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Plastics, particularly mesoplastics, dominate beach debris and act as carriers of hazardous chemicals, either initially present in plastics or absorbed from the surrounding environment. In this study, mesoplastics were collected from five beaches in the southern region of Spain to investigate their potential impact on marine life. In vitro assays employing fish liver cells (PLHC-1) were conducted to evaluate the toxicity of methanolic extracts derived from intact mesoplastics and after simulated photodegradation. LC-MS analysis of the methanolic extracts revealed the presence of organophosphate esters, phthalates, and phthalate alternatives. The extracts from photodegraded plastics generally showed higher cytotoxicity, ability to generate reactive oxygen species (ROS), and genotoxicity (micronuclei formation) than those from intact mesoplastics. All the extracts induced EROD activity in PLHC-1 cells, indicating the presence of significant amounts of CYP1A inducers in beach mesoplastics. Thus, mesoplastics contain chemicals able to induce cytotoxicity and genotoxicity in PLHC-1 cells, and further photodegradation of mesoplastics facilitates the release of additional chemicals, increasing the overall toxicity. This work also highlights the usefulness of cell-based assays to better define the risks of plastic pollution., 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.)

Guiana dolphins, Sotalia guianensis, are vulnerable to extinction along their distribution on the Brazilian coast and assessing chemical pollution is of utmost importance for their conservation. For this study, 51 carcasses of Guiana dolphins were sampled across the Brazilian coast to investigate legacy and emerging brominated flame retardants (BFRs) as well as the naturally-produced MeO-BDEs. PBDEs and MeO-BDEs were detected in all samples analyzed, whereas emerging BFRs were detected in 16 % of the samples, all in Rio de Janeiro state. PBDE concentrations varied between 2.24 and 799 ng.g -1 lipid weight (lw), emerging BFRs between 0.12 and 1.51 ng.g -1 lw and MeO-BDEs between 3.82 and 10,247 ng.g -1 lw. Concentrations of legacy and emerging BFRs and natural compounds varied considerably according to the sampling site and reflected both the local anthropogenic impact of the region and the diversity/mass of biosynthesizers. The PBDE concentrations are lower than what was found for delphinids in the Northern Hemisphere around the same sampling period and most sampling sites presented mean concentrations lower than the limits for endocrine disruption known to date for marine mammals of 460 ng.g -1 lw, except for sampled from Santa Catarina state, in Southern Brazil. Conversely, MeO-BDE concentrations are higher than those of the Northern Hemisphere, particularly close to the Abrolhos Bans and Royal Charlotte formation, that are hotspots for biodiversity. Despite the elevated concentrations reported for this group, there is not much information regarding the effects of such elevated concentrations for these marine mammals. The distinct patterns observed along the Brazilian coast show that organobrominated compounds can be used to identify the ecological segregation of delphinids and that conservation actions should be planned considering the local threats., 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 © 2023 The Authors. Published by Elsevier B.V. All rights reserved.)

Inhalation of airborne fine particulate matter (PM 2.5 ), dust ingestion, and dermal contact with dust are important pathways for human exposure to different contaminants, such as organophosphate esters (OPE), compounds that are widely used as flame retardants and plasticizers. There are limited studies assessing the extent of the contamination of OPE in indoor airborne PM 2.5 . This study offers a novel approach by examining various indoor environments, such as homes, workplaces, and means of transport, where people typically spend their daily lives. The goal is to provide a comprehensive assessment of daily exposure to these pollutants. Both PM 2.5 and dust samples were collected in order to determine the concentration levels of 17 different OPEs. Fifteen OPEs in PM 2.5 and 16 in dust samples were detected. Concentration levels in indoor air ranged from 4.37 to 185 ng/m 3 (median 24.4 ng/m 3 ) and from 3.02 to 36.9 μg/g for the dust samples (median 10.2 μg/g). Estimated daily intakes (EDIs) of OPEs were calculated for adults, yielding median values of 3.97 ng/(kg bw × day) for EDI Inhalation , 5.89 ng/(kg bw × day) for EDI Dermal , and 1.75 ng/(kg bw × day) for EDI Ingestion . Such levels lie below human health threshold risk limits, although in some cases they could be only 2 times below the threshold for carcinogenic risk, with a main contribution from tris(2-chloroethyl) phosphate (TCEP). Given this threshold proximity, additional exposure to these chemicals from other pathways, such as food ingestion, gas phase exposure, and/or inhalation of coarser particles (PM 10-2.5 ), could therefore lead to health limit exceedances.

Ship refit and repair operations in shipyards generate aerosol emissions with high potential for environmental impacts. Metal-bearing nano-, fine and coarse particles are incidentally formed and can be released to indoor and ambient air and the aquatic environment. This work aimed to further the understanding of these impacts by characterising particle size-resolved chemical composition (15 nm - 10 μm), organophosphate esters (OPEs) content (e.g., plasticisers) and cytotoxic and genotoxic potential. Results showed that nanoparticle emissions (20-110 nm) took place in bursts, coinciding with the use of mechanical abraders and spray-painting guns. Tracers of these activities were Sc, V, Cr, Co, Ni, Cu, Rb, Nb, and Cs. Key components were V and Cu, probably sourcing from nanoadditives in the coatings. Abrasion of coatings also emitted OPEs, especially from old paints. Toxicity assessments consistently evidenced hazardous potential for the different endpoints assessed, for a number of samples. Exposures to spray-painting aerosols were linked with reduced cell viability (cytotoxicity), significant generation of reactive oxygen species (ROS), and increases in micronuclei frequency (genotoxicity). Even though spray-painting did not contribute significantly to aerosol mass or number concentrations, it was a major driver of potential health effects. Results suggest that aerosol chemical composition (e.g., content in nano-sized Cu or V) may have a larger impact on toxicity than aerosol concentration. While direct human exposures may be prevented using personal and collective protective equipment and environmental release can be minimised by enclosures and filtration systems, impacts on ambient air and the aquatic environment cannot be fully prevented. The continued use of good practices (exhaust, dilution, general ventilation systems, PPE, already in place) is encouraged to reduce inhalation exposures inside the tents. Understanding the size-resolved chemical and toxicological properties of aerosols is key to reducing human health and environmental impacts of ship refit operations in shipyards., 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 © 2023 The Authors. Published by Elsevier B.V. All rights reserved.)

Drinks are an essential part of human diet, which makes them a source of human exposure to plasticizers such as organophosphate esters (OPEs). The current study provides new information about sixteen OPE levels in 75 different samples (tap water, packed water, cola drinks, juice, wine and hot drinks). Tap water mean levels (40.9 ng/L) were statistically higher than packed water mean levels (4.82 ng/L), mainly due to the contribution of tris(2-chloroisopropyl) phosphate (TCIPP) and tris(2-butoxyethyl) phosphate (TBOEP) that may come from PVC water pipes. Over 90% of samples presented at least one OPE, where regular cola drinks had the highest mean concentrations (2876 ng/L). There was a significantly higher presence of OPEs in added sugar beverages than sugar free drinks, especially for 2-ethylhexyl diphenyl phosphate (EHDPP), which might be related not only to packaging materials but to the added sugar content. Estimated daily intakes (EDIs) in normal and high-exposure scenarios were 2.52 ng/kg bw/day and 7.43 ng/kg bw/day, respectively. Human risk associated with beverages ingestion showed regular cola drinks, juice and tap water as the groups with the highest hazard quotients (HQs). Although OPE exposure was below to safety limits, it should be noted that EHDPP values for regular cola group must be cause of concern, and other routes of exposure such as food ingestion or air inhalation should be also considered., 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 © 2023 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

We revisit current understanding of the chemical complexity of different kinds of particulate vulcanised elastomers widely used in playgrounds and sports fields, adding new data on trace element and organophosphate ester contents of used tyre and EDPM crumb rubber. Enrichments in elements such as Zn, S, Co, Bi and Nd relate to the vulcanised mixtures created during manufacture. Zinc concentrations vary across an order of magnitude, being highest in our used tyre particulate samples (up to 2.4 %). In contrast, other trace element variations are due to coloured pigments causing increases in Cu and Zr (blue), Cr (green), and Fe and Sn (red and yellow) concentrations. The use of pale fillers such as CaCO 3 and clay minerals (rather than carbon black) strongly influences Ca and Al concentrations, which are much higher in the coloured EPDM than in black used tyre crumb rubber. Representatives from all three of the main organophosphate ester (OPE) groups, namely chlorinated (e.g. TCEP, TCIPP, TDCPP), alkyl (e.g. TEHP, TEP, TNBP, TBOEP) and aryl (e.g. TPHP, EHDPP, TCP) were identified, confirming how these chemicals are commonly used in modern rubber compounding as flame retardants and plasticisers. Elevated concentrations of TEHP (up to 117 μg/g) in coloured-coated used tyre turf infill crumb rubbers were traced to the coating rather than the crumb rubber itself. The presence and weathering behaviour of OPEs in recreational crumb rubber materials deserve closer investigation. The ecological "onehealth" impact of potentially toxic substances present in recreational crumb rubbers will depend on if and how they are released during play and sports activities, maintenance procedures, and natural weathering. We argue that detailed chemical data on these materials should be available to buyers, as manufacturers strive to reduce ecotoxin content as part of the quest towards sustainable use and recycling of vulcanised elastomers., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Teresa Moreno reports financial support was provided by Fundacion ACS., (Copyright © 2023 The Authors. Published by Elsevier B.V. All rights reserved.)

Marine mammals are one of the groups of animals most affected by marine pollution including that by organic compounds which, besides bearing recognised harmful effects to adults, they may also affect foetuses through placental transfer. In this study we analysed samples of fin whale (Balaenoptera physalus) females and their foetuses collected in the western Iceland summer feeding grounds in 2018. Three different families of organic pollutants: organophosphate esters (OPEs); halogenated flame retardants (HFRs); and short chain chlorinated paraffins (SCCPs), were analysed and their placental transfer investigated. HFRs were detected in 87.5% of females and 100% of foetus samples with concentrations that ranged between nd-15.4 and 6.37-101 ng/g lipid weight (lw), respectively. OPEs were detected in all samples, both from females (85.8-567 ng/g lw) and foetuses (nq-1130 ng/g lw). SCCPs were detected in 87.5% of female samples and 100% of foetal samples with concentrations that ranged between nd-30.9 and nq-574 ng/g lw, respectively. For OPE compounds, a significant negative correlation was observed between the logarithm maternal transfer ratio and their log K ow, indicating that a high lipophilicity reduced placental transfer rate. Interestingly, the decabromodiphenyl ethane (DBDPE) was the compound with the highest log K ow but also the one that was transferred the most from mothers to foetuses, calling for in-depth research on this pollutant. These results constitute the first evidence of mother-calf transfer of plasticizers and flame retardants in fin whales. Further investigations are needed to determine their potential effects on this species and other groups of animals., 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 © 2022 The Authors. Published by Elsevier Ltd.. All rights reserved.)

This study aimed to the examination of the levels and effects of organobromine compounds (polybrominated diphenyl ethers: PBDEs and methoxylated brominated diphenyl ethers: MeO-PBDEs), in Sparus aurata native to the Lagoon of Bizerte. For that, different biomarkers of exposure (somatic indices, superoxide dismutase, and catalase activities) and effect (malondialdehyde level, histopathologic alterations, and DNA damage) as well as pollutant levels were measured in specimens collected from this impacted ecosystem and the Mediterranean Sea as a reference site. Bizerte Lagoon PBDE fish levels were higher than the Mediterranean Sea, whereas MeO-PBDEs were higher in the reference site. Fish from Bizerte Lagoon presented a higher hepatosomatic index, lower catalase and superoxide dismutase activity, higher level of malondialdehyde, and higher percentage of DNA tail in comparison to fish from the reference area. The histological study of the liver indicated substantial lesions in fish from the polluted site. The results showed strong positive correlations between the concentrations of the PBDE or MeO-PBDE and the MDA and DNA tail % levels and negative correlations for the activities of enzymes of SOD and CAT. Consequently, these findings could suggest a potential link between exposure to these pollutants and the observed biomarker responses in the Bizerte Lagoon seabream. Taken together, these results highlight the importance of biomarker selection and the selected sentinel fish species as useful tools for biomonitoring of aquatic pollution., (© 2022. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Flame retardants (FRs) are widely used in consumer products including furniture foam and electronic equipment such as computers, monitors and TVs. Over time, FRs can easily migrate into the surrounding environments. Since brominated FRs (BFRs) has been determined of high concern due to their environmental persistence, bioaccumulation and potential toxicity, novel FRs have emerged. The present study was aimed at identifying and quantifying the indoor levels of 41 legacy and novel FRs, which include 20 OPFRs and 21 HFRs (8 PBDEs, 3 HBCDDs, 5 NBFRs and 5 DECs) in Tarragona Province (Catalonia, Spain). The results have confirmed the presence of both legacy and novel FRs in air and dust of homes, schools and offices. To the best of our knowledge, this is the first European study measuring OPFRs at office environments and also confirming the presence of the following OPFRs: TEP, TCIPP, T2IPPP, TPPO, DCP, TMCP and B4IPPPP in indoor air, even some of them at high levels. OPFRs in general and TCIPP in particular showed high concentrations in air (94,599 pg/m 3 and 72,281 pg/m 3 , respectively) and dust (32,084 ng/g and 13,496 ng/g, respectively) samples collected in indoor environments. HBCDDs were found at high levels in dust (32,185 ng/g), whereas the presence of PBDEs and DECs were low in both matrices (<160 pg/m 3 in air and <832 ng/g in dust). NBFRs showed higher levels than the two legacy FRs groups, which is supported by the current restrictions of these FRs (640 pg/m 3 in air and 1291 ng/g in dust). Samples of schools had significantly lower levels of NBFRs, but significantly higher concentrations of HFRs in air than in home samples, while dust levels of HFRs were significantly lower than those in samples of offices. Regarding human health risks, the current assessment suggests that those derived from exposure to FRs were lower -although close- to assumable risks, evidencing the potential of FRs for non-carcinogenic and carcinogenic risks, mainly due to the exposure to TCIPP, which was the main contributor together with ΣHBCDDs and also EHDPP., 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 © 2021 The Authors. Published by Elsevier B.V. All rights reserved.)

Concentrations of organophosphate esters (OPEs) plasticizers were analysed in the present study. Fifty-five fish samples belonging to three highly commercial species, European sardine (Sardina pilchardus), European anchovy (Engraulis encrasicolus), and European hake (Merluccius merluccius), were taken from the Western Mediterranean Sea. OPEs were detected in all individuals, except for two hake samples, with concentrations between 0.38 and 73.4 ng/g wet weight (ww). Sardines presented the highest mean value with 20.5 ± 20.1 ng/g ww, followed by anchovies with 14.1 ± 8.91 ng/g ww and hake with 2.48 ± 1.76 ng/g ww. The lowest OPE concentrations found in hake, which is a partial predator of anchovy and sardine, and the higher δ 15 N values (as a proxy of trophic position), may indicate the absence of OPEs biomagnification. Eleven out of thirteen tested OPEs compounds were detected, being diphenyl cresyl phosphate (DCP) one of the most frequently detected in all the species. The highest concentration values were obtained for tris(1,3-dichloro-2-propyl) phosphate (TDClPP), trihexyl phosphate (THP), and tris(2-butoxyethyl) phosphate (TBOEP), for sardines, anchovies, and hakes, respectively. The human health risk associated with the consumption of these fish species showing that their individual consumption would not pose a considerable threat to public health regarding OPE intake., (Copyright © 2021 The Authors. Published by Elsevier Ltd.. All rights reserved.)

This study aimed to devise innovative, tailor-made, appealing, tasty and semi-industrialized dishes, using sustainable and under-utilized seafood species (bib, common dab, common carp, blue mussel and blue whiting), that can meet the specific nutritional and functional needs of children (8-10-years), pregnant women (20-40-years) and seniors (≥60-years). Hence, contests were organised among cooking schools from 6 European countries and the best recipes/dishes were reformulated, semi-industrially produced and chemically and microbiologically evaluated. The dishes intended for: (i) children and pregnant women had EPA + DHA and I levels that reached the target quantities, supporting the claim as "high in I"; and (ii) seniors were "high in protein" (24.8%-Soup&#95;S and 34.0%-Balls&#95;S of the energy was provided by proteins), "high in vitamin B12", and had Na contents (≤0.4%) below the defined limit. All dishes reached the vitamin D target value. Sausages&#95;C, Roulade&#95;P, Fillet&#95;P and Balls&#95;S had a well-balanced protein/fat ratio. Roulade&#95;P presented the highest n-3 PUFA/n-6 PUFA ratio (3.3), while Sausages&#95;C the lowest SFA/UNS ratio (0.2). Dishes were considered safe based on different parameters (e.g. Hg-T, PBDEs, Escherichia coli). All represent dietary sources contributing to meet the reference intakes of target nutrients (33->100%), providing valuable options to overcome nutritional and functional imbalances of the three groups., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Loggerhead turtles (Caretta caretta) voluntarily ingest floating plastic debris and hence are chronically exposed to plastic additives, but very little is known about the levels of these compounds in their tissues. This work studied the presence of organophosphate esters (OPEs) on sea turtles collected from two different areas in the western Mediterranean, some of their prey and some floating plastic debris. OPEs were detected in all the samples analysed and ∑OPEs ranged from 12.5 to 384 ng/g wet weight (ww) in the turtles from the Catalan coasts, with a mean value of 21.6 ng/g ww, and from 6.08 to 100 ng/g ww in the turtles the Balearic Islands, with a mean value of 37.9 ng/g ww. Differences in ∑OPEs were statistically significant, but turtles from the two regions did not differ in their OPE profiles. As per turtle's prey, ∑OPEs ranged from 4.55 to 90.5 ng/g ww. Finally, marine plastic litter showed ∑OPEs concentrations between 10.9 and 868 ng/g. Although most compounds were present in both potential sources of contamination, prey and plastic debris, the OPE profiles in loggerhead turtles and these sources were different. Some OPEs, such as tris(2-isopropylphenyl) phosphate (T2IPPP), tripropyl phosphate (TPP) and tris(2-butoxyethyl) phosphate (TBOEP), were detected in plastic debris and turtle muscle but not in their prey, thus suggesting that ingestion of plastic debris was their main source. Contrarily, the levels of triethyl phosphate (TEP), diphenyl cresyl phosphate (DCP), 2-isopropylphenyl diphenyl phosphate (2IPPDPP) and 4-isopropylphenyl diphenyl phosphate (4IPPDPP) in turtle muscle were much higher than in jellyfish, their main prey, thus indicating a biomagnification potential. Regular ingestion of plastic debris and contamination from their prey may explain why ∑OPEs in loggerhead turtles is much higher than the values reported previously for teleost fishes and marine mammals from the western Mediterranean., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

The influence of the type of smoking process (natural/liquid; hot/cold) and salt (NaCl or KCl) on the levels of polybrominated diphenyl ethers (PBDEs) and polycyclic aromatic hydrocarbons (PAHs) in smoked salmon was evaluated. One parent compound - BDE 47 - and two methoxylated forms - 2'-MeO-BDE-68 and 6-MeO-BDE-47 - were detected in all the samples. Among the 14 PAHs analysed, naphthalene was the most abundant followed by phenanthrene and fluorene. Only smoked salmon treated with NaCl presented quantifiable levels of chrysene and benzo[b]fluoranthene. Among the four smoking processes evaluated, natural smoke led to higher levels of PAHs. Risk characterization tools, such as hazard index (HI) and incremental lifetime cancer risk (ILCR), showed that the risk of both PBDEs and PAHs to human health through the consumption of smoked salmon was very low., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Delta ecosystems are areas of high ecologic and economic values, where wildlife commonly shares the territory with intensive agricultural activities, particularly, rice cultivation and seafood production. This work aimed at evaluating the occurrence of a wide spectrum of pesticides and transformation products in the water of irrigation and drainage channels of the Ebro River Delta (NE Spain) during the main rice-growing season, when pesticide application is at its peak. Furthermore, the impact that these contaminants may have on local ecosystems and seafood production activities was assessed. A total of 35 pesticides, mainly associated with rice cultivation, out of the 66 analyzed were detected. Bentazone, propanil, MCPA, acetamiprid, and triallate were found at the μg/L level. Cybutryne, despite being banned in the European Union, was measured for the first time in the area and at concentrations above its environmental quality standard (11-49 ng/L). Sixteen additional banned pesticides were also detected at trace levels, likely due to their desorption from soil and sediment particles. Despite its dilution when discharged into the bay, this study demonstrates that the agricultural use of pesticides may have important effects on water quality and may cause a serious hazard for aquatic non-target organisms, although other factors such as temperature and salinity may play also a relevant role. Bentazone, cybutryne, dicofol, imidacloprid, MCPA, and propanil may pose a moderate to high risk for aquatic organisms at the concentration levels measured during the rice-growing season. The co-occurrence of pesticides may result in a high risk for aquatic organisms in all sampling locations. The finding of the EU Watch List insecticides imidacloprid and acetamiprid at concentrations above their maximum acceptable method detection limit calls for control of their use and revision of their legal status., 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 © 2020 Elsevier Ltd. All rights reserved.)

This study aimed to evaluate the presence of ultraviolet filters (UV-Fs), benzotriazoles, pyrethroids and per- and polyfluoroalkyl substances (PFASs) in freshwater and wastewater from the northern Antarctic Peninsula region. All water samples analyzed contained UV-Fs residues and high concentrations were detected in anthropogenic impacted sites (< LOD up to 1300 ng/L). Likewise, benzotriazoles were detected in all water samples (< LOQ-920 ng/L). Regarding suspended particulate matter, almost all UV-Fs and all benzotriazoles were measured at concentrations ranging from < LOQ to 33 µg/g dry weight. Pyrethroids were also detected (< LOQ-250 ng/L) and their presence implies the existence of a gateway to the Antarctica Peninsula from other regions. The data confirmed the presence of PFASs (< LOD-7500 ng/L) in this area, in agreement with previous studies. In light of these results, extended monitoring in Antarctica should be carried out to perform a reliable environmental risk assessment leading to propose recommendations to minimize the anthropic impact.

There is a worldwide growing use of chemicals by our developed, industrialized, and technological society. More than 100,000 chemical substances are thus commonly used both by industry and households. Depending on the amount produced, physical-chemical properties, and mode of use, many of them may reach the environment and, notably, the aquatic receiving systems. This may result in undesirable and harmful side-effects on both the human and the ecosystem's health. Mediterranean rivers are largely different from Northern and Central European rivers in terms of hydrological regime, climate conditions (e.g. air temperature, solar irradiation, precipitation), and socio-economics (e.g. land use, tourism, crop types, etc.), with all these factors leading to differences in the relative importance of the environmental stressors, in the classes and levels of the pollutants found and their environmental fate. Furthermore, water scarcity might be critical in affecting water pollution because of the lowered dilution capacity of chemicals. This work provides raw chemical data from different families of microcontaminants identified in three selected Mediterranean rivers (the Sava, Evrotas, and Adige) collected during two sampling campaigns conducted in 2014 and 2015 in three different matrices, namely, water, sediments, and biota (fish). More than 200 organic micropollutants were analyzed, including relevant groups like pharmaceuticals, personal care products, perfluorinated compounds, pesticides, pyrethroid insecticides, flame retardants, and persistent organic pollutants. Data obtained were summarized with some basic statistics for all compound families and matrices analyzed. Observed occurrence and spatial patterns were interpreted both in terms of compound physical-chemical properties and local environmental pressures. Finally, their spatial distribution was examined and their ecotoxicological risk in the water phase was assessed. This allowed locating, at each basin, the most polluted sites ("hot spots") and identifying the respective river basin specific pollutants (RBSPs), prioritizing them in terms of the potential ecotoxicological risk posed to the aquatic ecosystems., 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 © 2020 Elsevier B.V. All rights reserved.)

Intensive and extensive use of pesticides has contributed to their wide distribution in soil, air, and water. Due to their detrimental effects on non-target organisms, different technologies have been considered for their removal. In this work, three hydrophobic pesticide active compounds, namely, chlorpyrifos, cypermethrin, and oxadiazon, were selected to study the potential for their removal from aqueous media by a microalgae consortium. An abiotic and a killed control (thermally inactivated dead microalgae biomass) were employed to clarify their removal pathways, and pesticide content was quantified in liquid and biomass phases for 7 days. At the final time, total degradation (biodegradation plus photodegradation) contributed to the removal of 55% of oxadiazon, 35% of chlorpyrifos, and 14% of cypermethrin. Furthermore, more than 60% of chlorpyrifos and cypermethrin were removed by sorption onto microalgae biomass. Overall, the three pesticides showed high removal from the liquid phase. O,O-diethyl thiophosphate was identified in the liquid phase as a transformation product of chlorpyrifos formed by microalgae degradation. Phycoremediation was coupled with anaerobic degradation of the microalgae biomass containing the retained pesticides by sorption through biochemical methane potential tests. Anaerobic digestion was not inhibited by the pesticides as verified by methane production yields. The removal efficiency of the pesticides in the digestate was as follows: chlorpyrifos > cypermethrin > oxadiazon. These results highlight the potential of low-cost algal-based systems for the treatment of wastewater or effluents from agrochemical industries. The integration of wastewater treatment with biogas production through anaerobic digestion is a biorefinery approach that facilitates the economic feasibility of the process., 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 © 2020 Elsevier B.V. All rights reserved.)

PBDEs, HBCD, novel DBDPE, PBEB and HBB, dechloranes, OPFRs and natural MeO-PBDEs were monitored in muscle of striped dolphins (Stenella coeruleoalba) from the Mediterranean Sea collected in three time periods (1990, 2004-2009 and 2014-2018). PBDEs levels decreased about 60% in under three decades, from 5067 ± 2210 to 2068 ± 2642ngg -1 lw, evidencing the success of their ban. Most PBDEs were found in all the samples, with BDE-47, -99, -154, -100 and -153 as the main contributors. Found in 71.4% of the samples, α-HBCD was stable through time and usually -1 lw. Dec 602 was the main dechlorane with stable concentrations around 1200 ngg -1 lw, but a declining trend might have started in the last years. OPFRs concentrations were stable and showed the highest concentrations of all FRs in 2014-2018: 6253 ± 11,293ngg -1 lw. TBOEP and TNBP contributed to most of the OPFR concentration, the former with decreasing levels by 96%. MeO-PBDEs showed mean concentrations between 600 and 700ngg -1 lw in all periods. Non-targeted analysis allowed the identification and semi-quantification of additional chlorinated pollutants, such as polychlorinated terphenyls (PCTs) (levels decreasing by 81% to a current 770 ngg -1 lw mean) and polychlorinated diphenyl ethers (PCDEs) (decreasing by 83% to a current 3200ngg -1 lw) in Mediterranean marine mammals for the first time., 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., (Crown Copyright © 2020. Published by Elsevier B.V. All rights reserved.)

Plastic litter pollution is increasing in the seas and oceans worldwide, raising concern on the potential effects of plasticizer additives on marine fauna. In this study, muscle samples of 30 bogues (Boops boops; Linneaus, 1758) from the North Western Mediterranean Sea were analysed to assess the concentrations of 19 organophosphate flame retardant (OPFR) compounds and to inspect any relationship with microplastic ingestion and relative levels of anthropization. Out of the 19 OPFRs analysed, 6 compounds were detected, being tri-n-butyl phosphate (TNBP), 2-ethylhexyldiphenyl phosphate (EHDPP) and triphenylphosphine oxide (TPPO) the most abundant. As expected, OPFR concentrations were higher in samples collected off the most anthropized area of the city of Barcelona than in those from the Cap de Creus Marine Protected Area, while no significant correlation was detected between OPFR concentrations and microplastic ingestion. The results of this manuscript provide a first evidence of OPFR presence in the muscle of the bogue and identify the coastal area off Barcelona as a possible concentration area for contaminants, further supporting the use of the bogue as an indicator species of plastic pollution in the Mediterranean Sea., 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 © 2020 Elsevier Ltd. All rights reserved.)

The presence of pyrethroid compounds in hepatic tissue of Guiana dolphins (Sotalia guianensis) is reported for the first time. Twelve pyrethroids were determined in 50 animals from eight locations of the Brazilian coast. The highest average concentration of total pyrethroids (∑PYR) was 1166 ng.g -1 lw, with values ranging from 148 to 5918 ng.g -1 lw, in Ilha Grande Bay, Rio de Janeiro State, while the Espírito Santo State had the highest median, 568 ng.g -1 lw. Permethrin was the predominant compound in most areas, contributing for 42% to 81% of the ∑PYR, whereas cypermethrin was the most abundant compound in Guanabara and Sepetiba bays (79% and 81%, respectively), both located in Rio de Janeiro State. Biological factors were not correlated with pyrethroids concentration. Tetramethrin and es/fenvalerate compounds were negatively correlated to the age, suggesting degradation/metabolization capacity in these animals that increases throughout life. Despite being metabolized and excreted, the wide use of these pollutants is reflected in relevant concentrations found in Guiana dolphins. This is the first study evaluating pyrethroids in a representative number of hepatic samples and covering >2600 km of coast. The overall lack of information on pyrethroids in cetaceans highlights the importance of understanding the profile and distribution of these pollutants in dolphins which exclusively inhabit the Southwestern Atlantic coast., 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 © 2020 Elsevier B.V. All rights reserved.)

Pesticides introduced inadvertently or deliberately into environment by global agricultural practices have caused growing public concern, therefore the search of approaches for elimination of such xenobiotics should be motivated. The degradation of hydrophobic pesticides including chlorpyrifos, dicofol and cypermethrin were assayed with the white-rot fungus Trametes versicolor. Experiments were set at realistic concentration as 5 μg L -1 , and both culture medium and biologic matrix were analyzed for pollutants residues. Results showed that the first step was due to a fast adsorption, which also played an important role, accounting for more than 90% removal in average. Then mass balances proposal evidenced the biodegradation of the adsorbed pollutants, demonstrating efficient depletion as 94.7%, 87.9% and 93.1%, respectively. Additionally, the related degradation metabolites were identified using ultra performance liquid chromatography coupled to high resolution mass spectrometry. Two compounds, namely O,O-diethyl thiophosphate and diethyl phosphate were detected as transformation products of chlorpyrifos, whereas dicofol was degraded into benzaldehyde that is first time to be reported. It also confirms the degradation capability of T. versicolor. Our results suggest that T. versicolor is a potential microorganism for bioremediation of hydrophobic pesticide contaminated environments., Competing Interests: Declaration of competing interest We declare that no conflict of interest exists in the submission of this manuscript., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Pollution of the marine environment by litter composed of plastics is a growing concern. Chemical additives such as organophosphate flame retardants (OPFRs), which are added to plastics to improve their qualities, are in focus because they allegedly cause adverse effects on marine fauna. Here we analyse OPFR levels in the muscle of fin whales because, as a mysticete, this cetacean obtains its food by filter-feeding and is thus highly vulnerable to marine litter. Moreover, the fin whale performs long-range migrations from low-latitude areas in winter to high-latitude areas in summer, a trait that makes it a potentially good large-scale biomonitor of pollution. We also analyse OPFR levels in its main prey, the krill Meganyctiphanes norvegica, to assess transfer through diet. The samples analysed consisted of muscle tissue from 20 fin whales and whole-body homogenates of 10 krill samples, all collected off West Iceland. From the 19 OPFRs analysed, we detected 7 in the fin whale and 5 in the krill samples. Tri-n-butyl phosphate (TNBP), Isopropylated triphenyl phosphate (IPPP) and Triphenylphosphine oxide (TPPO) were the most abundant compounds found in both species. Mean ∑OPFR concentration, expressed on a lipid weight basis, was 985 (SD = 2239) ng g -1 in fin whale muscle, and 949 (SD = 1090) ng g -1 in krill homogenates. These results constitute the first evidence of the presence of OPFRs in the tissues of fin whales. Furthermore, they seem to support the non-significance of bioaccumulation of OPFRs through lifespan and of biomagnification trough the food web., 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 © 2020 Elsevier B.V. All rights reserved.)

Silicone (polydimethylsiloxane or PDMS) wristbands and cotton T-shirts were used to assess the exposure of e-waste recyclers in Dhaka, Bangladesh to polybrominated diphenyl ethers (PBDEs), novel brominated flame retardants (NBFRs), dechlorane plus (DPs), and organophosphate esters (OPEs). The median surface-normalized uptake rates of PBDEs, NBFRs, DPs, and OPEs were 170, 8.5, 4.8, and 270 ng/dm 2 /h for wristbands and 5.4, 2.0, 0.94, and 23 ng/dm 2 /h for T-shirts, respectively. Concentrations of Tris(2-chloroethyl) phosphate (TCEP), Tris(1,3-dichloro-2-propyl) phosphate (TDCIPP), Tri-m-cresyl phosphate (TmCP), Bis(2-ethlyhexyl) tetrabromophthalate (BEH-TEBP), and Dechlorane plus (DPs) in wristbands were significantly correlated with those in T-shirts. Wristbands accumulated ~7 times more mass than T-shirts, especially of compounds expected to be mainly in the gas phase. We introduce the silicone "sandwich" method to approximate the easily releasable fraction (ERF) from T-shirts, hypothesized to be related to dermal exposure. ERFs varied from 6 to 75% of total chemical accumulated by T-shirts and were significantly negatively correlated with compounds' octanol-air partition coefficient (log K oa ). The median daily exposure doses via dermal transfer from the front of the T-shirt to the front body trunk were 0.32, 0.13, 0.11, and 9.1 ng/kg-BW/day for PBDEs, NBFRs, DPs, and OPEs, respectively. The evidence of e-waste recycler exposure to flame retardants in this low income country, lacking protective personal equipment, calls for measures to minimize their exposure and for chemical management regulations to consider exposures to chemicals in waste products., 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 © 2020. Published by Elsevier B.V.)

Occurrence of traditional (PBDEs) and novel (HBB, PBEB, DBDPE) brominated flame retardants, as well as the natural compounds of MeO-PBDEs, were studied in a shellfish species (Hexaplex trunculus) sampled from Bizerte Lagoon. PBDE and MeO-PBDE mean concentrations in murex soft tissues were 187 and 264 ng g -1  lw respectively. The alternative flame retardants were not identified. The sum of PBDE and MeO-PBDE levels recorded in murex from the investigated aquatic ecosystem were comparable or a relatively lower than those reported for other organisms from other regions across the world. The amount of PBDE and MeO-PBDE concentrations from the Bizerte Lagoon recorded in murex were comparable or a relatively lower than those recorded from other areas across the world for other species. There is not a danger to the population health with regard to PBDE intakes associated with the consumption of murex in Bizerte city. We believe that this is the first study of the analysis of these pollutants in marine gastropod mollusks from Tunisian aquatic areas.

PBDEs, HBCD, DBDPE, PBEB and HBB, dechloranes and OPFRs, as well as natural MeO-PBDEs were monitored in muscle tissue of three dolphin species from the southwestern Indian Ocean (Delphinus delphis, Sousa plumbea and Tursiops aduncus) collected between 2012 and 2015. The mean PBDE concentration was 416 ± 333 ng g -1 lw. BDE-47 was found in all samples and was almost half the total PBDE contamination. BDE-209, BDE-100 and BDE-99 were present in ≥85% of the samples. HBCD was detected in just two samples at 20 and 330 ng g -1 lw. PBEB and HBB were not detected, while DBDPE was in all samples but always below its limit of quantification. Dec 602 was the only quantifiable dechlorane at 232 ± 549 ng g -1 lw. Mean OPFR concentration was 10452 ± 11301 ng g -1 lw. TBOEP was found in all samples making up most of the total OPFR contamination. MeO-PBDEs were detected in all samples at 114 ± 137 ng g -1 lw. Data on flame retardants in biota and environmental samples from the southwestern Indian Ocean are scarce and, as a result, comparisons are difficult. However, data from other marine predators in the region, such as penguins, suggest that further studies are needed to determine if these concentrations are the consequence of a high local contamination or widespread thoughout the Indian Ocean., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

The study aim was to determine a range of relevant persistent and emerging pollutants in oysters produced in an aquaculture facility located in an important production area, to assure their safety for human consumption. Pollutants, including 16 PAHs, 3 butyltins (BTs), 29 flame retardants (FRs, including organophosphate and halogenated FRs), 35 pesticides (including 9 pyrethroid insecticides) and 13 personal care products (PCPs, including musks and UV filters), were determined in oysters' tissues collected during one year in four seasonal sampling surveys. The seasonal environmental pollution on the production site was evaluated by water and sediment analysis. Furthermore, oysters' nutritional quality was also assessed and related with the consumption of healthy seafood, showing that oysters are a rich source of protein with low fat content and with a high quality index all year around. Results showed that most analysed pollutants were not detected either in oyster tissues or in environmental matrixes (water and sediments). The few pollutants detected in oyster tissues, including both regulated and non-legislated pollutants, such as a few PAHs (fluorene, phenanthrene, anthracene, fluoranthene, pyrene and indenopyrene), FRs (TPPO, TDCPP, DCP, BDE-47, BDE-209 and Dec 602) and PCPs (galaxolide, galaxolidone, homosalate and octocrylene), were present at low levels (in the ng/g dw range) and did not represent a significant health risk to humans. The observed seasonal variations related to human activities (e.g. tourism in summer) highlights the need for environmental protection and sustainable resource exploration for safe seafood production., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Classic (polybromodiphenyl ethers, PBDEs) and emerging halogenated flame retardants (HFRs) such as hexabromobenzenze (HBB), pentabromoetilbenzene (PBEB), decabromodiphenyl ethane (DBDPE) and halogenated norbornenes (HNs), as well as naturally produced methoxylated-PBDEs (MeO-PBDEs), were analyzed in 12 sediment and 30 urchin (Paracentrotus lividus) samples collected from Bizerte Lagoon in northern Tunisia. Levels of HFRs in the sediments ranged from nd to 51.8 ng/g dry weight (dw), while MeO-PBDEs were not detected. As regards levels in urchins, concentrations of PBDEs, HNs and MeO-PBDEs ranged from 3.67 to 56.9, 4.52 to 116 and nd to 364 ng/g lipid weight (lw), respectively. Thus, levels of naturally occurring compounds were higher than those of an anthropogenic origin. As regards HFRs, the highest contribution comes from HNs with levels ranging between 9.98 and 143 ng/g lw. HN and PBDE concentrations in sea urchin are similar or slightly lower than other reports for other species, while total MeO-PBDE concentrations are higher. The comsumption of sea urchins in Bizerte city is not a threat to public health concerning PBDE intakes., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Eight PBDE congeners, three emerging brominated flame retardants, five dechloranes and eight MeO-PBDEs were monitored in tissues (muscular, adipose, brain) and fur of southern elephant seal and Antarctic fur seal of the South Shetland Islands, Antarctic Peninsula. Total PBDEs and total dechloranes concentrations ranged between n.d.-6 ng/g lw. While PBDEs were not detected in brain tissue, Dec 602 was found in brain tissue of both seal species indicating that dechloranes -with potential neurological toxicity- could cross the blood-brain barrier. Emerging brominated flame retardants were not detected in any sample and only two MeO-PBDEs, which are of natural origin, were found. The presence of the detected compounds in biota from the Antarctic evidences their long-range transportation, being of special interest the detection of emerging compounds such as dechloranes. This is the first time that these contaminants have been detected in marine mammals from the Antarctic. BDE-47 concentrations were lower than previously reported for the same species, suggesting a successful effect of the existing regulation and bans on PBDEs. CAPSULE ABSTRACT: Halogenated flame retardants were in tissues of Antarctic seals proving long-range transport. Dechloranes showed similar behaviour to PBDEs, additionally they crossed the BBB., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Fish samples of different species (i.e. rainbow trout (Onchorhynchus mykiss), barbel (Barbus barbus) and European chub (Squalius cephalus)) were collected from the Sava River Basin for a preliminary investigation of the levels of PCDD/Fs, PCBs, PBDEs and PFAS as a whole. Concentrations of PCDD/Fs, in terms of pg WHO-TEQ/g ww, were below the maximum limit established at the Commission Regulation (EU) No 1259/2011. On the contrary, when DL-PCBs were also included, levels increase up to 11.7 pg WHO-TEQ PCDD/Fs+DL-PCBs /g ww in a particular case, with two samples out of a total of ten exceeding the maximum set at this EU Regulation and the EQS established at the European Directive regarding priority substances in the field of water policy (0.0065 ng WHO-TEQ PCDD/Fs+DL-PCBs /g ww). A similar trend was also observed for NDL-PCBs, whit the same two samples, from the lower stretch of the river basin, exceeding the maximum limit allowed at the EU Regulation (125 ng/g ww). For PBDEs, levels found in all the samples exceeded the EQS (0.0085 ng/g ww) up to more than a thousand times and 40% of the samples presented PFOS values above the EQS. Data from this study were compared to values reported at the literature for fish from other geographical areas., (Copyright © 2018. Published by Elsevier B.V.)

The present study investigated the effects of maternal exposure to the widely used pyrethroid insecticides, permethrin and esfenvalerate, on fetal testicular steroidogenesis. Pregnant Sprague-Dawley rats were administered permethrin at doses of 1, 10, 50, or 100 mg/kg/day, or esfenvalerate at 0.1, 1, 7.5 or 15 mg/kg/day, by gavage, from gestation day (GD) 13 to 19. Testicular testosterone production and the expression of several key genes necessary for cholesterol and androgen synthesis and transport were assessed in GD 19 male fetuses. Dams treated with 100 mg/kg/day of permethrin or 15 mg/kg/day of esfenvalerate showed clinical signs of neurotoxicity. The highest dose of esfenvalerate also resulted in reduced maternal body weight gain throughout the treatment period. In the fetal testes, mRNA expressions of HMG-CoA synthase and reductase, SR-B1, StAR, P450scc, 3βHSD, P450 17A1, and 17βHSD were not affected by exposure to either pyrethroid. No significant change was observed in ex vivo testosterone production. In conclusion, in utero exposure to permethrin or esfenvalerate has no effect on the testosterone biosynthesis pathway in the fetal rat testis up to maternal toxic doses., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Determining the exposure and magnitude at which various pollutants are differentially assimilated at the breeding and non-breeding grounds of migratory wildlife is challenging. Here, the possibility of applying the migratory connectivity framework to understanding contamination in birds is illustrated by considering flame retardants in inviable eggs of a migratory raptor, the black kite (Milvus migrans). The occurrence and concentration of legacy and emerging compounds in eggs from the southeastern peri-urban area of Madrid city, central Spain, were compared with those from Doñana National Park in southern Spain. A much higher occurrence and concentration of multiple polybrominated diphenyl ethers and Dechlorane 602 were found in Madrid than Doñana, but the opposite patterns were found for Dechlorane Plus. Individuals from these and other breeding areas in western Europe showed a strong intermixing pattern over widespread wintering areas in Africa, as assessed by ringing recoveries and movements tracked by satellite devices. This diffuse migratory connectivity reveals breeding areas as the main contamination grounds. High contamination burdens sequestered in eggs point to rapid assimilation of these compounds before laying, associated with important emission sources in Madrid, especially landfills of partially incinerated urban refuse, and other anthropogenic operations. Diet composition regarding aquatic vs. terrestrial prey, and bioaccumulation and biomagnification processes are suggested to explain differential assimilation of some compounds, especially Dechlorane Plus in Doñana, although a local emission source polluting this area cannot be ruled out. Insight from the migratory connectivity framework can help to disentangle large-scale patterns of contaminant uptake and refocus attention on key regions and potential causes of chemical hazards in declining migratory species and human populations., (Copyright © 2018 Elsevier Inc. All rights reserved.)

The interest for environmental issues and the concern resulting from the potential exposure to contaminants were the starting point to develop methodologies in order to evaluate the consequences that those might have over both the environment and human health. Considering the feature of POPs, including PBDEs, such as bioaccumulation, biomagnification, long-range transport and adverse effects even long time after exposure, risk assessment of POPs requires specific approaches and tools. In this particular context, the MERLIN-Expo tool was used to assess the aquatic environmental exposure of Adige River to PBDEs and the accumulation of PBDEs in humans through the consumption of possible contaminated local aquatic food. The aquatic food web models provided as output of the deterministic simulation the time trend of concentrations for twenty years of BDE-47 and total PBDEs, expressed using the physico-chemical properties of BDE-47, in aquatic organisms of the food web of Adige River. For BDE-47, the highest accumulated concentrations were detected for two benthic species: Thymallus thymallus and Squalius cephalus whereas the lowest concentrations were obtained for the pelagic specie Salmo trutta marmoratus. The trend obtained for the total PBDEs, calculated using the physico-chemical properties of BDE-47, follows the one of BDE-47. For human exposure, different BDE-47 and total PBDEs concentration trends between children, adolescent, adults and elderly were observed, probably correlated with the human intake of fish products in the daily diet and the ability to metabolize these contaminants. In detail, for the adolescents, adults and elderly a continuous accumulation of the target contaminants during the simulation's years was observed, whereas for children a plateau at the end of the simulation period was perceived., (Copyright © 2018 Elsevier Inc. All rights reserved.)

The goal of this work is to study the presence of 17 different pyrethroids and chlorpyrifos in animal origin food samples, including chicken, beef, fish, eggs and milk. The samples were analyzed by GC/NCI-MS/MS in order to determine their insecticide concentration levels, the relation between the amount of insecticides and the lipid content, as well as their isomeric composition. Bifenthrin, cypermethrin, cyhalothrin, permethrin, deltamethrin and chlorpyrifos have been detected in real samples. The highest levels find were verified for chlorpyrifos (45.7 μg L -1 , 17.5 μg kg -1 ww) and cypermethrin (2.75 μg L -1 , 14.7 μg kg -1 ww) in milk and beef, respectively. The estimate of daily intake showed that none of these insecticides exceeded the safety limits of the acceptable daily intake values. A strong correlation between the amount of pesticides and lipid content was found for beef, fish and chicken samples. Regarding the isomers, a predominance of cis isomers in samples contaminated with cypermethrin was verified., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

UV filters (UV-Fs) constitute a heterogeneous group of chemicals used as protection against the effects of UV radiation, widely used in all sort of goods and ubiquitous in the environment. The presence of these chemicals in fish is a matter of concern, because many UV-Fs display hormonal activity. In this study, muscle, gills, and liver from 11 Mugil liza individuals from the highly urbanized Guanabara Bay (Rio de Janeiro, Brazil) were analysed in order to detect eight UV-Fs and metabolites (4-dihydroxybenzophenone [BP1] (2-hydroxy-4-methoxybenzophenone [BP3], 4-methylbenzylidiene camphor [4MBC], ethylhexyl methoxycinnamate [EHMC], ethylhexyl dimethyl p-aminobenzoic acid [ODPABA], octocrylene [OC], 4-hydroxybenzophenone [4HB], and 4,4'-dihydroxybenzophenone [4DHB]) using liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). Results showed that both target UV-Fs and metabolites were ubiquitous in the analysed tissues. Lower concentrations were observed in muscle and gills (3.07-31.6ngg -1 dry weight (dw)), whereas in liver significant amounts of metabolites (5.47-451ngg -1 dw) were present. With the concentrations determined in the fish, an estimation of the daily intake revealed that consumption of muscle in the diet represent from 0.3 to 15.2ng UV-Fs (kg body weight -1 ) d -1 , higher than those reported in fish for selected persistent organic pollutants (POPs)., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Emerging chemical contaminants [e.g. toxic metals speciation, flame retardants (FRs) and perfluorinated compounds (PFCs), among others], that have not been historically recognized as pollutants nor their toxicological hazards, are increasingly more present in the marine environment. Furthermore, the effects of environmental conditions (e.g. temperature and pH) on bioaccumulation and elimination mechanisms of these emerging contaminants in marine biota have been poorly studied until now. In this context, the aim of this study was to assess, for the first time, the effect of warmer seawater temperatures (Δ = + 4°C) and lower pH levels (Δ = - 0.4 pH units), acting alone or combined, on the bioaccumulation and elimination of emerging FRs (dechloranes 602, 603 and 604, and TBBPA), inorganic arsenic (iAs), and PFCs (PFOA and PFOS) in two estuarine bivalve species (Mytilus galloprovincialis and Ruditapes philippinarum). Overall, results showed that warming alone or combined with acidification promoted the bioaccumulation of some compounds (i.e. dechloranes 602, 604, TBBPA), but also facilitated the elimination of others (i.e. iAs, TBBPA). Similarly, lower pH also resulted in higher levels of dechloranes, as well as enhanced iAs, PFOA and PFOS elimination. Data also suggests that, when both abiotic stressors are combined, bivalves' capacity to accumulate contaminants may be time-dependent, considering significantly drastic increase observed with Dec 602 and TBBPA, during the last 10 days of exposure, when compared to reference conditions. Such changes in contaminants' bioaccumulation/elimination patterns also suggest a potential increase of human health risks of some compounds, if the climate continues changing as forecasted. Therefore, this first study pointed out the urgent need for further research on the effects of abiotic conditions on emerging contaminants kinetics, to adequately estimate the potential toxicological hazards associated to these compounds and develop recommendations/regulations for their presence in seafood, considering the prevailing environmental conditions expected in tomorrow's ocean., (Copyright © 2017 Elsevier Inc. All rights reserved.)

Marine pollution has been increasing as a consequence of anthropogenic activities. The preservation of marine ecosystems, as well as the safety of harvested seafood, are nowadays a global concern. Here, we report for the first time the contamination levels of a large set of 99 emerging and persistent organic contaminants (butyltins (BTs), polycyclic aromatic hydrocarbons (PAHs), pesticides including pyrethroids, pharmaceuticals and personal care products (PCPs) and flame retardants) in roe/gonads of sea urchin Paracentrotus lividus. Sea urchins are a highly prized worldwide delicacy, and the harvesting of this seafood has increased over the last decades, particularly in South West Atlantic coast, where this organism is harvested mainly for exportation. Sampling was performed in three harvesting sites of the NW Portuguese coast subjected to distinct anthropogenic pressures: Carreço, Praia Norte and Vila Chã, with sea urchins being collected in the north and south areas of each site. Butyltins and pharmaceuticals were not found at measurable levels. Several PAHs, four pyrethroids insecticides, four PCPs and eleven flame retardants were found in roe/gonads of sea urchins, though in general at low levels. Differences among harvesting sites and between areas within each site were found, the lowest levels of contaminants being registered in Carreço. The accumulation of contaminants in sea urchins' roe/gonads seemed to reflect the low anthropogenic pressure felt in the sampling sites. Nevertheless, taking into account the low accumulated levels of chemicals, results indicate that sea urchins collected in South West Atlantic coast are safe for human consumption., (Copyright © 2017 Elsevier Inc. All rights reserved.)

This work monitors flame retardants in sediment, mussel and water samples from European fish farms. Polybrominated diphenyl ethers (PBDEs) were detected in 95% of the sediment and mussel samples with mean levels of 8.60±22.6ngg -1 dw in sediments and 0.07±0.18ngg -1 dw in mussels. BDE-209 was the main contributor for the sediments and BDE-47 was found in about 60% of the samples of both matrices. Pentabromoethylbenzene (PBEB) and hexabromobenzene (HBB) were detected in 42% of the sediments, but not in mussels. Decabromodiphenyl ethane (DBDPE) was found in about 55% of the samples of both matrices. The same happened for dechloranes in mussels, but they were detected in 92% of the sediments. Syn-DP and anti-DP were always the main contributors. Methoxylated PBDEs (MeO-PBDEs) were detected in all mussels and some sediments, mainly 6-MeO-BDE-47 and 2'-MeO-BDE-68. Organophosphorus flame retardants (OPFRs) were found in all matrices with concentrations of 0.04-92.8ngg -1 dw in sediment, 0.50-102ngg -1 dw in mussel and 0.43-867ngl -1 in water. Only OPFRs were analysed in water samples as halogenated flame retardants and MeO-PBDEs are highly unlikely to be detected in water due to their physicochemical properties. Flame retardants have no application in fish farming so results should reflect the impact of human activity on the farm locations. A large majority of the most contaminated samples were collected from sampling spots that were at urban shores or in enclosed water bodies not completely open to the sea., (Copyright © 2017 Elsevier B.V. All rights reserved.)

This study evaluates the current situation regarding PBDE and HBCD levels in different river fish species. We collected published data in the last five years in different countries around the world. These levels of pollution were compared with Environmental Quality Standards (EQS) for biota established by the European Directive in the field of water policy. Although HBCD situation is not critical, with only some values exceeding the limit about 5 times, the PBDE levels clearly exceeded the established EQS, with 25% of fish samples exceeding up to ten thousand times. Although it is expected that levels of pollution by PBDEs will decrease over the next years due to the ban in their use, it is not expected that this decrease will reach the EQS values by the end of 2021, as demanded by the European Directive. Hence, it is necessary to implement new strategies in order to minimize the impact of PBDEs on the environment., (Copyright © 2017 The Authors. Published by Elsevier Inc. All rights reserved.)

Information on the occurrence of organobrominated compounds in bivalves from Tunisia is scarce. To the best of our knowledge, this is the first report of these compounds in clams from Tunisia. The aim of this study is to measure natural and synthetic organobrominated compound concentrations and evaluate congener distribution and pollution sources in a clam species (Ruditapes decussatus) from three sites of the Bizerte Lagoon. Total synthetic organobrominated pollutant levels in clam ranged from 34.8 to 188ngg -1 lw. For natural organobrominated compounds, concentrations varied from 18.2 to 49.5ngg -1 lw. Total PBDE and MeO-PBDE concentrations in clams from the Bizerte Lagoon were similar or slightly lower than those reported for other species from other locations around the world. The health risks associated with the consumption of this species were assessed and posed no threat to public health concerning PBDE intakes., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

The present study uses bird eggs of seven wild species as a biomonitoring tool for sunscreens occurrence. Seven UV filters (UV-Fs), including 3 hydroxy-metabolites of oxybenzone (benzophenone 3, BP3) were characterized in unhatched eggs from Doñana Natural Space (Spain). High frequency of detection was observed for all UV-Fs, ranging from 95% to 100%. The oxybenzone metabolite 4-hydroxybenzophenone (4HB) was ubiquitous at concentrations in the range 12.0-3348 ng g -1 dry weight (dw). The parent compound, oxybenzone, was also present in all samples at lower concentrations (16.9-49.3 ng g -1 dw). Due to the three BP3's metabolites, benzophenone 1 (BP1), 4HB, and 4,4'-dihydroxybenzophenone (4DHB) presence in unhatched eggs, it can be inferred that parent compounds are absorbed into the bird through the upper gut and the OH-derivatives formed are transferred by the mother to the egg before the lying. White stork (Ciconia ciconia) and western marsh harrier (Circus aeruginosus) were the most contaminated species, with mean total UV-Fs concentrations of 834 and 985 ng g -1 dw, respectively. Results evidenced that biomagnification process across the bird species studied cannot be ruled out.

Pregnant Sprague-Dawley rats were administered the insecticide α-cypermethrin at doses of 0.1, 1, 5, or 10mg/kg/day, or di-isobutyl phthalate (DIBP) at 250mg/kg/day, by gavage, from gestation day (GD) 13 to 19. Testicular testosterone production and the expression of several key genes related to cholesterol and androgen synthesis and transport were assessed in GD 19 male fetuses. Dams treated with 10mg/kg/day of α-cypermethrin showed clinical signs of neurotoxicity and reduced body weight gain. α-Cypermethrin had no significant effect on post-implantation loss, fetal weight, incidence of male fetuses per litter, or anogenital distance of the male fetuses. In the fetal testes, mRNA expressions of HMG-CoA synthase and reductase, SRB1, StAR, P450scc, 3βHSD, P450 17A1, and 17βHSD were not affected by exposure to α-cypermethrin. Testosterone production by the fetal testis was significantly reduced at 5 and 10mg/kg/day of α-cypermethrin, although to a much smaller extent than in DIBP-exposed fetuses., (Copyright © 2017 Elsevier Inc. All rights reserved.)

Recent studies demonstrated that the common pyrethroid insecticides are present in aquatic biota tissues. In this study, 123 samples of unhatched eggs of 16 wild bird species collected from 2010 to 2012 in Doñana National and Natural Park were analysed to determine 13 pyrethroids. This study represents the first time that pyrethroids are detected in tissues of terrestrial biota, 93% of these samples being positive to those pollutants. Levels of total pyrethroids ranged from not detected to 324 ng g -1 lw. The samples were characterized by stable isotope analysis. Species with diets based on anthropogenic food showed higher levels of pyrethroids and lower values of δ 15 N. Finally, we characterized the isomers of pyrethroids and discerned some isomeric- and enantiomeric-specific accumulations. In particular, tetramethrin and cyhalothrin showed an enantiomeric-selective accumulation of one enantiomer, highlighting the need to assess toxicological effects of each enantiomer separately to be able to make a correct risk assessment of pyrethroids in birds., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Pyrethroids are the most popular drug against sea lice in salmon farming. Although they are more toxic to insects, they have toxic effects in mammals. Pyrethroids were detected in 100% of farmed salmon with a mean concentration of 1.31 ± 1.39 ng g -1 ww and in 50% of wild salmon with a mean of 0.02 ± 0.03 ng g -1 ww. Cypermethrin and deltamethrin, the active ingredients of anti-sea lice formulations, represented 77   ±  27% of the total contamination of farmed salmon. Although farmed salmon had higher concentrations than wild salmon, the daily intake of pyrethroids through salmon consumption was several orders of magnitude below the accepted daily intake (ADI). Thus, the pyrethroids treatment on salmon does not pose a threat on the health of the consumers., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Although it is known that emerging contaminants are widespread all over the globe, there is a gap of information about their distribution in some geographical areas, such as Latin America. The present bibliographic work reviews the available literature about the presence of organic emerging contaminants in Latin American freshwater and marine biota between 2002 and 2016 and includes 23 works from Argentina, Brazil, Chile, Colombia, Mexico, and Nicaragua. In particular, the present review provides an overview of the occurrence of continuously present contaminants such as pharmaceuticals, personal care products, and pyrethroid insecticides, as well as the new groups of persistent organic pollutants, the halogenated flame retardants and the perfluoroalkyl substances. A wide overview is provided, considering not only occurrence data but also effects and potential transfer through the food chain. Environ Toxicol Chem 2017;36:1716-1727. © 2016 SETAC., (© 2016 SETAC.)

A preliminary assessment of the bioaccessibility of contaminants of emerging concern (CeCs), including perfluorinated compounds (PFCs; i.e. PFOS and PFUnA), brominated flame retardants (BFRs; i.e. BDE47, BDE100, α-HBCD) and pharmaceuticals and personal care products (PPCPs; i.e. venlafaxine, methylparaben and UV-filter OC) was performed in seafood species available in the European markets. Additionally, the effect of steaming on CeCs bioaccessibility was also investigated for the first time. Overall, steaming affected differentially contaminants' concentrations, for instance, decreasing PFOS levels in flounder, but increasing both BDE47 and BDE100. CeCs bioaccessibility varied according to seafood species and contaminant group, i.e. in general, lower bioaccessibility values were obtained for PBDEs (<70%, except for mackerel), while PFCs and PPCPs revealed higher bioaccessibility percentages (between 71 and 95%). The lowest bioaccessibility value was obtained for α-HBCD (mussel; 14%), whereas the highest percentage was observed in venlafaxine (mullet; 95%). Our preliminary study reports also, for the first time, the effects of steaming on CeCs bioaccessibility. In most cases, bioaccessibility was not affected by cooking, however, a decrease was observed in PBDEs and venlafaxine bioaccessibility in steamed mussels and mullet, respectively, thus lowering the potential health risks associated with seafood consumption., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Pyrethroid pesticides were analysed in liver of striped dolphin (Stenella coeruleoalba) from the Alboran Sea (south of Spain, Mediterranean Sea). The occurrence and bioaccumulation of pyrethroid insecticides in marine mammal tissues from the northern hemisphere had never been determined before. Pyrethroids were detected in 87% of the specimens with a mean total concentration of 300 ng g -1 lw ± 932 (range 2.7-5200 ng g -1 lw). Permethrin and tetramethrin were the main contributors to the pyrethroid profiles, with enantiospecific accumulation for the first and isomer specific accumulation for the latter. Bioaccumulation of pyrethroids was unlike that of persistent organic pollutants (POPs), as pyrethroid concentrations were not correlated to the maturity stage of the specimens. Concentrations slightly increased from calves to juveniles, whereas juveniles presented similar concentrations to adults. Metabolization of pyrethroids after achieving sexual maturity might account for this pattern., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

PBDEs (congeners 28, 47, 99, 100, 153, 154, 183, 209), HBCD (α, β, γ), emerging brominated flame retardants (PBEB, HBB and DBDPE), dechloranes (Dec 602, 603, 604, syn- and anti-DP), TBBPA, 2,4,6-TBP and MeO-PBDEs (8 congeners) were analysed in commercial seafood samples from European countries. Levels were similar to literature and above the environmental quality standards (EQS) limit of the Directive 2013/39/EU for PBDEs. Contaminants were found in 90.5% of the seafood samples at n. d.-356 ng/g lw (n. d.-41.1 ng/g ww). DBDPE was not detected and 2,4,6-TBP was detected only in mussels, but at levels comparable to those of PBDEs. Mussel and seabream were the most contaminated species and the Mediterranean Sea (FAO Fishing Area 37) was the most contaminated location. The risk assessment revealed that there was no health risk related to the exposure to brominated flame retardants via seafood consumption. However, a refined risk assessment for BDE-99 is of interest in the future. Moreover, the cooking process concentrated PBDEs and HBB., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Classic (polybromodiphenyl ethers, PBDEs) and emerging halogenated flame retardants (HFRs) such as decabromodiphenyl ethane (DBDPE) and halogenated norbornenes, as well as organophosphate flame retardants (OPFRs) were analysed in 52 sediments and 27 fish samples from three European river basins, namely the Evrotas (Greece), the Adige (Italy) and the Sava (Slovenia, Croatia, Bosnia and Herzegovina and Serbia). This is the first time that FR levels have been reported in these three European river basins. The highest contamination was found in the Adige and Sava rivers, whereas lower values were obtained for the Evrotas. The levels in sediment samples ranged between 0.25 and 34.0ng/g dw, and between 0.31 and 549ng/g dw, for HFRs and OPFRs respectively. As regards levels in fish, concentrations ranged between 9.32 and 461ng/g lw and between 14.4 and 650ng/g lw, for HFRs and OPFRs, respectively. Thus, whereas OPFR values were higher in sediments, similar concentrations (in the Evrotas) and even lower concentrations than HFRs (Sava) were found for OPFRs in the fish samples, indicating the lower bioaccumulation potential of OPFRs. Biota to sediment accumulation factors (BSAFs) were calculated and higher values were obtained for HFRs compared to those assessed for OPFRs., (Copyright © 2017 The Author(s). Published by Elsevier B.V. All rights reserved.)

The Tablas de Daimiel National Park (TDNP) is a unique floodplain ecosystem in central Spain, serving as permanent resting and breeding areas for many waterbird species. In the last decades, this biodiversity hotspot has been severely endangered by poorly treated wastewater discharges from upstream urban communities arriving through its two major contributors, the Cigüela and Guadiana rivers. In this work, we analysed the potential risk of this constant input of micropollutants (estrogens, dioxin-like compounds and other endocrine disruptors) for the resident wildlife. We sampled 12 locations in TDNP and in the nearby Navaseca Pond during 2013, and performed a series of in-vivo and in-vitro bioassays, including Daphnia magna post-exposure feeding inhibition and recombinant yeast-based assays for dioxin-like and estrogenic activities. These results were then compared with the chemical composition of the samples, analysed by GC-MS/MS and LC-MS/MS, and evaluated according to their toxic potential as toxic equivalents or TEQ. The Navaseca Pond, heavily impacted by wastewater from the town of Daimiel, showed the highest levels of toxic compounds, estrogenic activity, and Daphnia toxicity. Conversely, the less impacted TDNP sites showed low residue levels of contaminants, low estrogenicity and dioxin-like activity and negligible toxicity. The results indicates that the current good chemical status of TDNP is menaced by both the inflow of wastewater treatment plants effluents from Guadiana and Cigüela rivers into TDNP tributaries and, as it occurs in the Navaseca Pond, by direct sewage discharges., (Copyright © 2017 Elsevier B.V. All rights reserved.)