Estudio de disruptores endocrinos en el medio ambiente

[Resumen] En los últimos años los disruptores endocrinos (EDCs) están en el punto de mira de estudios ambientales y ecotoxicológicos. Entre ellos destacan los alquilfenoles y el bisfenol A, tanto por su amplio uso industrial y doméstico como por su elevada actividad estrogénica demostrando efectos adversos a niveles traza. Se descargan a las aguas a través de efluentes industriales y de estaciones depuradoras de aguas residuales afectando principalmente al medio acuático. Por ello se necesitan programas de monitorización ambiental que controlen la presencia de estos contaminantes en el medio ambiente, para garantizar su protección y la de la salud pública. A lo largo de esta memoria se propone metodología analítica que permiten determinar estos compuestos a niveles traza en agua, sedimento y biota. Se trata de métodos novedosos, sensibles, selectivos, que cumplen con los principios de la Química Verde y que mejoran los propuestos previamente en la bibliografía. Aplicando la metodología desarrollada se llevan a cabo los primeros estudios ambientales para evaluar la distribución espacio-temporal de estos contaminantes en Galicia y su comportamiento dentro de un mismo ecosistema (partición aguasedimento- biota). Además, se realizan dos estancias de investigación en las que se desarrollan métodos para el análisis de otros EDCs y compuestos emergentes en distintas matrices, como particulado atmosférico o alga.[Resumo] Nos últimos anos os disruptores endocrinos (EDCs) atópanse no punto de mira de estudos ambientais e ecotoxicolóxicos. Entre eles destacan os alquilfenois e o bisfenol A, ben polo seu amplo uso industrial e doméstico, ben pola súa gran actividade estroxénica, mostrando efectos adversos a niveis traza. Descárganse ás augas por medio de efluentes industriais e de estacións depuradoras de augas residuais afectando principalmente ó medio acuático. Por este motivo, requírense programas de monitorización ambiental que controlen a presenza destes compostos no medio ambiente para garantir a súa protección e a da saúde pública. Ao longo desta memoria desenrólase metodoloxía analítica para determina-los compostos a niveis de traza en auga, sedimento e biota. Trátase de métodos novos, sensibles, selectivos, que cumpren cos principios da Química Verde e melloran as propostas atopadas na bibliografía. Aplicando os métodos expostos, realízanse os primeiros estudos ambientais en Galicia para avalia-la distribución espazo-temporal destes contaminantes e o seu comportamento dentro dun mesmo ecosistema (partición auga-sedimento-biota). Ademais, lévanse a cabo dúas estancias de investigación nas que se propón métodos para a análise doutros EDCs e contaminantes emerxentes en distintas matrices ambientais, como partículas atmosféricas ou algas.[Abstract] Endocrine disrupting compounds (EDCs) have taken part in environmental and ecotoxicological studies in the last years. Alkylphenols and bisphenol A stand out among all of them because of their widely use and their high estrogenic activity (adverse effects at trace levels). These compounds enter into the environment through industrial and wastewater treatment plants effluents affecting the aquatic ecosystem. Consequently, monitoring programs that control the occurrence of these pollutants are needed in order to preserve the aquatic environment and protect human health. This Thesis describes different analytical methodologies to determine alkylphenols and bisphenol A in water, sediment and biota samples at trace levels. Novelty, sensitivity, selectivity and compliance with the Green Chemistry principles are the main advantages of these methods which improve the previous methodologies found in the literature. Primary environmental studies in Galicia are carried out applying the proposed methods, and the spatial-temporal distribution of these compounds and their behaviour into the same ecosystem (water-sediment-biota partition) are also evaluated. Furthermore, two short-stays based on the development of new methodology for the analysis of EDCs and emerging compounds in different matrices such as atmospheric particles or algae were performed

Flexible high resolution-mass spectrometry approach for screening new psychoactive substances in urban wastewater

The number of new psychoactive substances (NPS) on the recreational drug market has increased rapidly in the last years, creating serious challenges for public health agencies and law enforcement authorities. Epidemiological surveys and forensic analyses to monitor the consumption of these substances face some limitations for investigating their use on a large scale in a shifting market. The aim of this work was to develop a comprehensive and flexible screening approach for assessing the presence of NPS in urban wastewater by liquid chromatography-high resolution mass spectrometry (LC-HRMS). Almost 200 substances were selected as “priority NPS” among those most frequently and recently reported by the Early Warning Systems (EWS) of different agencies and were included in the screening. Wastewater samples were collected from several cities all over Europe in 2016 and 2017, extracted using different solid-phase cartridges and analysed by LC-HRMS. The screening workflow comprised two successive analytical steps and compounds were identified and confirmed following specific criteria from the current guidelines. Thirteen NPS were identified at different confidence levels by using analytical standards or information from libraries and literature, and about half of them were phenethylamines. As far as we know, this is the first time that four of them (i.e. 3,4-dimethoxy-α-pyrrolidinovalerophenone, para-methoxyamphetamine, 2-phenethylamine and α – methyltryptamine) have been found in urban wastewater. The proposed screening approach was successfully applied in the largest NPS European wastewater monitoring, providing an innovative and easily adapted procedure for investigating NPS. In the light of current challenges and specific future research issues, this approach may complement epidemiological information and help in establishing measures for public health protection

Screening of recently seized new psychoactive substances in urine of potential consumers and urban wastewater

Poster apresentado no VIII Meeting of the Spanish Mass Spectrometry Society (SEEM), 2017, Barcelona,EspanhaNewPsychoactive Substances (NPS) areconstantly being developed as legalsubstitution of traditional drugs of abuse.Although the traditional drugs maintain popular, new drugs are regularly introduced, changing the drug market ceaselessly. Monitoring NPS and its consumption is challengingas these compoundsare normally missed in routine drug analysis. Users do often not exactly know what they consume andinformation available islimitedof what is being sold. Furthermore, very little information exists onmetabolism of these newly introduced NPS. This highlights the needof applying a strategic workflow making use of modernanalytical techniques to face this novel public health safety challenge.The workflowpresented in this work consists of three stages: i)the creation of a databaseincluding approximately 200 NPS. These NPS wererecently reported to the National Early Warning Systems (EWS) ofSpain andItaly and the EWS of the European Monitoring Center for Drugsand Drug Addiction (EMCDDA). ii) The collection of urine samples of individuals suspected of drug consumption, pooled urine samples from festivals and urban wastewater samples. iii) The screening of NPS using ultra-high performance liquid chromatography coupled to high resolution massspectrometry with a hybrid quadrupole time-of-flight mass analyzer. Although the database is under constant development,including NPS reported to be present in wastewaters around Europe, new compounds appearing in the market, as well as metabolites reported in the literature, the workflow applied allowed the detection of several unchanged NPS in urine and pooled urine samples. In several cases, NPSwere also detected in wastewater samples, which indicatesthat consumptionof some of these compounds is elevated. The absence of reference standards for several NPS found, as well as for some NPS metabolites, made it unfeasible the full confirmation of some compounds in the urine/wastewater samples analyzed. However, accurate-mass full-spectrum data provided by HRMS allowed their tentative identification with high degree of reliability. The subsequent acquisition of reference standards, when available, will allow the unequivocal confirmation of their identity.N/

Polyethylene microplastics do not increase bioaccumuation or toxicity of nonylphenol and 4-MBC to marine zooplankton

Global production of synthetic polymers, led by polyethylene (PE), rose steadily in the last decades, and marine ecosystems are considered as a global sink. Although PE is not biodegradable, in coastal areas it fragments into microplastics (MP) readily taken up by biota, and have been postulated as vectors of hydrophobic chemicals to marine organisms. We have tested this hypothesis using two organisms representative of the marine plankton, the holoplanktonic copepod Acartia clausi, and the meroplanktonic larva of the Paracentrotus lividus sea-urchin, and two model chemicals with similar hydrophobic properties, the 4-n-Nonylphenol and the 4-Methylbenzylidene-camphor used as plastic additive and UV filter in cosmetics. Both test species actively ingested the MP particles. However, the presence of MP never increased the bioaccumulation of neither model chemicals, nor their toxicity to the exposed organisms. Bioaccumulation was a linear function of waterborne chemical disregarding the level of MP. Toxicity, assessed by the threshold (EC10) and median (EC50) effect levels, was either independent of the level of MP or even in some instances significantly decreased in the presence of MPs. These consistent results challenge the assumption that MP act as vectors of hydrophobic chemicals to planktonic marine organismsThis study has received funding by the Spanish Government (MINECO/AEI) through Projects PCIN-2015-187-C03-03 (JPI Oceans EPHEMARE), PCIN-2015-170-C02-01 (JPI Oceans BASEMAN), CTM2016-77945-C3, and CTM2017-84763-C3-2-R, by Xunta de Galicia through “Program of Consolidation and structuring of competitive research groups in the University system of Galicia” (Refs GRC2013-004, ED431C 2017/28 and ED431C 2017/36), and by the European Union through the European Regional Development Fund (ERDF). N. S.-G. was granted with a postdoctoral fellowship Mod. A (2016) by Axencia Galega de Innovación (GAIN), Xunta de GaliciaS

Monitoring Alcohol Consumption in Slovak Cities during the COVID-19 Lockdown by Wastewater-Based Epidemiology.

The consumption of alcohol in a population is usually monitored through individual questionnaires, forensics, and toxicological data. However, consumption estimates have some biases, mainly due to the accumulation of alcohol stocks. This study's objective was to assess alcohol consumption in Slovakia during the COVID-19 pandemic-related lockdown using wastewater-based epidemiology (WBE). Samples of municipal wastewater were collected from three Slovak cities during the lockdown and during a successive period with lifted restrictions in 2020. The study included about 14% of the Slovak population. The urinary alcohol biomarker, ethyl sulfate (EtS), was analyzed by liquid chromatography-tandem mass spectrometry (LC-MS/MS). EtS concentrations were used to estimate the per capita alcohol consumption in each city. The average alcohol consumption in the selected cities in 2020 ranged between 2.1 and 327 L/day/1000 inhabitants and increased during days with weaker restrictions. WBE can provide timely information on alcohol consumption at the community level, complementing epidemiology-based monitoring techniques (e.g., population surveys and sales statistics)

Compuestos orgánicos en aguas del estuario del Río Miño. Proyecto "TEAM-Miño"

Comunicación presentada al II Congreso Internacional de Ingeniería Civil y Territorio. Agua, Cultura y Sociedad. Vigo, 20 y 21 de Mayo de 2013.Los resultados de este trabajo se engloban en el Marco del proyecto TEAM-Miño “Transferencia de herramientas para la Evaluación, Ordenación, Gestión y Educación Ambiental en Estuarios” financiado por la Unión Europea (POCTEP 2007-2013), que pretende desarrollar herramientas comunes para la tipificación y clasificación del estado ecológico de las masas de agua de transición del sur de Galicia y norte de Portugal, con la finalidad de colaborar en la implantación de la Directiva Marco del Agua. Se han analizado 19 muestras de agua recogidas a lo largo del río Miño y sus afluentes. En ellas se han determinado diferentes contaminantes de amplio interés industrial y ambiental, como hidrocarburos aromáticos policíclicos (HAP), compuestos organoestánnicos, alquilfenoles y bisfenol A. Salvo excepciones, los niveles encontrados en las muestras no son elevados (<0,1 μg/L). La mayoría de los HAPs se encuentran por debajo de los límites de cuantificación del método analítico (MQL), siendo el compuesto mayoritario el naftaleno. Los compuestos organoestánnicos tampoco han sido detectados. Los alquilfenoles están presentes en todos los puntos muestreados (<MQL-1 μg/L), mientras que el bisfenol A se ha encontrado únicamente en dos de ellos, pero a altas concentraciones (>3 μg/L). En ningún caso las concentraciones medidas superan los límites establecidos en la Directiva 2008/105/CE

Three years of wastewater surveillance for new psychoactive substances from 16 countries

The proliferation of new psychoactive substances (NPS) over recent years has made their surveillance complex. The analysis of raw municipal influent wastewater can allow a broader insight into community consumption patterns of NPS. This study examines data from an international wastewater surveillance program that collected and analysed influent wastewater samples from up to 47 sites in 16 countries between 2019 and 2022. Influent wastewater samples were collected over the New Year period and analysed using validated liquid chromatography - mass spectrometry methods. Over the three years, a total of 18 NPS were found in at least one site. Synthetic cathinones were the most found class followed by phenethylamines and designer benzodiazepines. Furthermore, two ketamine analogues, one plant based NPS (mitragynine) and methiopropamine were also quantified across the three years. This work demonstrates that NPS are used across different continents and countries with the use of some more evident in particular regions. For example, mitragynine has highest mass loads in sites in the United States, while eutylone and 3-methylmethcathinone increased considerably in New Zealand and in several European countries, respectively. Moreover, 2F-deschloroketamine, an analogue of ketamine, has emerged more recently and could be quantified in several sites, including one in China, where it is considered as one of the drugs of most concern. Finally, some NPS were detected in specific regions during the initial sampling campaigns and spread to additional sites by the third campaign. Hence, wastewater surveillance can provide an insight into temporal and spatial trends of NPS use

Galician Feminist drama: a historical overview and an analysis of Antigona by Mª Xosé Queizán

O teatro foi ao longo da historia un xénero moi útil para lexitimar unha ideoloxía ou criticar o pensamento dominante. A partir da antedita premisa analizamos cal foi, e aínda é, a ligazón entre o teatro galego e o feminismoTraballo fin de mestrado (UDC.FIL). Literatura, cultura e diversidade. Curso 2012/201

Glucocorticoid mixtures of fluticasone propionate, triamcinolone acetonide and clobetasol propionate induce additive effects in zebrafish embryos

Many synthetic glucocorticoids from medical applications occur in the aquatic environment. Whether they pose a risk for fish health is poorly known. Here we investigate effects of glucocorticoids fluticasone propionate (FLU) and triamcinolone acetonide (TRI) as single steroids and as ternary mixtures with clobetasol propionate (CLO) in zebrafish embryos. Exposure to FLU and TRI in a range of concentrations between 0.099 and 120.08 μg/L led to concentration-related decrease in muscle contractions and increase in heart rate at 0.98 and 1.05 μg/L, respectively, and higher. Genes encoding for proteins related to glucose metabolism (g6pca, pepck1), immune system regulation (fkbp5, irg1l, socs3, gilz) and matrix metalloproteinases mmp-9 and mmp-13 showed expressional alterations, as well as genes encoding for the progestin receptor (pgr) and corticosteroid dehydrogenase (hsd11b2). FLU accelerated hatching and led to embryotoxicity (immobilization and edema). Ternary mixtures (FLU + TRI + CLO) induced the same physiological and toxicological effects at concentrations of individual glucocorticoids of 11.1–16.37 μg/L and higher. Heart rate was increased in the mixture at concentrations as low as 0.0885−0.11 μg/L of each steroid. Glucocorticoids in mixtures showed additive activity; the fold-changes of transcripts of 19 target genes were additive. Together, our data show that glucocorticoids act additively and their joint activity may be of concern for developing fish in contaminated environments

Analysis and occurrence of endocrine-disrupting chemicals in airborne particles

This article presents an overview of the analytical methods for the determination of target endocrine-disrupting chemicals (EDCs) in airborne particles. Among EDCs, we selected four important groups of compounds (alkylphenols, bisphenol A, phthalates, and natural and synthetic sex hormones) because of their worldwide production, environmental ubiquity and toxicity. Due to their physical and chemical properties (high molecular weight, low/medium polarity and volatility), these EDCs can be present in the atmosphere mainly associated with particulate matter. EDCs linked to small particles (PM10 and PM2.5) can penetrate into the respiratory system and damage human health. We discuss aspects of analytical methodology, such as sampling, extraction, and determination. We review levels found in outdoor and indoor samples. According to the results reported, human exposure to these compounds, especially in indoor environments, should be investigated in more depth, since some compounds, such as dibutyl phthalate and diethyl phthalate, reach levels of μg/m3.Applied Analytical Chemistry Research Group (QANAP), University Institute of Research in Environmental Studies, Department of Analytical Chemistry, University of A Coruña, Campus da Zapateira, Rua da Fraga 10, A Coruña, Spain Water and Soil Quality Research Group, Department of Environmental Chemistry, Institute of Environmental Assessment and Water Research (IDAEA-CSIC), Jordi Girona 18-26, Barcelona, Spain Catalan Institute for Water Research (ICRA), Universitat de Girona, Emili Grahit, Parc Científic i Tecnològic, 101, Edifici H2O, Girona, SpainPeer reviewe