Contaminated sediment can release hydrophobic organic contaminants (HOCs) and thereby act as a secondary source of primarily legacy hazardous substances to the water column. There is therefore a need for assessments of the release of HOCs from contaminated sediment for prioritization of management actions. In situ assessment of HOC sediment-to-water flux is currently done with (closed) benthic flux chambers, which have a sampling time exceeding one month. During this time, the water inside the chamber is depleted of oxygen and the effect of bioturbation on the sediment-to-water release of HOCs is largely ignored. Here we present a novel benthic flux chamber, which measures sediment-to-water flux of legacy HOCs within days, and includes the effect of bioturbation since ambient oxygen levels inside the chamber are maintained by continuous pumping of water through the chamber. This chamber design allows for sediment-to-water flux measurements under more natural conditions. The chamber design was tested in a contaminated Baltic Sea bay. Measured fluxes were 62–2300 ng m⁻² d⁻¹ for individual polycyclic aromatic hydrocarbons (PAHs), and 5.5–150 ng m⁻² d⁻¹ for polychlorinated biphenyls (PCBs). These fluxes were 3–23 times (PAHs) and 12–74 times (PCBs) higher than fluxes measured with closed benthic chambers deployed in parallel at the same location. We hypothesize that the observed difference in HOC flux between the two chamber designs are partly an effect of bioturbation. This hypothesized effect of bioturbation was in accordance with literature data from experimental studies.

Contaminated sediment can release hydrophobic organic contaminants (HOCs) and thereby act as a secondary source of primarily legacy hazardous substances to the water column. There is therefore a need for assessments of the release of HOCs from contaminated sediment for prioritization of management actions. In situ assessment of HOC sediment-to-water flux is currently done with (closed) benthic flux chambers, which have a sampling time exceeding one month. During this time, the water inside the chamber is depleted of oxygen and the effect of bioturbation on the sediment-to-water release of HOCs is largely ignored. Here we present a novel benthic flux chamber, which measures sediment-to-water flux of legacy HOCs within days, and includes the effect of bioturbation since ambient oxygen levels inside the chamber are maintained by continuous pumping of water through the chamber. This chamber design allows for sediment-to-water flux measurements under more natural conditions. The chamber design was tested in a contaminated Baltic Sea bay. Measured fluxes were 62-2300 ng m-2 d-1 for individual polycyclic aromatic hydrocarbons (PAHs), and 5.5-150 ng m-2 d-1 for polychlorinated biphenyls (PCBs). These fluxes were 3-23 times (PAHs) and 12-74 times (PCBs) higher than fluxes measured with closed benthic chambers deployed in parallel at the same location. We hypothesize that the observed difference in HOC flux between the two chamber designs are partly an effect of bioturbation. This hypothesized effect of bioturbation was in accordance with literature data from experimental studies.

Spreading livestock manure as fertilizer on farmlands is a widespread practice. It represents the major source of heavy metal(loid)s (HM) input in agricultural soils. Since zinc (Zn) is present at high concentrations in manure, it poses special environmental concerns related to phytotoxicity, groundwater contamination, and introduction in the food chain. Therefore, investigations on the fate and behavior of manure-borne Zn, when it enters the soil environment, are necessary to predict the environmental effects. Nevertheless, long-term field studies assessing Zn speciation in the organic waste matrix, as well as within the soil after manure application, are lacking. This study was designed to fill this gap. Using SEM-EDS and XAS analysis, we reported the following new results: (i) ZnS made up 100% of the Zn speciation in the pig slurry (the highest proportion of ZnS ever observed in organic waste); and (ii) ZnS aggregates were about 1-μm diameter (the smallest particle size ever reported in pig slurry). Moreover, the pig slurry containing ZnS was spread on the soil over an 11-year period, totaling 22 applications, and the resulting Zn speciation within the amended soil was analyzed. Surprisingly, ZnS, i.e. the only species responsible for a nearly 2-fold increase in the Zn concentration within the amended soil, was not detected in this soil. Based on SEM-EDS and XAS observations, we put forward the hypothesis that Zn in the pig slurry consisted of nano-sized ZnS crystallites that further aggregated. The low stability of ZnS nanoparticles within oxic and complex environments such as the studied soil was the key explanation for the radical change in pig slurry-borne Zn speciation after long-term amendments.

Spreading livestock manure as fertilizer on farmlands is a widespread practice. It represents the major source of heavy metal(loid)s (HM) input in agricultural soils. Since zinc (Zn) is present at high concentrations in manure, it poses special environmental concerns related to phytotoxicity, groundwater contamination, and introduction in the food chain. Therefore, investigations on the fate and behavior of manure-borne Zn, when it enters the soil environment, are necessary to predict the environmental effects. Nevertheless, long-term field studies assessing Zn speciation in the organic waste matrix, as well as within the soil after manure application, are lacking. This study was designed to fill this gap. Using SEM-EDS and XAS analysis, we reported the following new results: (i) ZnS made up 100% of the Zn speciation in the pig slurry (the highest proportion of ZnS ever observed in organic waste); and (ii) ZnS aggregates were about 1-?m diameter (the smallest particle size ever reported in pig slurry). Moreover, the pig slurry containing ZnS was spread on the soil over an 11-year period, totaling 22 applications, and the resulting Zn speciation within the amended soil was analyzed. Surprisingly, ZnS, i.e. the only species responsible for a nearly 2-fold increase in the Zn concentration within the amended soil, was not detected in this soil. Based on SEM-EDS and XAS observations, we put forward the hypothesis that Zn in the pig slurry consisted of nano-sized ZnS crystallites that further aggregated. The low stability of ZnS nanoparticles within oxic and complex environments such as the studied soil was the key explanation for the radical change in pig slurry-borne Zn speciation after long-term amendments. (Résumé d'auteur)

International audience | Abstract Spreading livestock manure as fertilizer on farmlands is a widespread practice. It represents the major source of heavy metal(loid)s (HM) input in agricultural soils. Since zinc (Zn) is present at high concentrations in manure, it poses special environmental concerns related to phytotoxicity, groundwater contamination, and introduction in the food chain. Therefore, investigations on the fate and behavior of manure-borne Zn, when it enters the soil environment, are necessary to predict the environmental effects. Nevertheless, long-term field studies assessing Zn speciation in the organic waste matrix, as well as within the soil after manure application, are lacking. This study was designed to fill this gap. Using SEM-EDS and \XAS\ analysis, we reported the following new results: (i) ZnS made up 100% of the Zn speciation in the pig slurry (the highest proportion of ZnS ever observed in organic waste); and (ii) ZnS aggregates were about 1-μm diameter (the smallest particle size ever reported in pig slurry). Moreover, the pig slurry containing ZnS was spread on the soil over an 11-year period, totaling 22 applications, and the resulting Zn speciation within the amended soil was analyzed. Surprisingly, ZnS, i.e. the only species responsible for a nearly 2-fold increase in the Zn concentration within the amended soil, was not detected in this soil. Based on SEM-EDS and \XAS\ observations, we put forward the hypothesis that Zn in the pig slurry consisted of nano-sized ZnS crystallites that further aggregated. The low stability of ZnS nanoparticles within oxic and complex environments such as the studied soil was the key explanation for the radical change in pig slurry-borne Zn speciation after long-term amendments.

The increased use of pesticides has caused concern over the possible direct association of exposure to combinations of these compounds with bee health problems. There is growing proof that bees are regularly exposed to mixtures of agrochemicals, but most research has been focused on managed bees living in farmland, whereas little is known about exposure of wild bees, both in farmland and urban habitats. To determine exposure of wild bumblebees to pesticides in agricultural and urban environments through the season, specimens of five different species were collected from farms and ornamental urban gardens in three sampling periods. Five neonicotinoid insecticides, thirteen fungicides and a pesticide synergist were analysed in each of the specimens collected. In total, 61% of the 150 individuals tested had detectable levels of at least one of the compounds, with boscalid being the most frequently detected (35%), followed by tebuconazole (27%), spiroxamine (19%), carbendazim (11%), epoxiconazole (8%), imidacloprid (7%), metconazole (7%) and thiamethoxam (6%). Quantifiable concentrations ranged from 0.17 to 54.4 ng/g (bee body weight) for individual pesticides. From all the bees where pesticides were detected, the majority (71%) had more than one compound, with a maximum of seven pesticides detected in one specimen. Concentrations and detection frequencies were higher in bees collected from farmland compared to urban sites, and pesticide concentrations decreased through the season. Overall, our results show that wild bumblebees are exposed to multiple pesticides when foraging in agricultural and urban landscapes. Such mixtures are detected in bee tissues not just during the crop flowering period, but also later in the season. Therefore, contact with these combinations of active compounds might be more prolonged in time and widespread in the environment than previously assumed. These findings may help to direct future research and pesticide regulation strategies to promote the conservation of wild bee populations.

The increased use of pesticides has caused concern over the possible direct association of exposure to combinations of these compounds with bee health problems. There is growing proof that bees are regularly exposed to mixtures of agrochemicals, but most research has been focused on managed bees living in farmland, whereas little is known about exposure of wild bees, both in farmland and urban habitats. To determine exposure of wild bumblebees to pesticides in agricultural and urban environments through the season, specimens of five different species were collected from farms and ornamental urban gardens in three sampling periods. Five neonicotinoid insecticides, thirteen fungicides and a pesticide synergist were analysed in each of the specimens collected. In total, 61% of the 150 individuals tested had detectable levels of at least one of the compounds, with boscalid being the most frequently detected (35%), followed by tebuconazole (27%), spiroxamine (19%), carbendazim (11%), epoxiconazole (8%), imidacloprid (7%), metconazole (7%) and thiamethoxam (6%). Quantifiable concentrations ranged from 0.17 to 54.4 ng/g (bee body weight) for individual pesticides. From all the bees where pesticides were detected, the majority (71%) had more than one compound, with a maximum of seven pesticides detected in one specimen. Concentrations and detection frequencies were higher in bees collected from farmland compared to urban sites, and pesticide concentrations decreased through the season. Overall, our results show that wild bumblebees are exposed to multiple pesticides when foraging in agricultural and urban landscapes. Such mixtures are detected in bee tissues not just during the crop flowering period, but also later in the season. Therefore, contact with these combinations of active compounds might be more prolonged in time and widespread in the environment than previously assumed. These findings may help to direct future research and pesticide regulation strategies to promote the conservation of wild bee populations. | We are grateful to Defra (Research Project PS2372) for funding this work and to the five farmers for allowing us to work on their property. We are also grateful to the Sheepdrove Trust for contributing to the costs of the analytical work.

Perfluoroalkyl substances (PFASs) have been detected in organisms worldwide, including Polar Regions. The polar bear (Ursus maritimus), the top predator of Arctic marine ecosystems, accumulates high concentrations of PFASs, which may be harmful to their health. The aim of this study was to investigate which factors (habitat quality, season, year, diet, metabolic state [i.e. feeding/fasting], breeding status and age) predict PFAS concentrations in female polar bears captured on Svalbard (Norway). We analysed two perfluoroalkyl sulfonates (PFSAs: PFHxS and PFOS) and C8-C13 perfluoroalkyl carboxylates (PFCAs) in 112 plasma samples obtained in April and September 2012–2013. Nitrogen and carbon stable isotope ratios (δ15N, δ13C) in red blood cells and plasma, and fatty acid profiles in adipose tissue were used as proxies for diet. We determined habitat quality based on movement patterns, capture position and resource selection functions, which are models that predict the probability of use of a resource unit. Plasma urea to creatinine ratios were used as proxies for metabolic state (i.e. feeding or fasting state). Results were obtained from a conditional model averaging of 42 general linear mixed models. Diet was the most important predictor of PFAS concentrations. PFAS concentrations were positively related to trophic level and marine diet input. High PFAS concentrations in females feeding on the eastern part of Svalbard, where the habitat quality was higher than on the western coast, were likely related to diet and possibly to abiotic factors. Concentrations of PFSAs and C8-C10 PFCAs were higher in fasting than in feeding polar bears and PFOS was higher in females with cubs of the year than in solitary females. Our findings suggest that female polar bears that are exposed to the highest levels of PFAS are those 1) feeding on high trophic level sea ice-associated prey, 2) fasting and 3) with small cubs.

Accepted manuscript version. Published version available in <a href=https://doi.org/10.1016/j.envpol.2017.04.100> Environmental Pollution 2017, 229 :146-158. </a> | Perfluoroalkyl substances (PFASs) have been detected in organisms worldwide, including Polar Regions. The polar bear (Ursus maritimus), the top predator of Arctic marine ecosystems, accumulates high concentrations of PFASs, which may be harmful to their health. The aim of this study was to investigate which factors (habitat quality, season, year, diet, metabolic state [i.e. feeding/fasting], breeding status and age) predict PFAS concentrations in female polar bears captured on Svalbard (Norway). We analysed two perfluoroalkyl sulfonates (PFSAs: PFHxS and PFOS) and C₈-C₁₃ perfluoroalkyl carboxylates (PFCAs) in 112 plasma samples obtained in April and September 2012–2013. Nitrogen and carbon stable isotope ratios (δ¹⁵N, δ¹³C) in red blood cells and plasma, and fatty acid profiles in adipose tissue were used as proxies for diet. We determined habitat quality based on movement patterns, capture position and resource selection functions, which are models that predict the probability of use of a resource unit. Plasma urea to creatinine ratios were used as proxies for metabolic state (i.e. feeding or fasting state). Results were obtained from a conditional model averaging of 42 general linear mixed models. Diet was the most important predictor of PFAS concentrations. PFAS concentrations were positively related to trophic level and marine diet input. High PFAS concentrations in females feeding on the eastern part of Svalbard, where the habitat quality was higher than on the western coast, were likely related to diet and possibly to abiotic factors. Concentrations of PFSAs and C₈-C₁₀ PFCAs were higher in fasting than in feeding polar bears and PFOS was higher in females with cubs of the year than in solitary females. Our findings suggest that female polar bears that are exposed to the highest levels of PFAS are those 1) feeding on high trophic level sea ice-associated prey, 2) fasting and 3) with small cubs.

The 2010 Deepwater Horizon (DWH) oil spill released millions of barrels of oil and dispersant into the Gulf of Mexico. The timing of the spill coincided with the spawning season of Crassostrea virginica. Consequently, gametes released in the water were likely exposed to oil and dispersant. This study aimed to (i) evaluate the cellular effects of acute exposure of spermatozoa and oocytes to surface slick oil, dispersed mechanically (HEWAF) and chemically (CEWAF), using flow-cytometric (FCM) analyses, and (ii) determine whether the observed cellular effects relate to impairments of fertilization and embryogenesis of gametes exposed to the same concentrations of CEWAF and HEWAF. Following a 30-min exposure, the number of spermatozoa and their viability were reduced due to a physical action of oil droplets (HEWAF) and a toxic action of CEWAF respectively. Additionally, reactive oxygen species (ROS) production in exposed oocytes tended to increase with increasing oil concentrations suggesting that exposure to dispersed oil resulted in an oxidative stress. The decrease in fertilization success (1-h), larval survival (24-h) and increase in abnormalities (6-h and 24-h) may be partly related to altered cellular characteristics. FCM assays are a good predictor of sublethal effects especially on fertilization success. These data suggest that oil/dispersant are cytotoxic to gametes, which may affect negatively the reproduction success and early development of oysters.

The 2010 Deepwater Horizon (DWH) oil spill released millions of barrels of oil and dispersant into the Gulf of Mexico. The timing of the spill coincided with the spawning season of Crassostrea virginica. Consequently, gametes released in the water were likely exposed to oil and dispersant. This study aimed to (i) evaluate the cellular effects of acute exposure of spermatozoa and oocytes to surface slick oil, dispersed mechanically (HEWAF) and chemically (CEWAF), using flow-cytometric (FCM) analyses, and (ii) determine whether the observed cellular effects relate to impairments of fertilization and embryogenesis of gametes exposed to the same concentrations of CEWAF and HEWAF. Following a 30-min exposure, the number of spermatozoa and their viability were reduced due to a physical action of oil droplets (HEWAF) and a toxic action of CEWAF respectively. Additionally, reactive oxygen species (ROS) production in exposed oocytes tended to increase with increasing oil concentrations suggesting that exposure to dispersed oil resulted in an oxidative stress. The decrease in fertilization success (1-h), larval survival (24-h) and increase in abnormalities (6-h and 24-h) may be partly related to altered cellular characteristics. FCM assays are a good predictor of sublethal effects especially on fertilization success. These data suggest that oil/dispersant are cytotoxic to gametes, which may affect negatively the reproduction success and early development of oysters.

Environmental concerns have been raised on the adverse health effects of vehicle emissions in micro-scale traffic-crowded street canyons, especially for pedestrians and residents living in near-road buildings. Viaduct design is sometimes used to improve transportation efficiency but possibly affects urban airflow and the resultant exposure risk, which have been rarely investigated so far. The personal intake fraction (P_IF) is defined as the average fraction of total emissions that is inhaled by each person of a population (1 ppm = 1 × 10⁻⁶), and the daily carbon monoxide (CO) pollutant exposure (Et) is estimated by multiplying the average concentration of a specific micro-environment within one day. As a novelty, by considering time activity patterns and breathing rates in various micro-environments for three age groups, this paper introduces IF and Et into computational fluid dynamic (CFD) simulation to quantify the impacts of street layouts (street width/building height W/H = 1, 1.5, 2), source location, viaduct settings and noise barriers on the source-exposure correlation when realistic CO sources are defined. Narrower streets experience larger P_IF (1.51–5.21 ppm) and CO exposure, and leeward-side buildings always attain higher vehicular pollutant exposure than windward-side. Cases with a viaduct experience smaller P_IF (3.25–1.46 ppm) than cases without a viaduct (P_IF = 5.21–2.23 ppm) if the single ground-level CO source is elevated onto the viaduct. With two CO sources (both ground-level and viaduct-level), daily CO exposure rises 2.80–3.33 times but P_IF only change slightly. Noise barriers above a viaduct raise concentration between barriers, but slightly reduce vehicular exposure in near-road buildings. Because people spend most of their time indoors, vehicular pollutant exposure within near-road buildings can be 6–9 times that at pedestrian level. Although further studies are still required to provide practical guidelines, this paper provides effective methodologies to quantify the impacts of street/viaduct configurations on human exposure for urban design purpose.

Environmental concerns have been raised on the adverse health effects of vehicle emissions in micro-scale traffic-crowded street canyons, especially for pedestrians and residents living in near-road buildings. Viaduct design is sometimes used to improve transportation efficiency but possibly affects urban airflow and the resultant exposure risk, which have been rarely investigated so far. The personal intake fraction (P_IF) is defined as the average fraction of total emissions that is inhaled by each person of a population (1ppm=1×10-6), and the daily carbon monoxide (CO ) pollutant exposure (Et) is estimated by multiplying the average concentration of a specific micro-environment within one day. As a novelty, by considering time activity patterns and breathing rates in various micro-environments for three age groups, this paper introduces IF and Et into computational fluid dynamic (CFD) simulation to quantify the impacts of street layouts (street width/ building height W/H=1, 1.5, 2), source location, viaduct settings and noise barriers on the source-exposure correlation when realistic CO sources are defined. Narrower streets experience larger P_IF (1.51-5.21 ppm) and CO exposure, and leeward-side buildings always attain higher vehicular pollutant exposure than windward-side. Cases with a viaduct experience smaller P_IF (3.25-1.46 ppm) than cases without a viaduct (P_IF=5.21-2.23 ppm) if the single ground-level CO source is elevated onto the viaduct. With two CO sources (both ground-level and viaduct-level), daily CO exposure rises 2.80-3.33 times but P_IF only change slightly. Noise barriers above a viaduct raise concentration between barriers, but slightly reduce vehicular exposure in near-road buildings. Because people spend most of their time indoors, vehicular pollutant exposure within near-road buildings can be 6-9 times that at pedestrian level. Although further studies are still required to provide practical guidelines, this paper provides effective methodologies to quantify the impacts of street/viaduct configurations on human exposure for urban design purpose.

This study aimed to assess the effects of Basagran® on zebrafish (Danio rerio) embryos. The embryos were exposed to Basagran® at concentrations ranging from 120.0 to 480.6 mg/L, and the effects on embryo development (up to 96 h) and bacterial communities of 96 h-larvae were assessed. The embryo development response was time-dependent and concentration-dependent (106.35 < EC50 < 421.58 mg/L). The sensitivity of embryo-related endpoints decreased as follows: blood clotting in the head and/or around the yolk sac > delay or anomaly in yolk sac absorption > change in swimming equilibrium > development of pericardial and/or yolk sac oedema > scoliosis. A PCR-DGGE analysis was used to evaluate changes in the structure, richness, evenness and diversity of bacterial communities after herbicide exposure. A herbicide-induced structural adjustment of bacterial community was observed.In this study, it was successfully demonstrated that Basagran® affected zebrafish embryos and associated bacterial communities, showing time-dependent and concentration-dependent embryos' developmental response and structural changes in bacterial community. Thus, this work provides for the first time a complementary approach, which is useful to derive robust toxicity thresholds considering the embryo-microbiota system as a whole. The aquatic hazard assessment will be strengthened by combining current ecotoxicological tests with molecular microbiology tools.

This study aimed to assess the effects of Basagran® on zebrafish (Danio rerio) embryos. The embryos were exposed to Basagran® at concentrations ranging from 120.0 to 480.6 mg/L, and the effects on embryo development (up to 96 h) and bacterial communities of 96 h-larvae were assessed. The embryo development response was time-dependent and concentration-dependent (106.35 < EC50 < 421.58 mg/L). The sensitivity of embryo-related endpoints decreased as follows: blood clotting in the head and/or around the yolk sac > delay or anomaly in yolk sac absorption > change in swimming equilibrium > development of pericardial and/or yolk sac oedema > scoliosis. A PCR-DGGE analysis was used to evaluate changes in the structure, richness, evenness and diversity of bacterial communities after herbicide exposure. A herbicide-induced structural adjustment of bacterial community was observed. In this study, it was successfully demonstrated that Basagran® affected zebrafish embryos and associated bacterial communities, showing time-dependent and concentration-dependent embryos' developmental response and structural changes in bacterial community. Thus, this work provides for the first time a complementary approach, which is useful to derive robust toxicity thresholds considering the embryo-microbiota system as a whole. The aquatic hazard assessment will be strengthened by combining current ecotoxicological tests with molecular microbiology tools. | published

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.

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 lw ± 932 (range 2.7–5200 ng g 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. | This work has been financially supported by the Generalitat de Catalunya (Consolidated Research Groups 2014 SGR 418 – Water and Soil Quality Unit), Loro Parque Foundation (Project Flame), CEPSA and EcoCet Project (CGL2011-25543, National Research Plan by the Ministry of Economy and Competitiveness). R. de Stephanis and J. Giménez were supported by the Spanish Ministry of Economy and Competitiveness, through the Severo Ochoa Programme for Centres of Excellence in R+D+I (SEV-2012-0262) and R. de Stephanis by the Subprograma Juan de la Cierva. Thanks are due to the Consejería de Agricultura, Pesca y Medio Ambiente and the Agencia de Medio Ambiente y Agua of the Junta de Andalucía, specially to María Soledad Vivas, Carolina Fernández and Eduardo Fernández, to Centro de Recuperación de Especies Marinas Amenazadas (CREMA), specially to Juan José Castillo, and to all the people who helped in the sample collection.

The exposure to legacy polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDDs) and unrestricted 1,2-bis (2,4,6-tribromophenoxy) ethane (BTBPE), bis (2-ethylhexyl)-2,3,4,5-tetrabromophthalate (BEH-TEBP) and 2-ethylhexyl-2,3,4,5-tetrabromo-benzoate (EH-TBB) was examined in tail feathers of 76 birds belonging to ten predatory species inhabiting Pakistan. In addition, different feather types of six individuals of Black kite (Milvus migrans) were compared for their brominated flame retardant (BFR) levels. Black kite was found to be the most contaminated species with a median (minimum-maximum) tail feather concentration of 2.4 (0.70–7.5) ng g−1 dw for ∑PBDEs, 1.5 (0.5–8.1) ng g−1 dw for ∑HBCDDs and 0.10 (<LOQ-0.1) ng g−1 dw for BTBPE. Among unrestricted BFRs, BTBPE was detected only in Black kite and Little owl (Athene noctua), whereas BEH-TEBP and EH-TBB were not detected in any species. BDE-47 was found to be the most prevalent BFR compound in aquatic species, while BDE-99 and -153 were more abundant in terrestrial species. For HBCDDs, α-isomer was generally recorded as the most prevalent BFR in both terrestrial and aquatic species. The concentrations of BFRs differed significantly (all P < 0.01) among species, trophic guilds and between habitats, the latter for PBDEs only (P < 0.04), whereas differences among taxonomic affiliations and groups with different feeding regimes were not significant (P > 0.05 for both). Similarly, no significant concentration differences were observed among different feather types (all P > 0.05) suggesting their similar exposure. While variables such as species, trophic guild and δ15N values were evaluated as major predictors for BFR accumulation in the studied species, we predict that combined effects of just mentioned factors may govern the intra- and interspecific differences in BFR contamination profiles. We urge for further investigation of BFR exposure and potential toxicological effects in predatory birds from Asia with a more extensive sample size per species and location.

The exposure to legacy polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDDs) and unrestricted 1,2-bis (2,4,6-tribromophenoxy) ethane (BTBPE), bis (2-ethylhexyl)-2,3,4,5-tetrabromophthalate (BEH-TEBP) and 2-ethylhexyl-2,3,4,5-tetrabromo-benzoate (EH-TBB) was examined in tail feathers of 76 birds belonging to ten predatory species inhabiting Pakistan. In addition, different feather types of six individuals of Black kite (Milvus migrans) were compared for their brominated flame retardant (BFR) levels. Black kite was found to be the most contaminated species with a median (minimum-maximum) tail feather concentration of 2.4 (0.70-7.5) ng g(-1) dw for Sigma PBDEs, 1.5 (0.5-8.1) ng g(-1) dw for Sigma HBCDDs and 0.10 (<LOQ-0.1) ng g(-1) dw for BTBPE. Among unrestricted BFRs, BTBPE was detected only in Black kite and Little owl (Athene noctua), whereas BEH-TEBP and EH-TBB were not detected in any species. BDE-47 was found to be the most prevalent BFR compound in aquatic species, while BDE-99 and -153 were more abundant in terrestrial species. For HBCDDs, alpha-isomer was generally recorded as the most prevalent BFR in both terrestrial and aquatic species. The concentrations of BFRs differed significantly (all P < 0.01) among species, trophic guilds and between habitats, the latter for PBDEs only (P < 0.04), whereas differences among taxonomic affiliations and groups with different feeding regimes were not significant (P > 0.05 for both). Similarly, no significant concentration differences were observed among different feather types (all P > 0.05) suggesting their similar exposure. While variables such as species, trophic guild and delta N-15 values were evaluated as major predictors for BFR accumulation in the studied species, we predict that combined effects of just mentioned factors may govern the intra- and interspecific differences in BFR contamination profiles. We urge for further investigation of BFR exposure and potential toxicological effects in predatory birds from Asia with a more extensive sample size per species and location.

Use of titanium dioxide nanoparticles (TiO2 NPs) has become a part of our daily life and the high environmental concentrations predicted to accumulate in aquatic ecosystems are cause for concern. Although TiO2 has only limited reactivity, at the nanoscale level its physico-chemical properties and toxicity are different compared with bulk material. Phytoplankton is a key trophic level in fresh and marine ecosystems, and the toxicity provoked by these nanoparticles can affect the structure and functioning of ecosystems. Two microalgae species, one freshwater (Chlamydomonas reinhardtii) and the other marine (Phaeodactylum tricornutum), have been selected for testing the toxicity of TiO2 in NP and conventional bulk form and, given its photo-catalytic properties, the effect of UV-A was also checked. Growth inhibition, quantum yield reduction, increase of intracellular ROS production, membrane cell damage and production of exo-polymeric substances (EPS) were selected as variables to measure.TiO2 NPs and bulk TiO2 show a relationship between the size of agglomerates and time in freshwater and saltwater, but not in ultrapure water. Under two treatments, UV-A (6 h per day) and no UV-A exposure, NPs triggered stronger cytotoxic responses than bulk material. TiO2 NPs were also associated with greater production of reactive oxygen species and damage to membrane. However, microalgae exposed to TiO2 NPs and bulk TiO2 under UV-A were found to be more sensitive than in the visible light condition. The marine species (P. tricornutum) was more sensitive than the freshwater species, and higher Ti internalization was measured. Exopolymeric substances (EPS) were released from microalgae in the culture media, in the presence of TiO2 in both forms. This may be a possible defense mechanism by these cells, which would enhance processes of homoagglomeration and settling, and thus reduce bioavailability.

Use of titanium dioxide nanoparticles (TiO2 NPs) has become a part of our daily life and the high environmental concentrations predicted to accumulate in aquatic ecosystems are cause for concern. Although TiO2 has only limited reactivity, at the nanoscale level its physico-chemical properties and toxicity are different compared with bulk material. Phytoplankton is a key trophic level in fresh and marine ecosystems, and the toxicity provoked by these nanoparticles can affect the structure and functioning of ecosystems. Two microalgae species, one freshwater (Chlamydomonas reinhardtii) and the other marine (Phaeodactylum tricornutum), have been selected for testing the toxicity of TiO2 in NP and conventional bulk form and, given its photo-catalytic properties, the effect of UV-A was also checked. Growth inhibition, quantum yield reduction, increase of intracellular ROS production, membrane cell damage and production of exo-polymeric substances (EPS) were selected as variables to measure. TiO2 NPs and bulk TiO2 show a relationship between the size of agglomerates and time in freshwater and saltwater, but not in ultrapure water. Under two treatments, UV-A (6 h per day) and no UV-A exposure, NPs triggered stronger cytotoxic responses than bulk material. TiO2 NPs were also associated with greater production of reactive oxygen species and damage to membrane. However, microalgae exposed to TiO2 NPs and bulk TiO2 under UV-A were found to be more sensitive than in the visible light condition. The marine species (P. tricornutum) was more sensitive than the freshwater species, and higher Ti internalization was measured. Exopolymeric substances (EPS) were released from microalgae in the culture media, in the presence of TiO2 in both forms. This may be a possible defense mechanism by these cells, which would enhance processes of homoagglomeration and settling, and thus reduce bioavailability. | This research has been funded by the Junta de Andalucía (PE2011-RNM-7812 project and FQM-110 group) and the Spanish National Research Plan (CTM2012-38720-C03-03) and FEDER fundings (MAT2013-40823-R). | Peer reviewed