Bed sediments and a dated sediment core were collected upstream and downstream from the city of Lyon (France) to assess the spatial and temporal trends of contamination by per- and polyfluoroalkyl substances (PFASs) in this section of the Rhône River. Upstream from Lyon, concentrations of total PFASs (ΣPFASs) in sediments are low (between 0.19 and 2.6 ng g⁻¹ dry weight - dw), being characterized by a high proportion of perfluorooctane sulfonate (PFOS). Downstream from Lyon, and also from a fluoropolymer manufacturing plant, ΣPFASs concentrations reach 48.7 ng g⁻¹ dw. A gradual decrease of concentrations is reported at the coring site further downstream (38 km). Based on a dated sediment core, the temporal evolution of PFASs is reconstructed from 1984 to 2013. Prior to 1987, ΣPFASs concentrations were low (≤2 ng g⁻¹ dw), increasing to a maximum of 51 ng g⁻¹ dw in the 1990s and then decreasing from 2002 to the present day (∼10 ng g⁻¹ dw). In terms of the PFAS pattern, the proportion of perfluoroalkyl sulfonic acids (PFSAs) has remained stable since the 1980s (∼10%), whereas large variations are reported for carboxylic acids (PFCAs). Long chain- (C > 8) PFCAs characterized by an even number of perfluorinated carbons represent about 74% of the total PFAS load until 2005. However, from 2005 to 2013, the relative contribution of long chain- (C > 8) PFCAs with an odd number of perfluorinated carbons reaches 80%. Such changes in the PFAS pattern likely highlight a major shift in the industrial production process. This spatial and retrospective study provides valuable insights into the long-term contamination patterns of PFAS chemicals in river basins impacted by both urban and industrial activities.

[Departement_IRSTEA]Eaux [TR1_IRSTEA]BELCA [ADD1_IRSTEA]Systèmes aquatiques soumis à des pressions multiples | International audience | Bed sediments and a dated sediment core were collected upstream and downstream from the city of Lyon (France) to assess the spatial and temporal trends of contamination by per- and polyfluoroalkyl substances (PFASs) in this section of the Rhône River. Upstream from Lyon, concentrations of total PFASs (ΣPFASs) in sediments are low (between 0.19 and 2.6 ng g−1 dry weight - dw), being characterized by a high proportion of perfluorooctane sulfonate (PFOS). Downstream from Lyon, and also from a fluoropolymer manufacturing plant, ΣPFASs concentrations reach 48.7 ng g−1 dw. A gradual decrease of concentrations is reported at the coring site further downstream (38 km). Based on a dated sediment core, the temporal evolution of PFASs is reconstructed from 1984 to 2013. Prior to 1987, ΣPFASs concentrations were low (≤2 ng g−1 dw), increasing to a maximum of 51 ng g−1 dw in the 1990s and then decreasing from 2002 to the present day (∼10 ng g−1 dw). In terms of the PFAS pattern, the proportion of perfluoroalkyl sulfonic acids (PFSAs) has remained stable since the 1980s (∼10%), whereas large variations are reported for carboxylic acids (PFCAs). Long chain- (C > 8) PFCAs characterized by an even number of perfluorinated carbons represent about 74% of the total PFAS load until 2005. However, from 2005 to 2013, the relative contribution of long chain- (C > 8) PFCAs with an odd number of perfluorinated carbons reaches 80%. Such changes in the PFAS pattern likely highlight a major shift in the industrial production process. This spatial and retrospective study provides valuable insights into the long-term contamination patterns of PFAS chemicals in river basins impacted by both urban and industrial activities.

Bed sediments and a dated sediment core were collected upstream and downstream from the city of Lyon (France) to assess the spatial and temporal trends of contamination by per- and polyfluoroalkyl substances (PFASs) in this section of the Rhône River. Upstream from Lyon, concentrations of total PFASs (tPFASs) in sediments are low (between 0.19 and 2.6 ng g-1 dry weight - dw), being characterized by a high proportion of perfluorooctane sulfonate (PFOS). Downstream from Lyon, and also from a fluoropolymer manufacturing plant, tPFASs concentrations reach 48.7 ng g-1 dw. A gradual decrease of concentrations is reported at the coring site further downstream (38 km). Based on a dated sediment core, the temporal evolution of PFASs is reconstructed from 1984 to 2013. Prior to 1987, tPFASs concentrations were low (≤ 2 ng g-1 dw), increasing to a maximum of 51 ng g-1 dw in the 1990s and then decreasing from 2002 to the present day (~10 ng g-1 dw). In terms of the PFAS pattern, the proportion of perfluoroalkyl sulfonic acids (PFSAs) has remained stable since the 1980s (~10%), whereas large variations are reported for carboxylic acids (PFCAs). Long chain- (C>8) PFCAs characterized by an even number of perfluorinated carbons represent about 74% of the total PFAS load until 2005. However, from 2005 to 2013, the relative contribution of long chain- (C>8) PFCAs with an odd number of perfluorinated carbons reaches 80%. Such changes in the PFAS pattern likely highlight a major shift in the industrial production process. This spatial and retrospective study provides valuable insights into the long-term contamination patterns of PFAS chemicals in river basins impacted by both urban and industrial activities.

Harmful algal blooms are a threat to aquatic organisms and coastal ecosystems. Among harmful species, the widespread distributed genus Alexandrium is of global importance. This genus is well-known for the synthesis of paralytic shellfish toxins which are toxic for humans through the consumption of contaminated shellfish. While the effects of Alexandrium species upon the physiology of bivalves are now well documented, consequences on reproduction remain poorly studied. In France, Alexandrium minutum blooms have been recurrent for the last decades, generally appearing during the reproduction season of most bivalves including the oyster Crassostrea gigas. These blooms could not only affect gametogenesis but also spawning, larval development or juvenile recruitment. This study assesses the effect of toxic A. minutum blooms on C. gigas reproduction. Adult oysters were experimentally exposed to A. minutum, at environmentally realistic concentrations (10² to 10³ cells mL⁻¹) for two months during their gametogenesis and a control group, not exposed to A. minutum was fed with a non-toxic dinoflagellate. To determine both consequences to next generation and direct effects of A. minutum exposure on larvae, the embryo-larval development of subsequent offspring was conducted with and without A. minutum exposure at 10² cells mL⁻¹. Effects at each stage of the reproduction were investigated on ecophysiological parameters, cellular responses, and offspring development. Broodstock exposed to A. minutum produced spermatozoa with decreased motility and larvae of smaller size which showed higher mortalities during settlement. Embryo-larval exposure to A. minutum significantly reduced growth and settlement of larvae compared to non-exposed offspring. This detrimental consequence on larval growth was stronger in larvae derived from control parents compared to offspring from exposed parents. This study provides evidence that A. minutum blooms, whether they occur during gametogenesis, spawning or larval development, can either affect gamete quality and/or larval development of C. gigas, thus potentially impacting oyster recruitment.

Harmful algal blooms are a threat to aquatic organisms and coastal ecosystems. Among harmful species, the widespread distributed genus Alexandrium is of global importance. This genus is well-known for the synthesis of paralytic shellfish toxins which are toxic for humans through the consumption of contaminated shellfish. While the effects of Alexandrium species upon the physiology of bivalves are now well documented, consequences on reproduction remain poorly studied. In France, Alexandrium minutum blooms have been recurrent for the last decades, generally appearing during the reproduction season of most bivalves including the oyster Crassostrea gigas. These blooms could not only affect gametogenesis but also spawning, larval development or juvenile recruitment. This study assesses the effect of toxic A. minutum blooms on C. gigas reproduction. Adult oysters were experimentally exposed to A. minutum, at environmentally realistic concentrations (102 to 103 cells mL−1) for two months during their gametogenesis and a control group, not exposed to A. minutum was fed with a non-toxic dinoflagellate. To determine both consequences to next generation and direct effects of A. minutum exposure on larvae, the embryo-larval development of subsequent offspring was conducted with and without A. minutum exposure at 102 cells mL−1. Effects at each stage of the reproduction were investigated on ecophysiological parameters, cellular responses, and offspring development. Broodstock exposed to A. minutum produced spermatozoa with decreased motility and larvae of smaller size which showed higher mortalities during settlement. Embryo-larval exposure to A. minutum significantly reduced growth and settlement of larvae compared to non-exposed offspring. This detrimental consequence on larval growth was stronger in larvae derived from control parents compared to offspring from exposed parents. This study provides evidence that A. minutum blooms, whether they occur during gametogenesis, spawning or larval development, can either affect gamete quality and/or larval development of C. gigas, thus potentially impacting oyster recruitment.

Microplastic (MP) pollution is an emerging issue in aquatic sciences. Little comparative information currently exists about the problem in coastal systems exposed to different levels of human impact. Here we report a year-long study on the abundance of MP in the water column of three estuaries on the east-coast of Australia. The estuaries are subject to different scales of human impact; the Clyde estuary has little human modification, the Bega estuary has a small township and single wastewater treatment works discharging to its waters, and the Hunter estuary which has multiple townships, multiple wastewater treatment plants, and heavy industry. MP abundance followed an expected pattern with the lowest abundance in the low-impact Clyde estuary (98 part. m³), moderate levels of MP in the moderately impacted Bega estuary (246 part. m³), and high MP abundance in the highly impacted Hunter estuary (1032 part. m³). The majority of particles were <200 μm and fragment-like rather than fiber-like. MP abundance was positively related to maximum antecedent rainfall in the Bega estuary, however there are no clear environmental factors that could explain MP variation in the other systems. MP were generally higher in summer and following freshwater inflow events. On the Hunter estuary MP abundance was at times as high as zooplankton abundance, and within the range of numbers reported in other highly impacted systems globally. The results confirm that higher levels of human impact lead to greater plastic pollution and highlight the need to examine aquatic ecosystems under a range of conditions in order to adequately characterize the extent of MP pollution in rivers and coastal systems.

© 2019 Elsevier Ltd Microplastic (MP) pollution is an emerging issue in aquatic sciences. Little comparative information currently exists about the problem in coastal systems exposed to different levels of human impact. Here we report a year-long study on the abundance of MP in the water column of three estuaries on the east-coast of Australia. The estuaries are subject to different scales of human impact; the Clyde estuary has little human modification, the Bega estuary has a small township and single wastewater treatment works discharging to its waters, and the Hunter estuary which has multiple townships, multiple wastewater treatment plants, and heavy industry. MP abundance followed an expected pattern with the lowest abundance in the low-impact Clyde estuary (98 part. m3), moderate levels of MP in the moderately impacted Bega estuary (246 part. m3), and high MP abundance in the highly impacted Hunter estuary (1032 part. m3). The majority of particles were <200 μm and fragment-like rather than fiber-like. MP abundance was positively related to maximum antecedent rainfall in the Bega estuary, however there are no clear environmental factors that could explain MP variation in the other systems. MP were generally higher in summer and following freshwater inflow events. On the Hunter estuary MP abundance was at times as high as zooplankton abundance, and within the range of numbers reported in other highly impacted systems globally. The results confirm that higher levels of human impact lead to greater plastic pollution and highlight the need to examine aquatic ecosystems under a range of conditions in order to adequately characterize the extent of MP pollution in rivers and coastal systems.

A novel FeSiCa rich material (IS), chicken manure (CM) and its biochar were investigated for their efficiency in simultaneous remediation of Cd and As uptake by the vegetable Brassica chinensis L. Wet chemistry analysis and X-ray powder diffraction, scanning electron microscopy/energy dispersive X-ray spectroscopy as well as Fourier transform infrared spectroscopy were used to reveal the mechanisms responsible for Cd and As fixation in the amended soils. The IS treatment performed best in reducing Cd uptake, while the combination of IS and CM was the optimal one for As fixation. The precipitation/co-precipitation (in cadmium silicate/phosphate/phosphate hydroxide, cadmium iron and manganese oxides under alkaline conditions, and calcium/magnesium/ferric arsenates) and specific chemisorption (by amorphous iron/manganese oxides) were proved to be more efficient in simultaneously lowering As and Cd phytoavailability than was organic complexation. These findings demonstrate that FeSiCa and FeSiCaC amendments are highly efficient and promising in-situ remediation systems for safe crop production on soils contaminated with Cd and As.

International audience | A novel FeSiCa rich material (IS), chicken manure (CM) and its biochar were investigated for their efficiency in simultaneous remediation of Cd and As uptake by the vegetable Brassica chinensis L. Wet chemistry analysis and X-ray powder diffraction, scanning electron microscopy/energy dispersive X-ray spectroscopy as well as Fourier transform infrared spectroscopy were used to reveal the mechanisms responsible for Cd and As fixation in the amended soils. The IS treatment performed best in reducing Cd uptake, while the combination of IS and CM was the optimal one for As fixation. The precipitation/co-precipitation (in cadmium silicate/phosphate/phosphate hydroxide, cadmium iron and manganese oxides under alkaline conditions, and calcium/magnesium/ferric arsenates) and specific chemisorption (by amorphous iron/manganese oxides) were proved to be more efficient in simultaneously lowering As and Cd phytoavailability than was organic complexation. These findings demonstrate that FeSiCa and FeSiCaC amendments are highly efficient and promising in-situ remediation systems for safe crop production on soils contaminated with Cd and As.

The nanoscale size of plastic debris makes them potential efficient vectors of many pollutants and more especially of metals. In order to evaluate this ability, nanoplastics were produced from microplastics collected on a beach exposed to the North Atlantic Gyre. The nanoplastics were characterized using multi-dimensional methods: asymmetrical flow field flow fractionation and dynamic light scattering coupled to several detectors. Lead (II) adsorption kinetics, isotherm and pH-edge were then carried out. The sorption reached a steady state after around 200 min. The maximum sorption capacity varied between 97% and 78.5% for both tested Pb concentrations. Lead (II) adsorption kinetics is controlled by chemical reactions with the nanoplastics surface and to a lesser extent by intraparticle diffusion. Adsorption isotherm modeling using Freundlich model demonstrated that NPG are strong adsorbents equivalent to hydrous ferric oxides such as ferrihydrite (log Kadsfreundlich=8.36 against 11.76 for NPG and ferrihydrite, respectively). The adsorption is dependent upon pH, in response to the Pb(II) adsorption by the oxygenated binding sites developed on account of the surface UV oxidation under environmental conditions. They could be able to compete with Fe or humic colloids for Pb binding regards to their amount and specific areas. Nanoplastics could therefore be efficient vectors of Pb and probably of many other metals as well in the environment.

International audience | The nanoscale size of plastic debris makes them potential efficient vectors of many pollutants and more especially of metals. In order to evaluate this ability, nanoplastics were produced from microplastics collected on a beach exposed to the North Atlantic Gyre. The nanoplastics were characterized using multi-dimensional methods: asymmetrical flow field flow fractionation and dynamic light scattering coupled to several detectors. Lead (II) adsorption kinetics, isotherm and pH-edge were then carried out. The sorption reached a steady state after around 200 min. The maximum sorption capacity varied between 97% and 78.5% for both tested Pb concentrations. Lead (II) adsorption kinetics is controlled by chemical reactions with the nanoplastics surface and to a lesser extent by intraparticle diffusion. Adsorption isotherm modeling using Freundlich model demonstrated that NPG are strong adsorbents equivalent to hydrous ferric oxides such as ferrihydrite (log against 11.76 for NPG and ferrihydrite, respectively). The adsorption is dependent upon pH, in response to the Pb(II) adsorption by the oxygenated binding sites developed on account of the surface UV oxidation under environmental conditions. They could be able to compete with Fe or humic colloids for Pb binding regards to their amount and specific areas. Nanoplastics could therefore be efficient vectors of Pb and probably of many other metals as well in the environment.

Endocrine disrupting chemicals (EDCs) include a wide array of pollutants, such as some metals and other toxic elements, which may cause changes in hormonal homeostasis. In addition to affecting physiology of individuals directly, EDCs may alter the transfer of maternal hormones to offspring, i.e. causing transgenerational endocrine disruption. However, such effects have been rarely studied, especially in wild populations. We studied the associations between environmental elemental pollution (As, Cd, Cu, Ni, Pb) and maternally-derived egg thyroid hormones (THs) as well as nestling THs in great tits (Parus major) using extensive sampling of four pairs of polluted and reference populations across Europe (Finland, Belgium, Hungary, Portugal). Previous studies in these populations showed that breeding success, nestling growth and adult and nestling physiology were altered in polluted zones compared to reference zones. We sampled non-incubated eggs to measure maternally-derived egg THs, measured nestling plasma THs and used nestling faeces for assessing local elemental exposure. We also studied whether the effect of elemental pollution on endocrine traits is dependent on calcium (Ca) availability (faecal Ca as a proxy) as low Ca increases toxicity of some elements. Birds in the polluted zones were exposed to markedly higher levels of toxic elements than in reference zones at the populations in Finland, Belgium and Hungary. In contrast to our predictions, we did not find any associations between overall elemental pollution, or individual element concentrations and egg TH and nestling plasma TH levels. However, we found some indication that the effect of metals (Cd and Cu) on egg THs is dependent on Ca availability. In summary, our results suggest that elemental pollution at the studied populations is unlikely to cause overall TH disruption and affect breeding via altered egg or nestling TH levels with the current elemental pollution loads. Associations with Ca availability should be further studied.

Endocrine disrupting chemicals (EDCs) include a wide array of pollutants, such as some metals and other toxic elements, which may cause changes in hormonal homeostasis. In addition to affecting physiology of individuals directly, EDCs may alter the transfer of maternal hormones to offspring, i.e. causing transgenerational endocrine disruption. However, such effects have been rarely studied, especially in wild populations. We studied the associations between environmental elemental pollution (As, Cd, Cu, Ni, Pb) and maternally-derived egg thyroid hormones (THs) as well as nestling THs in great tits (Parus major) using extensive sampling of four pairs of polluted and reference populations across Europe (Finland, Belgium, Hungary, Portugal). Previous studies in these populations showed that breeding success, nestling growth and adult and nestling physiology were altered in polluted zones compared to reference zones. We sampled non-incubated eggs to measure maternally-derived egg THs, measured nestling plasma THs and used nestling faeces for assessing local elemental exposure. We also studied whether the effect of elemental pollution on endocrine traits is dependent on calcium (Ca) availability (faecal Ca as a proxy) as low Ca increases toxicity of some elements. Birds in the polluted zones were exposed to markedly higher levels of toxic elements than in reference zones at the populations in Finland, Belgium and Hungary. In contrast to our predictions, we did not find any associations between overall elemental pollution, or individual element concentrations and egg TH and nestling plasma TH levels. However, we found some indication that the effect of metals (Cd and Cu) on egg THs is dependent on Ca availability. In summary, our results suggest that elemental pollution at the studied populations is unlikely to cause overall TH disruption and affect breeding via altered egg or nestling TH levels with the current elemental pollution loads. Associations with Ca availability should be further studied. | published

Concentrations of organohalogenated contaminants (OHCs) can show significant temporal and spatial variation in the environment and wildlife. Most of the variation is due to changes in use and production, but environmental and biological factors may also contribute to the variation. Nestlings of top predators are exposed to maternally transferred OHCs in the egg and through their dietary intake after hatching. The present study investigated spatial and temporal variation of OHCs and the role of age and diet on these variations in plasma of Norwegian white-tailed eagle (Haliaeetus albicilla) nestlings. The nestlings were sampled at two locations, Smøla and Steigen, in 2015 and 2016. The age of the nestlings was recorded (range: 44 – 87 days old) and stable carbon and nitrogen isotopes (δ¹³C and δ¹⁵N) were applied as dietary proxies for carbon source and trophic position, respectively. In total, 14 polychlorinated biphenyls (PCBs, range: 0.82 – 59.05 ng/mL), 7 organochlorinated pesticides (OCPs, range: 0.89 – 52.19 ng/mL), 5 polybrominated diphenyl ethers (PBDEs, range: 0.03 – 2.64 ng/mL) and 8 perfluoroalkyl substances (PFASs, range: 4.58 – 52.94 ng/mL) were quantified in plasma samples from each location and year. The OHC concentrations, age and dietary proxies displayed temporal and spatial variations. The age of the nestlings was indicated as the most important predictor for OHC variation as the models displayed significantly decreasing plasma concentrations of PCBs, OCPs, and PBDEs with increasing age, while concentrations of PFASs were significantly increasing with age. Together with age, the variations in PCB, OCP and PBDE concentrations were also explained by δ¹³C and indicated decreasing concentrations with a more marine diet. Our findings emphasise age and diet as important factors to consider when investigating variations in plasma OHC concentrations in nestlings.

Concentrations of organohalogenated contaminants (OHCs) can show significant temporal and spatial variation in the environment and wildlife. Most of the variation is due to changes in use and production, but environmental and biological factors may also contribute to the variation. Nestlings of top predators are exposed to maternally transferred OHCs in the egg and through their dietary intake after hatching. The present study investigated spatial and temporal variation of OHCs and the role of age and diet on these variations in plasma of Norwegian white-tailed eagle (Haliaeetus albicilla) nestlings. The nestlings were sampled at two locations, Smøla and Steigen, in 2015 and 2016. The age of the nestlings was recorded (range: 44 - 87 days old) and stable carbon and nitrogen isotopes (δ13C and δ15N) were applied as dietary proxies for carbon source and trophic position, respectively. In total, 14 polychlorinated biphenyls (PCBs, range: 0.82 - 59.05 ng/mL), 7 organochlorinated pesticides (OCPs, range: 0.89 - 52.19 ng/mL), 5 polybrominated diphenyl ethers (PBDEs, range: 0.03 - 2.64 ng/mL) and 8 perfluoroalkyl substances (PFASs, range: 4.58 - 52.94 ng/mL) were quantified in plasma samples from each location and year. The OHC concentrations, age and dietary proxies displayed temporal and spatial variations. The age of the nestlings was indicated as the most important predictor for OHC variation as the models displayed significantly decreasing plasma concentrations of PCBs, OCPs, and PBDEs with increasing age, while concentrations of PFASs were significantly increasing with age. Together with age, the variations in PCB, OCP and PBDE concentrations were also explained by δ13C and indicated decreasing concentrations with a more marine diet. Our findings emphasise age and diet as important factors to consider when investigating variations in plasma OHC concentrations in nestlings. | acceptedVersion

peer reviewed | Concentrations of organohalogenated contaminants (OHCs) can show significant temporal and spatial variation in the environment and wildlife. Most of the variation is due to changes in use and production, but environmental and biological factors may also contribute to the variation. Nestlings of top predators are exposed to maternally transferred OHCs in the egg and through their dietary intake after hatching. The present study investigated spatial and temporal variation of OHCs and the role of age and diet on these variations in plasma of Norwegian white-tailed eagle (Haliaeetus albicilla) nestlings. The nestlings were sampled at two locations, Smøla and Steigen, in 2015 and 2016. The age of the nestlings was recorded (range: 44 – 87 days old) and stable carbon and nitrogen isotopes (δ13C and δ15N) were applied as dietary proxies for carbon source and trophic position, respectively. In total, 14 polychlorinated biphenyls (PCBs, range: 0.82 – 59.05 ng/mL), 7 organochlorinated pesticides (OCPs, range: 0.89 – 52.19 ng/mL), 5 polybrominated diphenyl ethers (PBDEs, range: 0.03 – 2.64 ng/mL) and 8 perfluoroalkyl substances (PFASs, range: 4.58 – 52.94 ng/mL) were quantified in plasma samples from each location and year. The OHC concentrations, age and dietary proxies displayed temporal and spatial variations. The age of the nestlings was indicated as the most important predictor for OHC variation as the models displayed significantly decreasing plasma concentrations of PCBs, OCPs, and PBDEs with increasing age, while concentrations of PFASs were significantly increasing with age. Together with age, the variations in PCB, OCP and PBDE concentrations were also explained by δ13C and indicated decreasing concentrations with a more marine diet. Our findings emphasise age and diet as important factors to consider when investigating variations in plasma OHC concentrations in nestlings. © 2018 Elsevier Ltd | 230465