Emerging organic contaminants in aquatic environments: state-of-the-art and recent scientific contributions

Els contaminants emergents són contaminants prèviament desconeguts o no reconeguts com a tals, la presència dels quals en el medi ambient no és necessàriament nova, però sí la preocupació pels possibles efectes perillosos sobre la salut humana i la dels ecosistemes. A causa de llur recent descobriment o reconeixement com a contaminants, la informació que se'n disposa sobre la presència, el destí i la toxicitat en ambients aquàtics, i sobre els mètodes analítics per a detectar- los en diverses matrius ambientals és escassa. En els darrers anys, el grup liderat pel professor d'investigació Damià Barceló Cullerès ha participat intensament en l'estudi de nombroses classes de contaminants emergents (estrògens, fàrmacs, drogues, nanopartícules, plaguicides polars, etc.). Aquest article repassa les contribucions més recents fetes pel grup en aquest camp dels contaminants emergents en les línies de desenvolupament de mètodes analítics, programes de vigilància ambiental i estudis de biodisponibilitat, degradació i toxicitat.Emerging contaminants are previously unknown or unrecognized contaminants whose presence in the environment is not necessarily new but which raise concern due to their potentially dangerous effects on the ecosystem and on human health. Due to their recent discovery or recognition as contaminants, information about the occurrence, fate, and toxicity of these compounds in the aquatic environment, as well as analytical methods for their detection in various environmental matrices, is scarce. We have intensively studied many of these classes of emerging contaminants (estrogens, pharmaceuticals, illicit drugs, nanoparticles, polar pesticides, etc.). This article reviews the most recent contributions made by our group to the field of emerging contaminants with respect to the development of analytical methods, monitoring studies, and bioavailability, degradation, and toxicity studies

Fate and removal of pharmaceuticals and illicit drugs in conventional and membrane bioreactor wastewater treatment plants and by riverbank filtration

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).Peer reviewe

High-resolution mass spectrometry to complement monitoring and track emerging chemicals and pollution trends in European water resources

Currently, chemical monitoring based on priority substances fails to consider the majority of known environmental micropollutants not to mention the unexpected and unknown chemicals that may contribute to the toxic risk of complex mixtures present in the environment. Complementing component- and effect-based monitoring with wide-scope target, suspect, and non-target screening (NTS) based on high-resolution mass spectrometry (HRMS) data is recommended to support environmental impact and risk assessment. This will allow for detection of newly emerging compounds and transformation products, retrospective monitoring efforts, and the identification of possible drivers of toxicity by correlation with effects or modelling of expected effects for future and abatement scenarios. HRMS is becoming increasingly available in many laboratories. Thus, the time is right to establish and harmonize screening methods, train staff, and record HRMS data for samples from regular monitoring events and surveys. This will strongly enhance the value of chemical monitoring data for evaluating complex chemical pollution problems, at limited additional costs. Collaboration and data exchange on a European-to-global scale is essential to maximize the benefit of chemical screening. Freely accessible data platforms, inter-laboratory trials, and the involvement of international partners and networks are recommended

Drogas de abuso en las aguas subterráneas urbanas de Barcelona (España)

En este estudio se determinaron las concentraciones de drogas de abuso (DAS) y sus metabolitos en el agua subterránea urbana de Barcelona. Para este fin, se recogieron 37 muestras de aguas subterráneas en zonas urbanas y se analizaron 21 medicamentos incluyendo compuestos cocainicos, compuestos similares a la anfetamina, opioides, lisérgicos, cannabinoides y benzodiacepinas (con prescripción médica). Las mayores concentraciones en el agua subterránea (alrededor de 200 ng / L en SAP-4) y el mayor número de detectado el DAS se encuentran en zonas básicamente recargadas por un río que cruza la zona urbana recibe grandes cantidades de efluentes de plantas de tratamiento de aguas residuales (EDAR). En contraste, en el área urbana sin la influencia fluvial se encontraron concentraciones más bajas y un menor número de fármacos, lo que sugiere un origen local. De hecho, la cocaína y su metabolito fueron dominantes en los barrios más prósperos, mientras que el MDMA más barato era el fiscal dominante en los distritos más pobres. Las concentraciones medidas fueron siempre menores que los estimados a partir de la fracción de agua residual en las muestras de agua subterránea, lo que sugiere que el DAS se someten a procesos de eliminación, tanto en la reducción y condiciones oxidantes.This study is concerned with drugs of abuse (DAs) and their metabolites in Barcelona’s urban gr oundwater. To this end, 37 urban groundwater samples were collected and 21 drugs were analyzed including cocainics, amphetamine-like compounds, opioids, lysergics and cannabinoids and the prescribed drugs benzodiazepines. The highest groundwater concentrations (around 200 ng/L in SAP-4) and the largest number of detected DAs were found in zones basically recharged by a river that receives large amounts of effluents from waste water treatment plants (WWTPs). In contrast, the urbanized areas yielded lower concentrations and a smaller number of drugs, which suggests a local origin. In fact, cocaine and its metabolite were dominant in more prosperous neighbourhoods, whereas the cheaper MDMA was the dominant DA in poorer districts. Measured concentrations were consistently smaller than those estimated from the waste water fraction in groundwater samples, suggesting that DAs undergo removal processes in both reducing and oxidizing conditions.Universidad Nacional de La Plat

Assessing the effects of hydrological and chemical stressors on macroinvertebrate community in an Alpine river: the Adige river as a case study

In this study, the combined effects of hydrological and chemical stressors on benthic macroinvertebrates were evaluated in order to explore the response of the biological community to multiple stressors. The Adige River, located in the south‐eastern Alps, was selected as a case study because representative of the situation of a large river in which the variety of stressors present in the Alpine region act simultaneously. As expected, streamflow showed a seasonal pattern, with high flows in the spring-summer period; however, locally, the natural hydrological regime was altered by the presence of hydropower systems, which chiefly affected low flows. Multivariate analysis showed seasonal and spatial patterns in both chemical and hydrological parameters with a clear gradient in the concentration of nitrate, personal care, and pharmaceutical products moving from headwaters to the main stem of the river. The macroinvertebrate community composition was significantly different in summer and winter and between up and downstream sites. Streamflow alteration chiefly due to water use by hydropower affected community composition but not richness or diversity. Gammarus sp., Hirudinea, and Psychomyia sp., were positively correlated with flow variability, increasing their densities in the sites with higher streamflow variability because of hydropeaking. The results obtained in this study show that the composition of the macroinvertebrate community responded to seasonality and to changes in the main stressors along the river and highlights the importance of the spatial and temporal variability of stressors in this Alpine river. Taking into account, this variability will help the decision‐making process for improving basin management

Biomarkers of Morbid Obesity and Prediabetes by Metabolomic Profiling of Human Discordant Phenotypes

Metabolomic studies aimed to dissect the connection between the development of type 2 diabetes and obesity are still scarce. In the present study, fasting serum from sixty-four adult individuals classified into four sex-matched groups by their BMI [non-obese versus morbid obese] and the increased risk of developing diabetes [prediabetic insulin resistant state versus non-prediabetic non-insulin resistant] was analyzed by LC- and FIA-ESI-MS/MS-driven metabolomic approaches. Altered levels of [lyso]glycerophospholipids was the most specific metabolic trait associated to morbid obesity, particularly lysophosphatidylcholines acylated with margaric, oleic and linoleic acids [lysoPC C17:0: R=-0.56, p=0.0003; lysoPC C18:1: R=-0.61, p=0.0001; lysoPC C18:2 R=-0.64, p<0.0001]. Several amino acids were biomarkers of risk of diabetes onset associated to obesity. For instance, glutamate significantly associated with fasting insulin [R=0.5, p=0.0019] and HOMA-IR [R=0.46, p=0.0072], while glycine showed negative associations [fasting insulin: R=-0.51, p=0.0017; HOMA-IR: R=-0.49, p=0.0033], and the branched chain amino acid valine associated to prediabetes and insulin resistance in a BMI-independent manner [fasting insulin: R=0.37, p=0.0479; HOMA-IR: R=0.37, p=0.0468]. Minority sphingolipids including specific [dihydro]ceramides and sphingomyelins also associated with the prediabetic insulin resistant state, hence deserving attention as potential targets for early diagnosis or therapeutic intervention

Chemical and toxicological characterisation of anticancer drugs in hospital and municipal wastewaters from Slovenia and Spain

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Contaminants of emerging concern in the Basque coast (N Spain): Occurrence and risk assessment for a better monitoring and management decisions

The study of the presence in the aquatic environment of certain substances considered as contaminants of emerging concern (CEC) is a preliminary step to the analysis of the possible harmful effects on aquatic ecosystems and the establishment of the corresponding environmental quality standards. In order to monitor the occurrence of CECs in the aquatic environment, the European Commission established in 2015 and 2018 two watch-list of substances for Union-wide monitoring in the field of water policy (Decision (EU) 2015/495 and Decision (EU) 2018/840). In the coast of the Basque Country, southeast of the Bay of Biscay, 19 of these watch list substances were monitored quarterly from May 2017 to March 2019. Water samples were collected at the effluent of three wastewater treatment plants and five control points associated with receiving waters (transitional and coastal water bodies). The most frequently quantified substances were azithromycin (91%), imidacloprid (82%), clarithromycin (80%), diclofenac (78%) and erythromycin (73%), with frequencies of quantification higher in wastewaters (83–100%) than in receiving waters (70–85%). In general, concentrations in wastewater were also higher than in receiving waters, indicating a dilution effect in the environment. In receiving waters, six out of the nineteen substances monitored exceeded their respective Predicted No-Effect Concentrations: azithromycin (34%), imidacloprid (9%), 17β-estradiol (E2) (9%), clarithromycin (7%), ciprofloxacin (7%), and diclofenac (5%); and therefore, their levels could pose an environmental risk.This work was supported by the Basque Water Agency (URA) through the project “Network for monitoring the ecological and chemical status of transitional and coastal waters of the Basque coast”, and partly by the Generalitat de Catalunya (Consolidate Research Group 2017-SGR-14) and the Ministry of Science and Innovation of Spain (Project CEX2018-000794-S). Biotage is acknowledged for the gift of ISOLUTE® Na2SO4 drying cartridges. The authors acknowledge the help of the entities in charge of the management of the three studied WWTPs (Consorcio de Aguas Bilbao Bizkaia, Consorcio de Aguas de Busturialdea and Aguas del Añarbe), as well as the work of all sampling and laboratory technicians. This is contribution number 1002 from the Marine Research of AZTI-BRTA (Basque Research and Technology Alliance).Peer reviewe

ESAR-Net: a collaborative effort to expand the application of wastewater epidemiology in Spain

Resumen del trabajo presentado en el SETAC Europe 30th Annual Meeting, celebrado en modalidad virtual del 3 al 7 de mayo de 2020.Data obtained from wastewater analysis can provide rapid and complementary insights in illict drug consumption at community level. Drug use has been assessed through wastewater analysis at national level in, for example, Australia, Belgium, Finland and South Korea and has also provided annually a one week snapshot of illicit drug volumes consumed in European cities (http://www.emcdda.europa.eu/topics/ pods/waste-water-analysis). However, a wastewater monitoring program did not exist in Spain, but leading experts have formed a network (https://www.esarnet.es/) to promote wastewater-based epidemiology at national level and communicate their findings to authorities and policymakers. Within Europe, Spain is an important country of transit of both cocaine and cannabis, due to its cultural, linguistic and colonial ties to Latin America and its proximity to Morocco. The quantity of seized cocaine and cannabis and prevalence of use, locates Spain at the top of Europe. In this work, a national wastewater campaign has been performed to get more insight on the consumption of illicit drugs and NPS within Spain for the first time. Wastewater results from 14 Spanish cities were compared with previously reported data and other national indicators. The cities, located in 7 of the 17 autonomous communities, cover approximately 6 million inhabitants (12.8 of the Spanish population). Untreated wastewater samples were analyzed for urinary biomarkers of amphetamine, methamphetamine, MDMA, cocaine and cannabis. In addition to these conventional drugs, weekend samples were monitored for several new psychoactive substances (NPS) (i.e. phenethylamines and cathinones). The selected NPS are known as possible replacement of these conventional drugs or among those previously reported. Finally, enantiomeric profiling of amphetamine was performed for one city in order to assure the results were due to consumption and not illegal dumping of production residues. This demonstrates another application of wastewater-based epidemiology, which allows to identify the originof drugs in wastewater.This work has been supported by the Spanish State Research Agency (Agencia Estatal de Investigación, AEI) through the “Redes de Excelencia” programme, ESAR-Net, ref. CTM2016-81935-RED

Assessing alcohol consumption through wastewater-based epidemiology: Spain as a case study

Background In this study, an alternative and complementary method to those approaches currently used to estimate alcohol consumption by the population is described. This method, known as wastewater-based epidemiology (WBE), allows back-calculating the alcohol consumption rate in a given population from the concentrations of a selected biomarker measured in wastewater. Methods Composite (24-h) wastewater samples were collected at the inlet of 17 wastewater treatment plants located in 13 Spanish cities for seven consecutive days in 2018. The sampled area covered 12.8% of the Spanish population. Wastewater samples were analyzed to determine the concentration of ethyl sulfate, the biomarker used to back-calculate alcohol consumption. Results Alcohol consumption ranged from 4.5 to 46 mL/day/inhabitant. Differences in consumption were statistically significant among the investigated cities and between weekdays and weekends. WBE-derived estimates of alcohol consumption were comparable to those reported by its corresponding region in the Spanish National Health Survey in most cases. At the national level, comparable results were obtained between the WBE-derived annual consumption rate (5.7 ± 1.2 L ethanol per capita (aged 15+)) and that reported by the National Health Survey (4.7 L ethanol per capita (aged 15+)). Conclusions This is the largest WBE study carried out to date in Spain to estimate alcohol consumption rates. It confirms that this approach is useful for establishing spatial and temporal patterns of alcohol consumption, which could contribute to the development of health care management plans and policies. Contrary to established methods, it allows obtaining information in a fast and relatively economical wayThis work has been supported by the Spanish State Research Agency (AEI) (This work has been supported by the Spanish State Research Agency , CTM2017-84763-C3-1-R, CTM2017-84763-C3-3-R and CTM2017-84763-C3-2-R), Generalitat de Catalunya (expedient number SA-2018-780 and Consolidated Research Group 2017 SGR 01404-Water and Soil Quality Unit), and Galician Council of Culture, Education and Universities (ED481D 2017/003 and EM2014/004). Several of these projects are cofounded by the European Regional Development FundS