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The aquatic ecosystem is one of the most delicate environments, housing a diverse range of organisms, including fish, all of which are exposed to a wide variety of pollutants. The accumulation of these harmful substances in fish, which are part of the human diet, presents a significant health risk to humans. In our study, we have optimized an extraction technique to determine the presence of 25 high production volume chemicals in liver and skin samples taken from commonly consumed fish species. We have employed ultrasound-assisted extraction in conjunction with gas chromatography tandem mass spectrometry to achieve this goal. Apparent recoveries of the method ranged from 50% to 111% for both sample types with some exceptions such as most of the benzosulfonamides and benzothiazole. Additionally, the method's detection and quantification limits varied from 0.1 to 1.7 ng g−1 (dry weight, d.w) and 0.2–4.5 ng g−1 (d.w), respectively. Our investigation focused on three frequently consumed fish species in Tarragona: sea bass, sea bream, and turbot. Almost all of the samples we analysed contained traces of contaminants, with phthalates being the most commonly detected. The highest concentrations were observed for diethyl phthalate, with levels peaking at 8350 ng g−1 (d.w.). Organophosphate esters, such as triethyl phosphate and tributyl phosphate, also showed notable presence, with peak concentrations of 93.6 and 34.0 ng g−1 (d.w.), respectively. [Display omitted] • HPVC have been determined in fish and liver samples. • A method based on ultrasound-assisted extraction was optimized. • Most HPVC were present in the samples. • Benzothiazoles and benzosulfonamides determined for the first time in fish and liver. [ABSTRACT FROM AUTHOR]

Seafood plays an important role in diet because of its health benefits. However, the fact that chemical compounds such as high production volume chemicals may be present in seafood means that its consumption can be a potential risk for population. To assess the occurrence of HPVs and estimate the exposure and risk associated with their consumption, specimens of the most consumed seafood species in Catalonia and the Canary Islands, Spain, were collected and analysed. Results showed higher levels of HPVs in samples from Catalonia and a prevalence of phthalate esters and benzenesulfonamides over the other target compounds in samples from both locations. Multivariate analysis showed spatial differences between the mean concentration profiles of HPVs for the samples from Catalonia and the Canary Islands. Exposures were higher for the samples from Catalonia, although the intake of HPVs via seafood was not of any real concern in either of the locations. • HPVs were detected in all the analysed seafood samples. • HPV profiles enable the differentiation of Catalonia and Canary Islands samples. • Catalonia and Canary Islands seafood consumption pose no risk towards population. [ABSTRACT FROM AUTHOR]

Seafood consumption has become a potential exposure route towards high production volume chemicals (HPVs) due to the pathway of these compounds reaching the aquatic environment via industrial and domestic discharges. The present study focuses on the determination of phthalate esters (PAEs), organophosphate esters (OPEs), benzothiazoles (BTs), benzotriazoles (BTRs) and benzenesulfonamides (BSAs) in the ten most consumed fish species in Catalonia. A total of 120 commercially available seafood specimens were purchased throughout February 2019–February 2020 in three different stores (supermarket, local market, and local fishmonger) of the city of Tarragona, Spain, to cover the most typical places where seafood can be obtained. ΣOPEs, ΣBTs, ΣBSAs and ΣPAEs concentrations ranged between 5.99 and 139.45 ng g−1 w.w., 8.41–54.08 ng g−1 w.w., 8.38–304.47 ng g−1 w.w and 2.86–323.80 ng g−1 w.w., respectively. BTRs were not detected in any of the samples. PAEs and BSAs had similar contributions which combined represented nearly the 70% of detected compounds and sardine resulted as the species with the higher HPVs mean concentration. No considerable threat was posed due to the individual intake of these compounds via seafood consumption. • HPVs were determined in the ten most consumed seafood species from Catalonia. • HPVs mean concentrations trended as PAEs > BSAs > BTs > OPEs. • Sardine appeared as the most contaminated species. • No differences were found between low and high lipid content species. • Low risk concern is associated to the intake of HPVs present in seafood. [ABSTRACT FROM AUTHOR]

Phthalate esters are high production volume chemicals and are widely used as additives in the plastics industry. Since they are not chemically bound to the plastics, they can easily leach into the environment. They can also be transformed into phthalate monoesters via degradation or metabolization. As numerous studies have reported the negative effects of phthalate diesters and monoesters on marine biota, these contaminants are an emerging concern. In this article we review the most important analytical methods for determining phthalate esters in seawater, marine sediments and biota. The QuEChERS method and ultrasound-assisted extraction are the most common techniques for extracting solid samples, while solid-phase extraction is the most common technique for seawater samples. We also describe the occurrence and distribution of phthalate esters in the marine environment. Bis(2-ethylhexyl) phthalate, di-n-butyl phthalate and diisobutyl phthalate, as well as their metabolites, are the main compounds detected in the reviewed matrices. • Methods for determining phthalates in seawater, sediments and biota are reviewed. • GC and LC are the most applied techniques for PAE and MPE separation, respectively. • Extraction and clean-up techniques for liquid and solid marine samples are compared. • The presence of PAEs and MPEs in seawater, sediment and biota samples is discussed. • Little information about MPEs in seawater and sediment samples is available. [ABSTRACT FROM AUTHOR]

This paper investigates the occurrence and removal of 60 organic micropollutants (OMPs) including pharmaceuticals, personal care products, pesticides and per- and polyfluoroalkyl substances in a drinking water treatment plant (DWTP) treating raw water from the Ebro River (NE Spain). The behaviour of the OMPs was evaluated in each treatment: pre-ozonation, flocculation-coagulation-decantation-sand filtration, post-ozonation and granular activated carbon filtration. Thirty-one of the sixty OMPs studied were detected in source water with individual median concentrations below 10 ng L−1 for all the compounds except for caffeine (64.1 ng L−1). The highest concentration peaks in the source water were found for caffeine (124.5 ng L−1), terbuthylazine (52.0 ng L−1), imidacloprid (30.2 ng L−1) and paracetamol (25.6 ng L−1). Of the 31 compounds detected in the source water, 17 were also detected in the finished drinking water. Of these 17 compounds, 10 were PFASs, which indicated that this group of compounds had not been effectively removed throughout the drinking water treatments. The overall removal efficiencies of OMPs in the DWTP ranged from −50.9% to 100%. The most efficient removal technologies were ozonation and granular activated carbon. • 60 OMPs were monitored at an upgraded conventional drinking water treatment plant. • Treatment steps most markedly contributing to removal were pre-ozonation and GAC filtration. • The overall removal efficiency of the DWTP was 83.0%. • PFASs were not efficiently removed during water treatment. [ABSTRACT FROM AUTHOR]

• First nationwide study in Spain assessing exposure to phthalates by analysing sewage. • 17 sewage treatment plants serving 13 cities and ca. 6 million people sampled. • Estimated levels in urine close to levels reported in literature for 5 metabolites. • Average exposure levels for parent phthalates ranged from 2 to 1347 μg/(day∙inh). • Safe reference values of butylated phthalates exceeded in some sites. Phthalates are widely used plasticizers that produce endocrine-disrupting disorders. Quantifying exposure is crucial to perform risk assessments and to develop proper health measures. Herein, a wastewater-based epidemiology approach has been applied to estimate human exposure to six of the mostly used phthalates within the Spanish population. Wastewater samples were collected over four weekdays from seventeen wastewater treatment plants serving thirteen cities and ca. 6 million people (12.8 % of the Spanish population). Phthalate metabolite loads in wastewater were transformed into metabolite concentrations in urine and into daily exposure levels to the parent phthalates. Considering all the sampled sites, population-weighted overall means of the estimated concentrations in urine varied between 0.7 ng/mL and 520 ng/mL. Very high levels, compared to human biomonitoring data, were estimated for monomethyl phthalate, metabolite of dimethyl phthalate. This, together with literature data pointing to other sources of this metabolite in sewage led to its exclusion for exposure assessments. For the remaining metabolites, estimated concentrations were closer to those found in urine. Their 4-days average exposure levels ranged from 2 to 1347 μg/(day∙inh), exceeding in some sites the daily exposure thresholds set for di- i -butyl phthalate and di -n- buthyl phthalate by the European Food Safety Authority. [ABSTRACT FROM AUTHOR]

Wastewater-based epidemiology (WBE) has become a very useful tool to monitor a population's drug consumption or exposure to environmental and food contaminants. In this work, WBE has been applied to estimate tobacco consumption in seven Spanish regions. To this end, 24 h composite wastewater samples were taken daily for one week in 17 wastewater treatment plants, covering altogether a population of ca. 6 million inhabitants. The samples were treated by enzymatic deconjugation and the wastewater content of two human-specific nicotine metabolites (namely, cotinine and trans-3′-hydroxycotinine) was measured to estimate the daily consumption of nicotine. The population-weighted average nicotine consumption in the seven analyzed regions was 2.2 g/(day∙1000 inh.), without any daily pattern. This average estimated nicotine consumption value agreed with the value derived from official tobacco sales data. Differences in consumption among the seven studied regions were found, being Galicia, the region with the lowest rate, and the Basque Country and Catalonia those with the highest rates. However, no conclusive correlation was found between those values and the prevalence data taken from two different national surveys, nor sociodemographic and health data. This study demonstrates that this tool can complement other indicators in order to accurately assess tobacco consumption rates at regional and national levels and provides the most extensive application of the approach in the Spanish territory. Unlabelled Image • Nicotine metabolites measured in 17 wastewater treatment plants (WWTPs) • The nicotine consumed was estimated through wastewater-based epidemiology (WBE). • The mean per capita nicotine consumed daily was 2.2 mg (ca. 2.8 cigarettes). • Largest Spanish study on nicotine by WBE • The consumption estimates through WBE are consistent with official sales data. [ABSTRACT FROM AUTHOR]

· The method developed is based on direct injection of 900 µL. · Increasing the injection volume from 500 µL to 900 µL did not increase matrix effects. · Sub to low ng·L−1 MQLs were achieved without the need of pre-treatment of the sample. · Short chain PFASs are not removed from the drinking water treatment plant. · PFBA, PFPeA, PFHxS, PFOS, PFOA and PFHxA were the most abundant compounds. Per- and polyfluoroalkyl substances (PFASs) have been determined in waters intended for human consumption, causing concern due to their potential toxic effects in humans and the environment. Drinking water is acknowledged to be one of the major routes of exposure to PFASs, which has led to the implementation of regulatory guidelines for PFASs in drinking water. In this study a fast, simple, sensitive and cost-effective method is developed for the determination of 18 PFASs in river and drinking water. The proposed method consists of directly injecting 900 µL of sample into a liquid chromatograph coupled to a triple quadrupole mass analyser, which involves minimal sample treatment as the sample only needs to be filtered. The method was validated in influent and effluent water from a drinking water treatment plant. Strong matrix effects were found for some of the target PFASs, and matrix-matched calibration curves were performed to enable accurate (87–114%) and precise (%RSD between 3 and 18%) quantification (n = 5, at 5 and 75 ng·L−1) with very good sensitivity (method quantitation limits between 0.1 and 2.0 ng·L−1). The method was applied to water samples from the influent and effluent of a drinking water treatment plant located in Catalonia (Spain), as well as in tap water and bottled water. The most abundant PFAS in all the types of water was PFBA, which represents 48%, 49%, 66% and 69% of total PFASs found in influent, effluent, tap and bottled water respectively. Relative mean abundances and the sum of mean concentrations in influent and effluent water suggests poor removal of PFASs during drinking water treatment. The concentrations of PFASs in bottled waters were generally lower than those in tap waters. [ABSTRACT FROM AUTHOR]

Wastewater-based epidemiology (WBE) is a well-established approach that can provide objective and real-time data on the consumption of substances such as pharmaceuticals. However, most of the studies reported so far compares consumption data obtained using WBE with those derived from prescription data from public health systems, which is often incomplete and might represent a source of uncertainty. This study aims to compare the measured pharmaceutical consumption back calculated with the WBE approach with consumption derived from dispensed pharmaceuticals in two regions of Spain, managed by two different Health Systems. To do so, a group of 17 pharmaceuticals, including the most representative ones of every therapeutic family, were monitored in influent wastewater (IWW) samples collected over a week campaign in spring 2022 at four different wastewater treatment plants (WWTPs) in Spain: two WWTPs in Madrid city (center of Spain) and two WWTPs in Catalonia (Northeast of Spain). Population-normalized daily loads (PNDL) revealed that the patterns of pharmaceutical occurrence in the different WWTPs are very similar, being acetaminophen, 4-acetamidoantipyrine and valsartan the pharmaceuticals with the highest PNDL values: 17162 ± 1457 mg day -1 1000 inh -1 for acetaminophen, 2365 ± 696 and 2429 ± 263 mg day -1 1000 inh -1 for 4-acetamidoantipyrine, 2006 ± 541 and 2041 ± 352 mg day -1 1000 inh -1 for valsartan. Pharmaceutical PNLDs were then transformed into measured pharmaceutical consumption (MC) and compared with dispensed consumption (DC) data obtained from the pharmacies in the catchment area where the WWTPs are located. A ratio MC/DC within 0.8 to 1.2 was obtained for 11 out of the 17 studied pharmaceuticals. Highlighting a match in all the cardiovascular system pharmaceuticals, with the exception of losartan (1.29-1.39 ratio) and valsartan (1.35-1.43) in all WWTPs. In summary, the degree of correlation between MC/DC is higher than those previously reported comparing with the prescribed pharmaceutical consumption., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

The decline in fish populations and the depletion of marine resources have sparked concerns about sustainable fish production, driving the innovation of new aquaculture methods. While some argue that wild fish are healthier than farmed fish due to less exposure to contaminants and pathogens, wild fish can accumulate contaminants from more contaminated water sources. The slower growth of wild fish and their longer exposure to the environment may contribute to higher pollutant levels in fish tissues. In this study, we focus on 25 contaminants considered as high production volume chemicals (HPVCs), such as organophosphate esters (OPEs), benzothiazoles (BTs), benzosulfonamides (BSAs) and phthalates (PAEs). The compounds were extracted from the edible part of the fish using the QuEChERS method and analysed by gas chromatography-tandem mass spectrometry. A total of 74 samples were analysed from three of the most commonly consumed species in Catalonia, Spain (turbot, sea bass and sea bream). Two samples of each species were collected each month, one form farmed and one from wild origin. In general, the compounds were found in all the samples in a wide concentrations range, although no significant differences were observed between the mean concentration of wild and farmed samples. Although similar mean concentrations for the OPEs, BTs and BSAs were found between farmed and wild origin samples, PAEs were more frequently detected in farmed samples. Di-n-octyl phthalate and diethyl phthalate showed the highest concentrations in all fish samples, with values up to 19505 and 17605 ng g -1 (d.w.), in sea bass and sea bream, respectively. Di-(2-ethylexyl)-adipate proved to be the most relevant carcinogenic compound, with no associated health risk. Despite the detection of the studied HPVCs, no health risk was associated with the consumption of these three fish species., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Ltd.. All rights reserved.)

The common use of benzothiazoles, benzotriazoles and benzenesulfonamides has led to widespread ubiquity in several environmental matrices. Their occurrence in edible fish could represent an additional exposure route for the population. The present study aims to develop a method for the simultaneous determination of these three compound families in seafood samples. Based on QuEChERS extraction, different salt combinations and clean-up strategies have been evaluated to achieve the highest recoveries while reducing the matrix effect in low and high lipidic content species. The best results were obtained with the original method salts and the lipid-selective push-through clean-up, which combined with gas chromatography-tandem mass spectrometry led to recoveries between 50 and 112% with negligible matrix effects and method detection limits between 0.15-9.50 ng g -1 dw. The application of the method to commercially available samples confirmed the presence of BTs as well as BSAs, with the latter being determined in seafood for the first time. Exposure and risk assessment calculations indicated a minor risk for the population when consuming fish., Competing Interests: Declaration of Competing Interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Authors report financial support was provided by Spain Ministry of Science and Innovation., (Copyright © 2023 Elsevier B.V. All rights reserved.)

This manuscript introduces Wastewater-Based Epidemiology (WBE) and its potential in the assessment of diverse aspects related to public health. This methodology can provide data in a relatively short temporal and local scale (typically dialy-weekly at the municipal level) on consumption patterns of illicit drugs (e.g. cocaine or cannabis), licit substances of abuse (e.g. alcohol) by measuring their consumption biomarkers (i.e. the original unmetabolized substance or some of its metabolite) in wastewater. Besides discussing the fundaments, advantages and shortcomings of WBE, it reviews some of the main precedents at international level and most remarkable activities that have been taken place in this field in Spain. Finally, the Spanish Network of Wastewater-Based Epidemiology (ESAR-Net) as is presented. ESAR-Net is an Excellence Network that sums up the efforts of the most relevant Spanish researchers in the field of WBE, aiming to investigate future perspectives of this methodology and its impact on Public Health competences in Spain.