Plastic debris has become an environmental problem during recent years. Among the plastic debris, microplastics (<5 mm; MPLs) imply an extra problem due to their capacity to enter into the fauna through ingestion. In this work, we study the capacity of three MPLs, that include high-density polyethylene (HDPE), polystyrene (PS) and polystyrene carboxylate (PS-COOH), to sorb 18 perfluoroalkyl substances (PFASs; including carboxylic acids, sulphonates and one sulphonamide) from the surrounding waters (freshwater and seawater).Conclusions drawn from the results are that perfluoro sulphonates and sulphonamides have more tendency to be sorbed onto MPLs. In addition, PS and PS-COOH have more affinity for PFASs than HDPE. Finally, the increment of conductivity and pH of the water decreases the exposure time that is necessary to reach equilibrium. However, the presence of salts decreases the tendency of PFASs to be sorbed onto plastic surfaces. These results highlight the problem associated with the presence of MPLs in inland and marine waters since toxic compounds can be sorbed onto surrounding plastics that could be ingested by aquatic fauna.

Plastic debris has become an environmental problem during recent years. Among the plastic debris, microplastics (<5 mm; MPLs) imply an extra problem due to their capacity to enter into the fauna through ingestion. In this work, we study the capacity of three MPLs, that include high-density polyethylene (HDPE), polystyrene (PS) and polystyrene carboxylate (PS-COOH), to sorb 18 perfluoroalkyl substances (PFASs; including carboxylic acids, sulphonates and one sulphonamide) from the surrounding waters (freshwater and seawater). Conclusions drawn from the results are that perfluoro sulphonates and sulphonamides have more tendency to be sorbed onto MPLs. In addition, PS and PS-COOH have more affinity for PFASs than HDPE. Finally, the increment of conductivity and pH of the water decreases the exposure time that is necessary to reach equilibrium. However, the presence of salts decreases the tendency of PFASs to be sorbed onto plastic surfaces. These results highlight the problem associated with the presence of MPLs in inland and marine waters since toxic compounds can be sorbed onto surrounding plastics that could be ingested by aquatic fauna. | This work has been supported by INTEGRA-COAST project (CGL2014-56530-C4-1-R). It was also partly supported by the Generalitat de Catalunya (Consolidated Research Groups “2014 SGR 418-Water and Soil Quality Unit”, “2014 SGR 291- Catalan Institute for Water Research 2014 SGR 291”). GS acknowledges PhD scholarship (BES-2015-072281) and ML acknowledges her Juan de la Cierva – Incorporación research fellowship (JdC-2014-21736) both from the Spanish Ministry of Economy, Industry and Competitiveness. | Peer reviewed

Imposex is a disorder caused by organotins, mainly tributyltin, which results in the appearance of male sexual characteristics in females of gastropod mollusks. The main objective of this work was to make a critical analysis of the relationship between imposex and butyltin body burdens in Nucella lapillus and Nassarius reticulatus. Specifically, this study evaluates possible additive effects among butyltins, proposes scales of effects based on robust statistical criteria as alternatives to existing ones and defines the body burdens of TBT in N. lapillus and N. reticulatus corresponding to the assessment classes (ACs) of the Vas Deferens Sequence Index (VDSI) established by OSPAR. Data of organotin body burdens and biological effects was retrieved from the ICES Dataset and from scientific literature. All responses, except the percentage of females displaying Imposex (IMPF) in Nucella lapillus, showed a sigmoidal profile regarding to the body burden of mono- (MBT), di- (DBT) and tributyltin and sum of butyltins (SumBTs). TBT and the SumBTs were better indicators of the VDSI or Relative Penis Size Index/Relative Penis Length Index (RPSI/RPLI) responses than MBT or DBT in most cases. From a statistical point of view, RPSI/RPLI and VDSI were better indicators of contamination by TBT than IMPF, although both RPSI and RPLI showed lower sensitivity than VDSI. The model used for describing the joint effect of butyltins provided a statistically significant fitting to the data assuming a null effect for both MBT and DBT for N. lapillus, and a lower toxic contribution of MBT and DBT with respect to TBT for N. reticulatus. RPSI or RPLI values, equivalent to the ACs for VDSI, were proposed as alternative criteria when measuring moderate to high levels of imposex. TBT concentrations in N. reticulatus and N. lapillus tissues, corresponding to the ACs were calculated and provided valuable information for cross-species comparisons.

Imposex is a disorder caused by organotins, mainly tributyltin, which results in the appearance of male sexual characteristics in females of gastropod mollusks. The main objective of this work was to make a critical analysis of the relationship between imposex and butyltin body burdens in Nucella lapillus and Nassarius reticulatus. Specifically, this study evaluates possible additive effects among butyltins, proposes scales of effects based on robust statistical criteria as alternatives to existing ones and defines the body burdens of TBT in N. lapillus and N. reticulatus corresponding to the assessment classes (ACs) of the Vas Deferens Sequence Index (VDSI) established by OSPAR. Data of organotin body burdens and biological effects was retrieved from the ICES Dataset and from scientific literature. All responses, except the percentage of females displaying Imposex (IMPF) in Nucella lapillus, showed a sigmoidal profile regarding to the body burden of mono- (MBT), di- (DBT) and tributyltin and sum of butyltins (SumBTs). TBT and the SumBTs were better indicators of the VDSI or Relative Penis Size Index/Relative Penis Length Index (RPSI/ RPLI) responses than MBT or DBT in most cases. From a statistical point of view, RPSI/RPLI and VDSI were better indicators of contamination by TBT than IMPF, although both RPSI and RPLI showed lower sensitivity than VDSI. The model used for describing the joint effect of butyltins provided a statistically significant fitting to the data assuming a null effect for both MBT and DBT for N. lapillus, and a lower toxic contribution of MBT and DBT with respect to TBT for N. reticulatus. RPSI or RPLI values, equivalent to the ACs for VDSI, were proposed as alternative criteria when measuring moderate to high levels of imposex. TBT concentrations in N. reticulatus and N. lapillus tissues, corresponding to the ACs were calculated and provided valuable information for cross-species comparisons. | Sí

The sulphide-rich mine wastes accumulated in tailing dumps of La Concordia Mine (Puna of Argentina) have been exposed to the weathering action for more than 30 years. Since then, a series of redox reactions have triggered the generation of a highly acidic drainage -rich in dissolved metals-that drains into the La Concordia creek. The extent of metal and acid release in the site was analysed through field surveys and laboratory experiments. Static tests were conducted in order to predict the potential of the sulphidic wastes to produce acid, while Cu-, Zn-, Fe- and Pb-bearing phases present in the wastes were identified by XRD, SEM/EDS analysis and sequential extraction procedures. Finally, the release of these metals during sediment-water interaction was assessed in batch experiments carried out in a period of nearly two years. Field surveys indicate that the prolonged alteration of the mine wastes led to elevated electrical conductivity, pH values lower than 4 and metal concentrations that exceed the guide values for drinking water in the La Concordia stream regardless of the dominating hydrological conditions. The highly soluble Fe and Mg (hydrous)sulphates that form salt crusts on the tailings surfaces and the riverbed sediments play an important role in the control of metal mobility, as they rapidly dissolve in contact with water releasing Fe, but also Cu and Zn which are scavenged by such minerals. Another important proportion of the analysed metals is adsorbed onto Fe (hydr)oxides or form less soluble hydroxysulfates. Metals present in these phases are released to water more slowly, thus representing a potential long term source of heavy metal pollution. The obtained results are a contribution to the understanding of long term metal transformations and mobility in mine waste-impacted sites.

The sulphide-rich mine wastes accumulated in tailing dumps of La Concordia Mine (Puna of Argentina) have been exposed to the weathering action for more than 30 years. Since then, a series of redox reactions have triggered the generation of a highly acidic drainage -rich in dissolved metals-that drains into the La Concordia creek. The extent of metal and acid release in the site was analysed through field surveys and laboratory experiments. Static tests were conducted in order to predict the potential of the sulphidic wastes to produce acid, while Cu-, Zn-, Fe- and Pb-bearing phases present in the wastes were identified by XRD, SEM/EDS analysis and sequential extraction procedures. Finally, the release of these metals during sediment-water interaction was assessed in batch experiments carried out in a period of nearly two years. Field surveys indicate that the prolonged alteration of the mine wastes led to elevated electrical conductivity, pH values lower than 4 and metal concentrations that exceed the guide values for drinking water in the La Concordia stream regardless of the dominating hydrological conditions. The highly soluble Fe and Mg (hydrous)sulphates that form salt crusts on the tailings surfaces and the riverbed sediments play an important role in the control of metal mobility, as they rapidly dissolve in contact with water releasing Fe, but also Cu and Zn which are scavenged by such minerals. Another important proportion of the analysed metals is adsorbed onto Fe (hydr)oxides or form less soluble hydroxysulfates. Metals present in these phases are released to water more slowly, thus representing a potential long term source of heavy metal pollution. The obtained results are a contribution to the understanding of long term metal transformations and mobility in mine waste-impacted sites. | Fil: Nieva, Nancy Eugenia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Centro de Investigaciones en Ciencias de la Tierra. Universidad Nacional de Córdoba. Facultad de Ciencias Exactas Físicas y Naturales. Centro de Investigaciones en Ciencias de la Tierra; Argentina | Fil: Borgnino Bianchi, Laura Carolina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Centro de Investigaciones en Ciencias de la Tierra. Universidad Nacional de Córdoba. Facultad de Ciencias Exactas Físicas y Naturales. Centro de Investigaciones en Ciencias de la Tierra; Argentina | Fil: Garcia, Maria Gabriela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Centro de Investigaciones en Ciencias de la Tierra. Universidad Nacional de Córdoba. Facultad de Ciencias Exactas Físicas y Naturales. Centro de Investigaciones en Ciencias de la Tierra; Argentina

Mercury (Hg) is a pervasive contaminant reaching Antarctic environments through atmospheric transport and deposition. Seabirds as meso to top predators can accumulate high quantities of Hg through diet. Reproduction is one of the most sensitive endpoints of Hg toxicity in marine birds. Yet, few studies have explored Hg exposure and effects in Antarctic seabirds, where increasing environmental perturbations challenge animal populations. This study focuses on the Antarctic petrel Thalassoica antarctica from Svarthamaren, Antarctica, where the world's largest breeding population is thought to be in decline. Hg and the stable isotopes of carbon (δ13C, proxy of feeding habitat) and nitrogen (δ15N, trophic position/diet) were measured in red blood cells from 266 individuals over two breeding years (2012–13, 2013–14). Our aims were to 1) quantify the influence of individual traits (size and sex) and feeding ecology (foraging location, δ13C and δ15N values) on Hg exposure, and 2) test the relationship between Hg concentrations with body condition and breeding output (hatching success and chick survival). Hg concentrations in Antarctic petrels (mean ± SD, 0.84 ± 0.25, min-max, 0.42–2.71 μg g−1 dw) were relatively low when compared to other Antarctic seabirds. Hg concentrations increased significantly with δ15N values, indicating that individuals with a higher trophic level (i.e. feeding more on fish) had higher Hg exposure. By contrast, Hg exposure was not driven by feeding habitat (inferred from both foraging location and δ13C values), suggesting that Hg transfer to predators in Antarctic waters is relatively homogeneous over a large geographical scale. Hg concentrations were not related to body condition, hatching date and short-term breeding output. At present, Hg exposure is likely not of concern for this population. Nevertheless, further studies on other fitness parameters and long-term breeding output are warranted because Hg can have long-term population-level effects without consequences on current breeding success.

International audience | Mercury (Hg) is a pervasive contaminant reaching Antarctic environments through atmospheric transport and deposition. Seabirds as meso to top predators can accumulate high quantities of Hg through diet. Reproduction is one of the most sensitive endpoints of Hg toxicity in marine birds. Yet, few studies have explored Hg exposure and effects in Antarctic seabirds, where increasing environmental perturbations challenge animal populations. This study focuses on the Antarctic petrel Thalassoica antarctica from Svarthamaren, Antarctica, where the world's largest breeding population is thought to be in decline. Hg and the stable isotopes of carbon (δ13C, proxy of feeding habitat) and nitrogen (δ15N, trophic position/diet) were measured in red blood cells from 266 individuals over two breeding years (2012–13, 2013–14). Our aims were to 1) quantify the influence of individual traits (size and sex) and feeding ecology (foraging location, δ13C and δ15N values) on Hg exposure, and 2) test the relationship between Hg concentrations with body condition and breeding output (hatching success and chick survival). Hg concentrations in Antarctic petrels (mean ± SD, 0.84 ± 0.25, min-max, 0.42–2.71 μg g−1 dw) were relatively low when compared to other Antarctic seabirds. Hg concentrations increased significantly with δ15N values, indicating that individuals with a higher trophic level (i.e. feeding more on fish) had higher Hg exposure. By contrast, Hg exposure was not driven by feeding habitat (inferred from both foraging location and δ13C values), suggesting that Hg transfer to predators in Antarctic waters is relatively homogeneous over a large geographical scale. Hg concentrations were not related to body condition, hatching date and short-term breeding output. At present, Hg exposure is likely not of concern for this population. Nevertheless, further studies on other fitness parameters and long-term breeding output are warranted because Hg can have long-term population-level effects without consequences on current breeding success.

Heavy metals in urban soils may impose a threat to public health and may negatively affect urban tree viability. Vegetation spectroscopy techniques applied to bio-indicators bring new opportunities to characterize heavy metal contamination, without being constrained by laborious soil sampling and lab-based sample processing. Here we used Tilia tomentosa trees, sampled across three European cities, as bio-indicators i) to investigate the impacts of elevated concentrations of cadmium (Cd) and lead (Pb) on leaf mass per area (LMA), total chlorophyll content (Chl), chlorophyll a to b ratio (Chla:Chlb) and the maximal PSII photochemical efficiency (Fv/Fm); and ii) to evaluate the feasibility of detecting Cd and Pb contamination using leaf reflectance spectra. For the latter, we used a partial-least-squares discriminant analysis (PLS-DA) to train spectral-based models for the classification of Cd and/or Pb contamination. We show that elevated soil Pb concentrations induced a significant decrease in the LMA and Chla:Chlb, with no decrease in Chl. We did not observe pronounced reductions of Fv/Fm due to Cd and Pb contamination. Elevated Cd and Pb concentrations induced contrasting spectral changes in the red-edge (690–740 nm) region, which might be associated with the proportional changes in leaf pigments. PLS-DA models allowed for the classifications of Cd and Pb contamination, with a classification accuracy of 86% (Kappa = 0.48) and 83% (Kappa = 0.66), respectively. PLS-DA models also allowed for the detection of a collective elevation of soil Cd and Pb, with an accuracy of 66% (Kappa = 0.49). This study demonstrates the potential of using reflectance spectroscopy for biomonitoring of heavy metal contamination in urban soils.

International audience | Heavy metals in urban soils may impose a threat to public health and may negatively affect urban tree viability. Vegetation spectroscopy techniques applied to bio-indicators bring new opportunities to characterize heavy metal contamination, without being constrained by laborious soil sampling and lab-based sample processing. Here we used Tilia tomentosa trees, sampled across three European cities, as bio-indicators i) to investigate the impacts of elevated concentrations of cadmium (Cd) and lead (Pb) on leaf mass per area (LMA), total chlorophyll content (Chl), chlorophyll a to b ratio (Chla:Chlb) and the maximal PSII photochemical efficiency (Fv/Fm); and ii) to evaluate the feasibility of detecting Cd and Pb contamination using leaf reflectance spectra. For the latter, we used a partial-least-squares discriminant analysis (PLS-DA) to train spectral-based models for the classification of Cd and/or Pb contamination. We show that elevated soil Pb concentrations induced a significant decrease in the LMA and Chla:Chlb, with no decrease in Chl. We did not observe pronounced reductions of Fv/Fm due to Cd and Pb contamination. Elevated Cd and Pb concentrations induced contrasting spectral changes in the red-edge (690–740 nm) region, which might be associated with the proportional changes in leaf pigments. PLS-DA models allowed for the classifications of Cd and Pb contamination, with a classification accuracy of 86% (Kappa = 0.48) and 83% (Kappa = 0.66), respectively. PLS-DA models also allowed for the detection of a collective elevation of soil Cd and Pb, with an accuracy of 66% (Kappa = 0.49). This study demonstrates the potential of using reflectance spectroscopy for biomonitoring of heavy metal contamination in urban soils.

Integrated compensatory responses of physiological systems towards homeostasis are generally overlooked when it comes to analysing alterations in biochemical parameters indicative of such processes. Here an hypothesis-driven multivariate analysis accounting for interactive multibiomarker responses was used to investigate effects of long-term exposure of Carcinus maenas to Hazardous and Noxious Substances (HNS). Adult male crabs were exposed to low and high post-spill levels of acrylonitrile (ACN) or aniline (ANL) for 21d. Bioaccumulation, feeding behaviour, and biomarkers related to mode-of-action (MoA) (detoxification, neurotransmission and energy production) were evaluated over time. Distinct temporal patterns of response to low and high exposure concentrations were depicted, with a main set of interactive multibiomarker predictors identified for each HNS (five for ACN and three for ANL), useful to follow coupled evolvement of biomarker responses. ACN caused peripheral neurotoxic effects coupled with enhanced biotransformation and significant oxidative damage particularly relevant in gills. ANL elicited alterations in central neurotransmission affecting ventilation coupled with very low levels of oxidative damage in gills. Results indicate chronic toxicity data are determinant to improve HNS hazard assessment if the aim is to obtain reliable risk calculations, and develop effective predictive models avoiding overestimation but sufficiently protective. Accounting for multibiomarker interactions brought otherwise overlooked information about C. maenas responses and MoA of ACN and ANL.

Integrated compensatory responses of physiological systems towards homeostasis are generally overlooked when it comes to analysing alterations in biochemical parameters indicative of such processes. Here an hypothesis-driven multivariate analysis accounting for interactive multibiomarker responses was used to investigate effects of long-term exposure of Carcinus maenas to Hazardous and Noxious Substances (HNS). Adult male crabs were exposed to low and high post-spill levels of acrylonitrile (ACN) or aniline (ANL) for 21d. Bioaccumulation, feeding behaviour, and biomarkers related to mode-of-action (MoA) (detoxification, neurotransmission and energy production) were evaluated over time. Distinct temporal patterns of response to low and high exposure concentrations were depicted, with a main set of interactive multibiomarker predictors identified for each HNS (five for ACN and three for ANL), useful to follow coupled evolvement of biomarker responses. ACN caused peripheral neurotoxic effects coupled with enhanced biotransformation and significant oxidative damage particularly relevant in gills. ANL elicited alterations in central neurotransmission affecting ventilation coupled with very low levels of oxidative damage in gills. Results indicate chronic toxicity data are determinant to improve HNS hazard assessment if the aim is to obtain reliable risk calculations, and develop effective predictive models avoiding overestimation but sufficiently protective. Accounting for multibiomarker interactions brought otherwise overlooked information about C. maenas responses and MoA of ACN and ANL. Accounting for biomarker interactions drastically improves the quality of the model to diagnose toxic effects. © 2018 Elsevier | This article is a result of INNOVMAR - Innovation and Sustainability in the Management and Exploitation of Marine Resources (reference NORTE-01-0145-FEDER-000035), ECOSERVICES, supported by NORTE2020, PORTUGAL2020 Partnership Agreement, through ERDF . This work was partially funded by Strategic Funding UID/Multi/04423/2013 through FCT and ERDF .

Copper and zinc are metals that have been traditionally thought of as past contamination legacies. However, their industrial use is still extensive and current applications (e.g. nanoparticles and antifouling paints) have become additional marine environment delivery routes. Determining a pollutant's genotoxicity is an ecotoxicological priority, but in marine benthic systems putative substances responsible for sediment genotoxicity have rarely been identified. Studies that use sediment as the delivery matrix combined with exposures over life-history relevant timescales are also missing for metals. Here we assess copper and zinc's genotoxicity by exposing the ecologically important polychaete Alitta virens to sediment spiked with environmentally relevant concentrations for 9 months. Target bioavailable sediment and subsequent porewater concentrations reflect the global contamination range for coasts, whilst tissue concentrations, although elevated, were comparable with other polychaetes. Survival generally reduced as concentrations increased, but monthly analyses show that growth was not significantly different between treatments. The differential treatment mortality may have enabled the surviving worms in the high concentration treatments to capture more food thus removing any concentration treatment effects for biomass. Using the alkaline comet assay we confirm that both metals via the sediment are genotoxic at concentrations routinely found in coastal regions and this is supported by elevated DNA damage in worms from field sites. However, combined with the growth data it also highlights the tolerance of A. virens to DNA damage. Finally, using long term (decadal) monitoring data we show stable or increasing sediment concentrations of these metals for many areas. This will potentially mean coastal sediment is a significant mutagenic hazard to the benthic community for decades to come. An urgent reappraisal of the current input sources for these ‘old pollutants’ is, therefore, required.

peer reviewed | Copper and zinc are metals that have been traditionally thought of as past contamination legacies. However, their industrial use is still extensive and current applications (e.g. nanoparticles and antifouling paints) have become additional marine environment delivery routes. Determining a pollutant's genotoxicity is an ecotoxicological priority, but in marine benthic systems putative substances responsible for sediment genotoxicity have rarely been identified. Studies that use sediment as the delivery matrix combined with exposures over life-history relevant timescales are also missing for metals. Here we assess copper and zinc's genotoxicity by exposing the ecologically important polychaete Alitta virens to sediment spiked with environmentally relevant concentrations for 9 months. Target bioavailable sediment and subsequent porewater concentrations reflect the global contamination range for coasts, whilst tissue concentrations, although elevated, were comparable with other polychaetes. Survival generally reduced as concentrations increased, but monthly analyses show that growth was not significantly different between treatments. The differential treatment mortality may have enabled the surviving worms in the high concentration treatments to capture more food thus removing any concentration treatment effects for biomass. Using the alkaline comet assay we confirm that both metals via the sediment are genotoxic at concentrations routinely found in coastal regions and this is supported by elevated DNA damage in worms from field sites. However, combined with the growth data it also highlights the tolerance of A. virens to DNA damage. Finally, using long term (decadal) monitoring data we show stable or increasing sediment concentrations of these metals for many areas. This will potentially mean coastal sediment is a significant mutagenic hazard to the benthic community for decades to come. An urgent reappraisal of the current input sources for these ‘old pollutants’ is, therefore, required. Chronic exposure of zinc and copper via sediment at environmentally relevant concentrations induces DNA damage in a marine polychaete. © 2018 Elsevier Ltd