Detection, occurrence and fate of pharmaceuticals and personal care products in a typical Mediterranean Coastal Wetland

Trabajo presentado en la 2nd International Conference on Risk Assessment of Pharmaceuticals in the Environment (ICRAPHE), celebrada en Barcelona (España), del 28 al 29 de noviembre de 2019The >Anthropocene> as new geological area view as the period during which human activity has been the dominant influence on climate and the environment gains defenders year after year. An important anthropogenic hazard is the environmental contamination due to the release of chemical substances affecting ecosystems that is growing parallel to the increase of population. One of the most representative contaminant related to the human impact are the contaminants of emerging concern (CECs), particularly, pharmaceuticals and personal care products. The work focused on determination of 35 Pharmaceuticals and Personal Care Products in water and sediment samples of 33 sampling stations located in Albufera Natural Park (an area of 21 thousand hectares, it is located in Valencia, Spain). The extraction was based on solid-phase extraction (SPE) using Strata X cartridges treated with sodium dodecyl sulfate (SDS) or mixed mode weak anion exchange cartridges. The determination was carried out by liquid chromatography-tandem mass spectrometry (LC-MS/MS) with a triple-quad using two precursor ¿ product ion transitions for each compound with the exception of ibuprofen that only gave one product ion in the multiple selected reaction monitoring mode (MRM)

La contaminación por Fármacos y productos del cuidado personal en el Parque Natural de L'Albufera

Trabajo presentado en las I Jornadas Antropocen@, celebradas en Burjassot, Valencia (España), el 12 de diciembre de 2019Peer reviewe

Determination of 18 opioid compounds in urban wastewater (Valencia, Spain) by HPLC-MS/MS

Resumen del trabajo presentado en el SETAC Europe 30th Annual Meeting, celebrado en modalidad virtual del 3 al 7 de mayo de 202

Systematic assessment of extraction of pharmaceuticals and personal care products in water and sediment followed by liquid chromatography–tandem mass spectrometry

Two solid-phase extraction methods were systematically studied to determine 32 pharmaceuticals and personal care products in water and sediments by ultrahigh-performance liquid chromatography–tandem mass spectrometry. One involves HLB cartridges activated with sodium dodecyl sulfate before the passage of the sample to form an ion pair with cationic analytes, and the other uses mixed HLB–cation exchange cartridges. The accuracy of the sodium dodecyl sulfate method was good for most compounds (recoveries of 61–120% with relative standard deviation less than 23%). However, the recoveries for atorvastatin, codeine, paracetamol, flufenamic acid, and salicylic acid were approximately 50% and for omeprazole and triclocarban were even lower (from 0 to 12%). The detection limits were 1.65–25 ng L-1 in water and 0.33–4.00 ng g-1 (dry weight) in sediment. The recoveries for the mixed-mode cartridge (Strata-X-CW) method ranged from 57% to 120% with relative standard deviation less than 21%, with the exception of codeine [25% (water)], metformin [11% (sediment)], paracetamol [48% (sediment)], and salicylic acid [32% (sediment)]. The detection limits were 1.65–38.35 ng L-1 in water and 0.33–10 ng g-1 (dry weight) in sediment. Both methods followed the same pattern when applied to water. For sediments, the recoveries, which offer good performance, were not very high, although 60% of the compounds had recoveries greater 80%. The methods were applied to the analysis of surface water and sediments from the Albufera Natural Park (Spain). Twenty-seven of 32 analytes were detected in the samples analyzed.The research that led to these results received funding from the Spanish Ministry of Science, Innovation and Universities and the European Regional Development Fund through the project WETANDPAC (RTI2018-097158-B-C31) and from the Generalitat Valenciana through the project ANTROPOCEN@ (PROMETEO/2018/155). Daniele Sadutto acknowledges the Generalitat Valenciana for his Santiago Grisolia grant: “GRISOLIAP/ 2018/102, Ref CPI-18-118.”.Peer reviewe

Pharmaceutical contamination in a Mediterranean coastal Lagoon: an indicator of complex interactions between societies and wetlands

Trabajo presentado en el 29th Annual Meeting of the Society of Environmental Toxicology and Chemistry (SETAC Europe), celebrado en Helsinki (Finlandia) del 26 al 30 de Mayo 2018This field study assesses the occurrence of emerging contaminants (EC) of the Albufera Natural Park. This protected wetland has as an area of 21120 hectares and it is located 10 km to the South of Valencia City (Spain). It consists of a highly eutrophic coastal lagoon surrounded mainly by rice fields that occupy the primitive marshland. The Turia River, to the north, the Jucar River, to the South, and a network of irrigation channels bring fresh water to the Albufera system. The study was focus on about 30 compounds including Personal Care Products and Pharmaceutical Compounds, including acid, basic and neutral. The interest in detecting environmental contaminants in different matrices (mostly water, soil and sediment) is increasing in the last years. This for their relevant impact on the global ecosystem. The selected compounds, in this study, constitute an important block of organic contaminants frequently found for many reasons(2). The results evidenced the presence of many of the selected EC both in water and sediment. The most abundant ones are analgesic and anti-inflammatory drugs (salicylic acid, diclofenac), antihypertensive (furosemide), anticoagulant (warfarin), stimulants (caffeine) and preservatives (parabens). The relation-ship between the presence of these compounds and the anthropic pressure in the area was carefully analysedThis work has been supported by the Spanish Ministry of Economy and Competitiveness and the ERDF (European Regional Development Fund) through the project CGL2015-64454-C2-1 and by the Generalitat Valenciana through the project ANTROPOCEN@ (PROMETEO/2018/155). This work has been supported by the Spanish Ministry of Economy and Competitiveness and the ERDF (European Regional Development Fund) through the project CGL2015-64454-C2-1. D. Sadutto also knowledge the Generalitat Valenciana for his “Santiago Grisolía” grant “GRISOLIAP/2018/102, Ref CPI18-118”

Different types of Solid Phase Extraction for about 30 organic compounds successively determined by HPLC/MS-MS (QqQ)

Trabajo presentado en la XVIII Reunión Científica de la Sociedad Española de Cromatografía y Técnicas Afines (SECyTA 2018), celebrado en Granada del 2 al 4 de octubre del 2018In the last years, the interest in detecting environmental contaminants in different matrices (mostly sediment, soil and water) is increasing because their more relevant impact on the global ecosystem [1]. In this study, we focused on determination of Pharmaceutical Compounds and Personal Care Products. The study was conducted on about 30 compounds, including acid, basic and neutral. The selected compounds constitute an important block of organic contaminants frequently found for many reasons, such as industrial waste, expired or unused medicinal product not disposed in the right way, and excretion of drugs and their metabolites derived from therapeutic treatments [2]. Some of the selected compounds as metformine required a careful optimization of the extraction conditions. The analytical method was based on solvent extraction (if a solid matrix is used) followed by solid-phase extraction (SPE). The chromatographic separation was performed using an Agilent 1260 ultra-high performance liquid chromatography (UHPLC) with a Phenomenex Kinetex C18 column of 1.7 µm of particle size at constant flow rate of 0.2 mL min-1. The mobile phase consisted of deionized water and methanol, both with 0.1% formic acid (for positive mode) and with 0.1% ammonium fluoride (for negative mode), working in gradient mode. The UHPLC was coupled to an Agilent 6410 triple quadrupole mass spectrometer with an electrospray ionization source working both in positive (ES+) and negative mode (ES-). Different steps of the extraction procedure were considered to optimize the recovery of the compounds. Regarding the solid-phase extraction (SPE), 2 different stationary phases of cartridges were tested: Phenomenex Strata-X 33 µm Polymeric Reversed Phase 200 mg/6 mL and Phenomenex Strata-X-CW 33 µm Polymeric Weak Cation 200 mg/6 mL. Moreover the activation of cartridges was considered before the passage of sample with and without the use of a 2mM Sodium Dodecyl Sulfate (SDS) solution. In each test the extracts were reconstituted with 1 mL of 70:30 water/methanol like the chromathographic mobile phase. Sediment and water samples were analysed. The recovery¿ results obtained are very interesting, ranging from 30% to 120%. The use of SDS solution improves the recovery of a number of compounds (mostly of basic character). As well as Polymeric Cation stationary phase has given a good results for some compounds.This work has been supported by the Spanish Ministry of Economy and Competitiveness, the ERDF (European Regional Development Fund) through the project, CGL2015-64454-C2-1-R, and Santiago Grisolia program (GRISOLIAP/2018/102), Ref CPI-18-118.Peer reviewe

Detection and occurrence of 62 pesticides in a Typical Mediterranean Coastal Wetland by HPLC-MS/MS

Resumen del trabajo presentado en el SETAC Europe 30th Annual Meeting, celebrado en modalidad virtual del 3 al 7 de mayo de 2020.The use of pesticides is between two and three million tons per year, 70% of all pesticides being used in Europe and in The United States following by China (1). Their role is associated with the control of many insects, weeds and other organisms that can damage agricultural crops. The physicochemical properties of some of these compounds, such as their solubility in water, justifies the importance of monitoring their presence in surface water by runoff and in ground water by leaching (2). The purpose of this study was to establish the patterns and concentrations of pesticides in surface water from a typical Mediterranean wetland, the Albufera Natural Park (Valencia, Spain). To this end, this study was focused on the evaluation of the occurrence and environmental fate of 62 pesticides, some of the most widely used. This area consists of a highly eutrophic coastal lagoon surrounded mainly by rice fields. We took 52 samples in as many points of the Park. The sampling was performed two-time in the same year (2019), to value the different environmental distribution in the time. The extraction was based on solid-phase extraction (SPE) using cartridges of Reversed Phase (StrataX). The determination was carried out by liquid chromatography-tandem mass spectrometry (LC-MS/MS) with a triple-quad using two precursor → product ion transitions for almost all compounds in the Dynamic Multiple selected Reaction Monitoring mode (MRM). Chromatographic separation was performed using Luna® 3µm C18 column. The mobile phase consisted of deionized water and methanol, both with ammonium formate10 mM (positive mode). The results evidenced the presence of many selected Emerging Contaminant (EC) in surface water. The most abundant ones are herbicides and fungicides, as the prochloraz. This work produced an accurate outlook of a basal state for the Albufera Natural Park and could be developed in the context of a chronic monitoring of this site. Furthermore, the results pinpointed the need of further studies on the short and long term ecotoxicological impact in animal and vegetal species.This work has been supported by the Spanish Ministry of Economy and Competitiveness and the ERDF (European Regional Development Fund) through the project CICLIC subproject WETANPACK (RTI2018-097158-B-C31) and by the Generalitat Valenciana through the project ANTROPOCEN@ (PROMETEO/2018/155); D. Sadutto also knowledge the Generalitat Valenciana for his “Santiago Grisolía” grant “GRISOLIAP/2018/102, Ref CPI-18-118”

Screening Emerging Contaminants of Wastewater Origin in Boreal Sediments and Surface Waters

Resumen del trabajo presentado en el SETAC Europe 30th Annual Meeting, celebrado en modalidad virtual del 3 al 7 de mayo de 2020.Emerging contaminants are chemicals that have not previously been discovered in the environment and are typically not monitored and regulated under environmental laws. These chemicals have the potential to cause known or unknown environmental effects. Emerging contaminants can enter the aquatic environment through agricultural and urban runoff, as well as through municipal wastewater processing. Sources of these chemicals can be common household and hygiene products, medication for both humans and animals, industrial processes and pesticides from agriculture. The type of these chemicals can range from different pharmaceuticals and ingredients of personal care products (PCPs) to ingredients of plastic materials. In this study, chemicals from municipal wastewater treatment plant effluents in Finland were under investigation. Selected chemicals were screened from both sediment and water samples from different lakes, rivers and streams located in Western, Eastern and Southern Finland. The sampling sites were chosen according to their location in relation to active or decommissioned municipal wastewater treatment plants. The list of compounds to be screened comprised of 31 chemicals, mainly consisting of pharmaceuticals and personal care product ingredients, with the addition of for example Caffeine and Bisphenol A (BPA). The sediment samples underwent Liquid Phase Extraction (LPE) followed by Solid Phase Extraction (SPE). For water samples only SPE was performed after initial filtration. The samples were analyzed with High Performance Liquid Chromatography (HPLC) coupled with Tandem Mass Spectrometry (MS/MS). Out of the 31 screened chemicals 20 were detected, ranging from antibiotics, nonsteroidal anti-inflammatory drugs, cardiovascular disease medication, opiates and analgesics to PCP ingredients. The data gathered from this screening is valuable in developing current ecotoxicological testing to work better with new emerging contaminants and in enhancing the capabilities of tools used in risk assessment

The Albufera Natural Park (Valencia, Spain): the impact of Pharmaceutical and Personal Care compounds

Trabajo presentado en la GLOBAQUA Final Conference: Water river management under water scarcity and multiple stressors, celebrada en Barcelona del 18 al 19 de diciembre de 2018In the last years, the interest in detecting environmental contaminants in different matrices (mostly sediment, soil and water) is increasing because their more relevant impact on the global ecosystem. In this study, we focused on determination of Pharmaceutical Compounds and Personal Care Products. The study was conducted on about 30 compounds, including acid, basic and neutral. The selected compounds constitute an important block of organic contaminants frequently found for many reasons, such as industrial waste, expired or unused medicinal product not disposed in the right way, and excretion of drugs and their metabolites derived from therapeutic treatments. This field study is intended to propose an analytical methodology to assess and monitor the occurrence of emerging contaminants (EC) of the Albufera Natural Park. Has an area of 21120 hectares and it is located 10 km to the South of Valencia City. It consists of a highly eutrophic coastal lagoon surrounded mainly by rice fields that occupy the primitive marshland. The Turia River, to the north, the Jucar River, to the South, and a network of irrigation channels bring fresh water to the Albufera system. Different analytical methods to determine ca. 30 EC were developed and optimized to obtain the best efficiency and sensitivity. Samples analysed included 35 water samples and 20 sediment samples for L¿Albufera Lake and its surrounding area. Fig. 1 shows the location of the sampling points. The extraction is based on solid-phase extraction (SPE) using two different stationary phases of cartridges Reversed Phase and Polymeric Weak Cation Phase, provided suitable recoveries to extract this compounds from water or to clean up the sediment extracts. The determination was carried out by liquid chromatography-tandem mass spectrometry (LC-MS/MS) with a triple-quad using two precursor ¿ product ion transitions for each compound in the multiple selected reaction monitoring mode (MRM). The results evidenced the presence of many of the selected EC both in water and sediment. All selected pharmaceuticals were detected in water samples. The highest concentration was for thiamphenicol (up to 2 µg/L). In sediments, twenty-three pharmaceuticals were found, the most frequently detected (> half of the samples) were salicylic acid, buthylparaben, caffeine, clofibric acid, diclofenac, flufenamic acid, furosemide, thiamphenicol, tramadol, triclosan and warfarine. However, amoxicillin and ibuprofen were those at the highest concentrations, 84.8 and 100.1 ng/g dry weight (d.w.). The most abundant ones are analgesic and anti-inflammatory drugs (salicylic acid, diclofenac), antihypertensive (furosemide), anticoagulant (warfarin), stimulants (caffeine) and preservatives (parabens). These data pointed out that is important to optimize removal treatments and to create new barriers to avoid the discharges of EC to these sensitive environments. Overall, this methodology produced an accurate outlook of a basal state for the Albufera Natural Park and could be developed in the context of a chronic monitoring of this site. Furthermore, the results pinpointed the need of further studies on the short and long term ecotoxicological impact in animal and vegetal species.This work has been supported by the Spanish Ministry of Economy and Competitiveness and the ERDF (European Regional Development Fund) through the project CGL2015-64454-C2-1 and by the Generalitat Valenciana through the project ANTROPOCEN@(PROMETEO/2018/155). D. Sadutto knowledges the Generalitat Valenciana for his “Santiago Grisolía” grant “GRISOLIAP/2018/102, Ref CPI-18-118”. R. Álvarez-Ruiz also acknowledges the Spanish Ministry of Economy and Competitiveness and the ERDF (European Regional Development Fund) for his FPI grant BES-2016-078612.Peer reviewe

Pollution of wetlands with emerging contaminants due to the anthropic activity: The case of Valencia's Albufera Natural Park (Spain)

Trabajo presentado en la European Geosciences Union General Assembly (EGU), celebrada en Viena (Austria), del 7 al 12 de abril de 2019Currently, several scientist defend the starting of a new geological era, the “Anthropocene” where elements of earth are subjected to constant change, principally caused by anthropogenic forces (human-related) [1]. An important anthropogenic hazard is the environmental contamination that affects ecosystems [2]. Production, consumption and elimination of chemical compounds, such as pharmaceuticals and personal care products, are constantly growing and consequently also their presence in the environment. For this reason is very important to determine these compounds and to develop new analytical method. This study focused on determination of 30 Pharmaceuticals and Personal Care Products, including acid, basic and neutral [3]. Different analytical methods were developed and optimized to obtain the best efficiency and sensitivity. Samples analysed included water and sediment samples for L’Albufera Lake (Valencia, Spain) and its surrounding area. The extraction is based on solid-phase extraction (SPE) using a Reversed Phase and mixed mode with a Polymeric Weak Cation Phase. The determination was carried out by liquid chromatography-tandem mass spectrometry (LC-MS/MS) with a triple-quad using two precursor → product ion transitions for each compound in the multiple selected reaction monitoring mode (MRM). The results evidenced the presence of many of the selected EC both in water and sediment. The most abundant ones are analgesic and anti-inflammatory drugs (salicylic acid, diclofenac), antihypertensive (furosemide), anticoagulant (warfarin), stimulants (caffeine) and preservatives (parabens). These data pointed out that is important to optimize removal treatments and to create new barriers to avoid the discharges of EC to these sensitive environments. Overall, this methodology produced an accurate outlook of a basal state for the Albufera Natural Park and could be developed in the context of a chronic monitoring of this site. Furthermore, the results pinpointed the need of further studies on the short and long term ecotoxicological impact in animal and vegetal species.This work has been supported by the Generalitat Valenciana through the project ANTROPOCEN@ GVPROMETEO2018-155. D. Sadutto also knowledge the Generalitat Valenciana for his “Santiago Grisolía”gran