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The occurrence of classical and emerging halogenated flame retardants in bird samples collected between 2010–17 from the Castrejón reservoir (central Spain)was studied. Different wetland bird samples were analysed, including unhatched bird eggs and liver of dead nestlings. Polybrominated diphenylethers (PBDEs)were detected in all the samples at high concentration values, with levels up to 5167 ng/g lw. Dechloranes were found in 78% of analysed samples, but at lower concentration levels, between not detected (nd)and 2153 ng/g lw. The time trend evaluation over the sampling period showed an approximately 50% decline in mean concentrations of PBDEs. However, the most recent data for PBDEs (2016–17)still indicate that, in some cases, and based on reported LOECs, wetland birds were exposed to PBDE concentrations that are associated with possible ecological hazards. © 2019 Elsevier Ltd, This work has been funded by the Generalitat de Catalunya (Consolidated Research Group Water and Soil Quality Unit 2017 SGR 1404), and by the projects CGL2009-12753-C02-01/BOS , CGL2010-15726 and CGL2015-69445-P of the Spanish Ministerio of Economía y Competitividad . Biotage is acknowledged for providing SPE cartridges. We appreciate the help of Albert Estepa, Meritxell Mallén and Alba Martínez in the analytical work, and José C. Oliveros, Roberto Oliveros, Pilar Villalobos and Francisco Morales in the fieldwork. Appendix A

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., This work has been supported by the European Communities EU 7th Framework Programme Funding under Grant agreement no. 603629-ENV-2013-6.2.1-Globaqua and partly by the Generalitat de Catalunya (Consolidate Research Group 2017-SGR-01404) and by the Spanish Ministry of Science, Innovation and Universities (Projects CEX2018-000794-S and IBERAQUA-NET RED2018-102737-T). Special thanks are due to all partners of the GLOBAQUA consortium and the peer review panel for ensuring quality results and a fruitful collaboration within the frame of the project.

During the last years, the use of different omics techniques to evaluate the toxic effects of contaminants has increased. In the specific case of metabolomics, it has been applied for assessing the toxicity of chemicals of industrial origin considered persistent organic pollutants such as flame retardants (FRs) and perfluoroalkyl substances (PFASs). In this sense, this chapter offers a revision of the most commonly used metabolomics strategies for the evaluation of the toxicity of organic substances from industrial origin. These strategies are based on in vivo and in vitro experiments through the exposition to a single contaminant or to a mixture of contaminants. In the case of in vitro experiments for FRs, human hepatotoxic cell lines HepG2/C3A and mouse preadipocyte T3-L1 are the most frequently used due to their versatility. For PFASs, adrenocortical cell line is the most used one. Regarding in vivo experiments, aquatic organisms like microalgae, microcrustacean (i.e., Daphnia magna), filterers like bivalves, and fishes are used. The experiments with terrestrial organisms include earthworm–soil ecosystem (Wang et al., 2018b), chickens (Wigh, 2017), mice, and rats, and some works deal with humans in cohort studies. In general, the biomarkers identified are related to system activation of the stress defenses like adipogenesis, as well as carbohydrate and amino acid metabolisms, sugar metabolites, and energy molecules.

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., This research was supported by projects CTM2011-26372, CTM2013-57119, and CTM2014-57119-R of the Spanish National R+D Plan, and PICTO 2005N36155 of the Secretariat for Science and Technology and the Argentine Antarctic Institute. This study also received funding from the Generalitat de Catalunya (Consolidated Research Group “2017 SGR 01404—Water and Soil Quality Unit”) and from the European Union’s Seventh Framework Program for research, technological development, and demonstration under Grant Agreement No. 603437. This research is part of POLARCSIC activities. It reflects only the authors’ views. The Community is not liable for any use that may be made of the information contained therein. The authors would like to thank the logistical support provided by the Spanish, Argentinean, and Chilean Antarctic programs for conducting the fieldwork. The reviewers and editor are also acknowledged for their contribution to improve the article.

Despite the initial assumption that pyrethroid insecticides are “ideal” because they do not bioaccumulate and because they are able to be metabolized by mammals, recent studies have showed the opposite. Based on desorption kinetics from sediment, cyfluthrin has been reported as the most bioavailable compound, while λ-cyhalothrin was the less bioavailable. Bioaccumulation has been reported for several species. Franciscana dolphins from Brazil showed pyrethroid levels of 7.04–68.4 ng/g lw. A trend of levels connected to the age of dolphins was observed. Striped dolphins from the Spanish Mediterranean had a mean total concentration of 300 ± 932 ng/g lw. Pyrethroid levels in wild Iberian river fish were 12–4,940 ng/g lw. Pyrethroid profiles possibly reflected the local use of pesticides, and interspecies profile variation for fish was reported. While bioavailability of pyrethroids seemed considerably lower than that of POPs, concentrations of pyrethroids in striped dolphins and Iberian fish were comparable or higher than those of some POPs such as flame retardants. Mean total pyrethroid levels in unhatched eggs from wild birds collected in Spain were 1.93–162 ng/g lw, depending on the species and their feeding habits. Pyrethroid levels in human milk samples were 87–1,200 ng/g lw for a rural area in Mozambique, where they are used against the malaria vector, and 1.45–24.2 ng/g lw for urban and rural areas of Colombia, Spain and Brazil. The contamination in milk decreased exponentially with parity, supporting the hypothesis of maternal transfer of pyrethroids. The maternal transfer of pyrethroids has been observed using several tissues from mothers and foetuses of dolphins. Isomer-specific accumulation or metabolization of pyrethroids has been assessed with somewhat consistent results, although analysing environmental samples from the areas where biological samples are collected would allow more accurate observations.

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 (

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. © 2019 Elsevier Ltd, This work has been financially supported by the Generalitat de Catalunya (Consolidated Research Group 2017 SGR 1404 – Water and Soil Quality Unit). Biotage is acknowledged for providing SPE cartridges. We are grateful to Sabine Wintner and Geremy Cliff from the KwaZulu-Natal sharks board for their continued assistance in making samples available and for financial support from the International Fund for Animal Welfare (IFAW) to SP. This forms AEON publication number 188 and Iphakade publication number 224. HB is supported by the National Research Foundation . Appendix A

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. © 2018 Elsevier B.V., This work has been financially supported by the Generalitat de Catalunya (Consolidated Research Group 2017 SGR 01404 – Water and Soil Quality Unit). Biotage is acknowledged for providing SPE cartridges. The samples were collected with support of the Brazilian Antarctic Program (PROANTAR). The authors would like to thank the logistic support by Brazilian Navy and Aeronautics Forces. Project CNPq number (ESC). MBA has sandwich doctorate fellowship by CNPq – PDEE.

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.