Comparative toxicity of beach mesoplastics from South Spain: An in vitro approach.

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.

Assessment of Daily Exposure to Organophosphate Esters through PM2.5 Inhalation, Dust Ingestion, and Dermal Contact.

Inhalation of airborne fine particulate matter (PM2.5), 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 PM2.5. 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 PM2.5 and dust samples were collected in order to determine the concentration levels of 17 different OPEs. Fifteen OPEs in PM2.5 and 16 in dust samples were detected. Concentration levels in indoor air ranged from 4.37 to 185 ng/m3 (median 24.4 ng/m3) 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 EDIInhalation, 5.89 ng/(kg bw × day) for EDIDermal, and 1.75 ng/(kg bw × day) for EDIIngestion. 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 (PM10-2.5), could therefore lead to health limit exceedances.

Brominated flame retardants and natural organobrominated compounds in a vulnerable delphinid species along the Brazilian coast.

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.

Human exposure to organophosphate esters in water and packed beverages.

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.

Size-resolved chemical composition and toxicity of particles released from refit operations in shipyards.

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.

A new look at rubber recycling and recreational surfaces: The inorganic and OPE chemistry of vulcanised elastomers used in playgrounds and sports facilities.

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 CaCO3 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.

Transplacental transfer of plasticizers and flame retardants in fin whales (Balaenoptera physalus) from the North Atlantic Ocean.

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 Kow, indicating that a high lipophilicity reduced placental transfer rate. Interestingly, the decabromodiphenyl ethane (DBDPE) was the compound with the highest log Kow 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.

Biomarkers responses and polybrominated diphenyl ethers and their methoxylated analogs measured in Sparus aurata from the Lagoon of Bizerte, Tunisia.

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.

Emerging and legacy flame retardants in indoor air and dust samples of Tarragona Province (Catalonia, Spain).

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/m3 and 72,281 pg/m3, 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/m3 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/m3 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.

Organophosphate ester plasticizers in edible fish from the Mediterranean Sea: Marine pollution and human exposure.

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 δ15N 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.

Semi-industrial development of nutritious and healthy seafood dishes from sustainable species.

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_S and 34.0%-Balls_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_C, Roulade_P, Fillet_P and Balls_S had a well-balanced protein/fat ratio. Roulade_P presented the highest n-3 PUFA/n-6 PUFA ratio (3.3), while Sausages_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.

Effect of processing smoked salmon on contaminant contents.

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.

First study on the presence of plastic additives in loggerhead sea turtles (Caretta caretta) from the Mediterranean Sea.

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.

Anthropogenic contaminants in freshwater from the northern Antarctic Peninsula region.

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.

Biodegradation of hydrophobic pesticides by microalgae: Transformation products and impact on algae biochemical methane potential.

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.

Evaluation of the occurrence and fate of pesticides in a typical Mediterranean delta ecosystem (Ebro River Delta) and risk assessment for aquatic organisms.

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.

Temporal trends of halogenated and organophosphate contaminants in striped dolphins from the Mediterranean Sea.

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

Priority and emerging organic microcontaminants in three Mediterranean river basins: Occurrence, spatial distribution, and identification of river basin specific pollutants.

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.

Pyrethroid insecticides along the Southwestern Atlantic coast: Guiana dolphin (Sotalia guianensis) as a bioindicator.

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.

Exploring the degradation capability of Trametes versicolor on selected hydrophobic pesticides through setting sights simultaneously on culture broth and biological matrix.

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.