromycin, erythromycin, hydrochlorothiazide, irbesartan, losartan, salicylic acid and valsartan. Seasonal distribution profiles revealed different sources of pollutants associated to both, El Albujón watercourse (which receives the input of a WWTP) and other non-controlled discharges, into the lagoon. In summer the highest concentrations in seawater for most of the pharmaceuticals were detected close to main touristic nuclei, probably as consequence of sources such as the excretion from bathers and/or other non-controlled discharges, these being significantly higher than in autumn and winter for antibiotics. On the contrary, the mean concentration of lorazepam was significantly higher in colder seasons than in warmer ones. Sulfamethoxazole, erythromycin and especially clarithromycin showed hazard quotients higher than 1 in seawater at some areas of this lagoon indicating a potential risk to aquatic organisms in such specific areas.

In this work, a new multi-residue method using ultra-performance liquid chromatography (UPLC) quadrupole-time-of-flight mass spectrometry (Q-TOF-MS) was developed for screening and confirmation of 29 pharmaceutical compounds belonging to different therapeutical classes: analgesics and antiinflammatories, lipid regulating agents cholesterol lowering statin agents, psychiatric drugs, anti ulcer agents, histamine H2 receptor antagonist, antibiotics and beta-blockers. UPLC uses columns packed with 1.7 microm particles and enables elution of sample components in much narrower, more concentrated bands, resulting in better chromatographic resolution and increased peak height. The typical peak width was 5-10s at base, permitting very good separation of all compounds in 10 min, which represented an approximate three-fold reduction in the analysis time in comparison to conventional high-performance liquid chromatography (HPLC). Unequivocal identification of target pharmaceutical compounds was based on accurate mass measurement of the molecular ions in the TOF mode and by performing collision induced dissociation (CID) in the Q-TOF mode in order to generate accurate mass measurement of the product ions. Using lock mass correction the accurate masses calculated for the product ions deviated from the theoretical masses by 0.2 to 1.3 mDa (root mean square (RMS) value=0.67) and 0.7-6.4 ppm (RMS=3.53), respectively. Quantitation was carried out working in the TOF mode using the narrow window extracted ion chromatograms (nwXICs) of each compound (extracted using a 20 mDa window) yielding relative standard deviation (RSD) from 0.5 to 5.3% (run-to-run) and from 2.1 to 9.1% (day-to-day) and instrumental detection limits (IDLs) from 1 to 200 pg. Analysis of wastewater treatment plant (WWTP) samples gave method detection limits (MDLs) ranging from 10 to 500 ng/L. The UPLC-Q-TOF method was successfully applied to analyze pharmaceutical residues in WWTP samples.

Many technologies are being developed for the efficient removal of micropollutants from wastewater and, among them, fungal degradation is one of the possible alternative biological treatments. In this article, some factors that might affect pharmaceutically active compounds (PhACs) removal in a fungal treatment of real wastewater were identified in batch bioreactor treating reverse osmosis concentrate (ROC) from urban wastewater treatment plant (WWTP). We found that degradation of PhACs by Trametes versicolor was enhanced by addition of external nutrients (global removal of 44%). Moreover, our results point out that high aeration might be involved in the increase in the concentration of some PhACs. In fact, conjugation and deconjugation processes (among others) affect the removal assessment of emerging contaminants when working with real concentrations in comparison to experiments with spiked samples. Moreover, factors that could affect the quantification of micropollutants at lab-scale experiments were studied.

The seasonal occurrence and distribution of 69 pharmaceuticals along coastal watercourses during 6 sampling campaigns and their input through El Albujon watercourse to the Mar Menor lagoon were determined by UPLC–MS-MS, considering a total of 115 water samples. The major source of pharmaceuticals running into this watercourse was an effluent from the Los Alcazares WWTP, although other sources were also present (runoffs, excess water from irrigation, etc.). In this urban and agriculturally influenced watercourse different pharmaceutical distribution profiles were detected according to their attenuation, which depended on physicochemical water conditions, pollutant input variation, biodegradation and photodegradation rates of pollutants, etc. The less recalcitrant compounds in this study (macrolides, β-blockers, etc.) showed a relevant seasonal variability as a consequence of dissipation processes (degradation, sorption, etc.). Attenuation was lower, however, for diclofenac, carbamazepine, lorazepam, valsartan, sulfamethoxazole among others, due to their known lower degradability and sorption onto particulate matter, according to previous studies. The maximum concentrations detected were higher than 1000 ng L− 1 for azithromycin, clarithromycin, valsartan, acetaminophen and ibuprofen. These high concentration levels were favored by the limited dilution in this low flow system, and consequently some of them could pose an acute risk to the biota of this watercourse. Considering data from 2009 to 2010, it has been estimated that a total of 11.3 kg of pharmaceuticals access the Mar Menor lagoon annually through the El Albujon watercourse. The highest proportion of this input corresponded to antibiotics (46%), followed by antihypertensives (20%) and diuretics (18%).

A method based on ultra high performance liquid chromatography coupled to quadrupole linear ion trap mass spectrometry (UHPLC-QqLIT-MS) has been developed to investigate occurrence of 10 anthelmintic drugs from different structural groups (moxidectin, flubendazole, fenbendazole, levamisol, mebendazole, oxibendazole, albendazole, triclabendazole, febantel and praziquantel) in surface water. Analytes were pre-concentrated by solid phase extraction (SPE) using hydrophilic–lipophilic polymeric based sorbent. Quantification of investigated analytes was done using deuterated compounds as internal standards in order to minimize matrix effect. Analyte recoveries from spiked samples at two concentration levels were above 75% for most of the analytes. The main advantages of developed method are fast separation using UHPLC and therefore short analysis time, combined with good sensitivity which is demonstrated by low ng L −1 detection limits. The developed method was applied for analysis of anthelmintics in the Llobregat River (NE Spain) and its main tributaries (rivers Anoia and Cardener). Eight out of ten anthelmintics were detected in all analyzed samples with the concentrations in low ng L −1 level. The method fills the gap on analytical methodologies for determination of anthelmintic drugs in the environment.

Antibiotic resistance represents a growing global health concern due to the overuse and misuse of antibiotics. There is, however, little information about how the selective pressure of clinical antibiotic usage can affect environmental communities in aquatic ecosystems and which bacterial groups might be responsible for dissemination of antibiotic resistance genes (ARGs) into the environment. In this study, chemical and biological characterization of water and sediments from three water supply reservoirs subjected to a wide pollution gradient allowed to draw an accurate picture of the concentration of antibiotics and prevalence of ARGs, in order to evaluate the potential role of ARGs in shaping bacterial communities, and to identify the bacterial groups most probably carrying and disseminating ARGs. Results showed significant correlation between the presence of ARG conferring resistance to macrolides and the composition of bacterial communities, suggesting that antibiotic pollution and the spreading of ARG might play a role in the conformation of bacterial communities in reservoirs. Results also pointed out the bacterial groups Actinobacteria and Firmicutes as the ones probably carrying and disseminating ARGs. The potential effect of antibiotic pollution and the presence of ARGs on the composition of bacterial communities in lacustrine ecosystems prompt the fundamental question about potential effects on bacterial-related ecosystem services supplied by lakes and reservoirs. © 2013 Elsevier B.V., We thank Carles Borrego, Enrique Navarro, and Veronica Ribé for helpful discussions and comments to the article, and Jaime Ordóñez for help during field work. We also thank George A. Jacoby, Carmen Torres and Joan Jofre for providing us with bacterial strains. This research work was funded by the 1st Interdisciplinary Water Research Projects-ICRA Grants Program 2010 (Project RES2), the Spanish Ministry of Economy and Competitiveness for its financial support through the project SCARCE (Consolider-Ingenio 2010 CSD2009-00065), and by the European Union through the European Regional Development Fund (FEDER). This work was also partly supported by the Generalitat de Catalunya (Consolidated Research Group: Water and Soil Quality Unit 2009-SGR-965). Prof. Barceló acknowledges King Saud University for his visiting professorship.