Sea-spray (or sea-salt) aerosol (SSA) formation and their subsequent atmospheric transport and deposition have been suggested to play a prominent role in the occurrence of ionizable perfluoroalkyl substances (PFAS) in the maritime Antarctica and other remote regions. However, field studies on SSA’s role as vector of transport of PFAS are lacking. Following a multiphase approach, seawater (SW), the sea-surface microlayer (SML) and SSA were sampled simultaneously at South Bay (Livingston Island, Antarctica). Average PFAS concentrations were 313 pg L⁻¹, 447 pg L⁻¹, and 0.67 pg m⁻³ in SW, the SML and SSA, respectively. The enrichment factors of PFAS in the SML and SSA ranged between 1.2 and 5, and between 522 and 4690, respectively. This amplification of concentrations in the SML is consistent with the surfactant properties of PFAS, while the large enrichment of PFAS in atmospheric SSA may be facilitated by the large surface area of SSA and the sorption of PFAS to aerosol organic matter. This is the first field work assessing the simultaneous occurrence of PFAS in SW, the SML and SSA. The large measured amplification of concentrations in marine aerosols supports the role of SSA as a relevant vector for long-range atmospheric transport of PFAS.

The accumulation of Perfluoroalkyl substances (PFAS) in the SML and their enrichment in SSA is consistent with marine aerosols as a vector for PFAS transport.Sea-spray (or sea-salt) aerosol (SSA) formation and their subsequent atmospheric transport and deposition have been suggested to play a prominent role in the occurrence of ionizable perfluoroalkyl substances (PFAS) in the maritime Antarctica and other remote regions. However, field studies on SSA's role as vector of transport of PFAS are lacking. Following a multiphase approach, seawater (SW), the sea-surface microlayer (SML) and SSA were sampled simultaneously at South Bay (Livingston Island, Antarctica). Average PFAS concentrations were 313 pg L, 447 pg L, and 0.67 pg m in SW, the SML and SSA, respectively. The enrichment factors of PFAS in the SML and SSA ranged between 1.2 and 5, and between 522 and 4690, respectively. This amplification of concentrations in the SML is consistent with the surfactant properties of PFAS, while the large enrichment of PFAS in atmospheric SSA may be facilitated by the large surface area of SSA and the sorption of PFAS to aerosol organic matter. This is the first field work assessing the simultaneous occurrence of PFAS in SW, the SML and SSA. The large measured amplification of concentrations in marine aerosols supports the role of SSA as a relevant vector for long-range atmospheric transport of PFAS. | the mass of PFAS and Naþin SSA are in line with reported mea-surements. Such large enrichment factors in SSA have also beendescribed for experiments simulating the formation of SSA underlaboratory conditions (Reth et al., 2011). Underfield conditions,Casal et al. (2017a,2017b)has shown that the profile of PFCA inAntarctic fresh snow is particularly enriched with long-chain PFCA,consistent with the results reported here of high EFSSAfor PFOA,PFNA and PFDA. As snowflakes scavenge aerosols during deposi-tion, the large concentrations of PFAS in SSA are consistent withsnow deposition being a relevant source of PFAS in cold environ-ments, and SSA are an important source of PFAS to snow.As far as we know, this is thefirstfield study reporting thesimultaneous measurements of PFAS in SW, the SML and SSA. Eventhough there is some enrichment of PFAS at the SML of the surfaceocean, most of the large concentrations of PFAS in marine aerosolare due to the amplification of concentration during the formationof SSA. Such amplification of concentrations by more than twoorders of magnitude can be facilitated by various processes relatedto the accumulation of PFAS at the surface of the sea and aerosols. Ithas been suggested that SSA can be inverse micelles (Ellison et al.,1999;Gerard et al., 2016;Tervahattu et al., 2002). The criticalmicelle concentration for PFOA is of 0.00885 M (3.7 109ng L1)(Reth et al., 2011), thus orders of magnitude higher than PFOAconcentrations in the SML and in SSA. The targeted PFAS aredissociated at marine pH, acting as amphiphilic surfactants, butPFAS alone cannot form micelles in SSA by their own. However,marine aerosols are often coated with an OM layer (Tervahattuet al., 2002). PFAS can be part of this layer of lipids (fatty acids,hydrocarbons) in SSA or being adsorbed onto it. PFAS could be partof micelles together with surfactant-like OM, abundant in the SMLand SSA, but the confirmation of this would require future work.SSA have a large surface area, much larger than the SML. Assuminga thickness of 100mm for the SML, 1 L of SML water corresponds to10 m2of sea surface. On the other hand, SSA have sizes rangingfrom 0.01mmto1mm(Johansson et al., 2019), which means that 1 Lof SSAs having these aerosol sizes have a surface area of 600,000 m2and 6000 m2, respectively. Thus, SSA has a surface area between600 and 60,000 that of the SML, consistent with EFSSAorders ofmagnitude larger than EFSML. The large variability of EFSSAmay bethe result to different sizes of SSA and different characteristics ofthe highly variable SML. These issues will require further researchin order to improve the models for the long-range transport of PFASto Antarctica and elsewhere.4. ConclusionsPFAS were found to be ubiquitous in SW, the SML and SSA inSouth Bay from Livingston Island (southern Shetlands), a repre-sentative environment of the maritime Antarctica. Nevertheless,there were some differences in the relative abundance of PFAS inthe different matrixes, with PFSA and PFCA with carbon number ofC4 and C6, or C6 and C8eC10, respectively, being dominant in theSML and the underlying waters. High concentrations of PFBA werefound in SSA. The enrichment factors in the SML and SSA, defined asthe ratio of concentrations in the SML or SSA and that of SW,respectively, ranged between 1.2 and 5, and between 522 and 4692.The enrichment of PFAS in the SML is consistent with the amphi-philic properties of PFAS and their moderate hydrophobicity. Thelarge amplification of concentrations in SSA may be due to the largesurface area of SSA, the formation of inverse micelles by the largeamounts of surfactant like OM present in SSA, which may includePFAS and other organic compounds present in the SML, or tosorption of PFAS to OM present in SSA. The efficient transfer of PFASfrom the ocean to the atmosphere through the formation of SSAmay be relevant for atmospheric long-range transport of PFAS toAntarctica and other remote environments.Author statementGemma Casas: Conceptualization, Methodology, Formal anal-ysis, Investigation, Writing Original draft, Writing review&editing.Alicia Martinez-Varela: Methodology, Investigation. Jose LuisRoscales: Methodology, Investigation. Maria Vila-Costa: Method-ology, Investigation. Jordi Dachs: Conceptualization, Formal anal-ysis, Investigation, Writing review&editing. Bego~na Jimenez:Conceptualization, Methodology, Investigation, writing review&editing.Declaration of competing interestThe authors declare that they have no known competingfinancial interests or personal relationships that could haveappeared to influence the work reported in this paper.AcknowledgmentsWe thank the staff of the Marine Technology Unit (UTM-CSIC)for their logistical support during the sampling campaign at Liv-ingston Island, and M. Pizarro for technical assistance. This workwas supported by Spanish Ministry of science to GC and AMVthrough predoctoral fellowships, and through projects SENTINEL(CTM 2015-70535-P) and ISOMICS (CTM 2015-65691-R). This research is part of POLARCSIC activities. The research group of Global Change and Genomic Biogeochemistry receives support from the Catalan Government (2017SGR800). Special thanks toTERNUA for their non profit collaboration by sponsoring with technical ecofriendly clothing and gear equipment for Antarctic campaigns

The Paraná River basin is one of the most important in South America and is affected by human activities that take place on its margins. In particular, the De la Cruz stream flows through an industrial pole and the Arrecifes River goes mainly through agricultural fields. The aim of this study was to evaluate the water quality of the De la Cruz stream (S1) and the Arrecifes River (S2) by means of physicochemical parameters, including metals and pesticides concentrations. Since amphibians are good indicators of environmental quality, bioassays with Rhinella arenarum were carried on. For lethal and sublethal parameters, embryos and larvae were exposed to a dilution gradient of water samples and AMPHITOX Solution (AS) as negative control for 504 h. For the determination of oxidative stress biomarkers (Catalase -CAT-, Glutathione S-Transferase -GST-, Reduced Glutathione -GSH-, and lipid peroxidation -TBARS-), embryos and larvae were exposed to undiluted water samples and AS. For the determination of micronuclei, larvae at hind limb bud stage (S.28) were exposed to undiluted water samples, simultaneously with negative and positive controls (AS and cyclophosphamide 40 mg/L, respectively). Dissolved oxygen was low in both sites and the copper levels exceeded the Argentine limit for the protection of aquatic life. In embryos exposure, water sample from S1 caused lethal effects (504h-LC50 = 49 (28–71.6)%), increased TBARS levels, and GST and CAT activities. In larvae exposure, water sample from this site decreased CAT activity, while the water sample from S2 caused important lethal effects (504h-LC50 = 98.72 (60.60–302.52)%), low GSH levels and increased GST activity. Water samples from both sites induced higher micronuclei frequency than the negative control. This study alerts about the degradation of water quality of the studied sites including lethal and sublethal effects in R. arenarum that can jeopardize the native populations of this species.

The Paraná River basin is one of the most important in South America and is affected by human activities that take place on its margins. In particular, the De la Cruz stream flows through an industrial pole and the Arrecifes River goes mainly through agricultural fields. The aim of this study was to evaluate the water quality of the De la Cruz stream (S1) and the Arrecifes River (S2) by means of physicochemical parameters, including metals and pesticides concentrations. Since amphibians are good indicators of environmental quality, bioassays with Rhinella arenarum were carried on. For lethal and sublethal parameters, embryos and larvae were exposed to a dilution gradient of water samples and AMPHITOX Solution (AS) as negative control for 504 h. For the determination of oxidative stress biomarkers (Catalase -CAT-, Glutathione S-Transferase -GST-, Reduced Glutathione -GSH-, and lipid peroxidation -TBARS-), embryos and larvae were exposed to undiluted water samples and AS. For the determination of micronuclei, larvae at hind limb bud stage (S.28) were exposed to undiluted water samples, simultaneously with negative and positive controls (AS and cyclophosphamide 40 mg/L, respectively). Dissolved oxygen was low in both sites and the copper levels exceeded the Argentine limit for the protection of aquatic life. In embryos exposure, water sample from S1 caused lethal effects (504h-LC50 = 49 (28–71.6)%), increased TBARS levels, and GST and CAT activities. In larvae exposure, water sample from this site decreased CAT activity, while the water sample from S2 caused important lethal effects (504h-LC50 = 98.72 (60.60–302.52)%), low GSH levels and increased GST activity. Water samples from both sites induced higher micronuclei frequency than the negative control. This study alerts about the degradation of water quality of the studied sites including lethal and sublethal effects in R. arenarum that can jeopardize the native populations of this species. | Fil: Peluso, Julieta. Universidad Nacional de San Martín (UNSAM). Instituto de Investigación e Ingeniería Ambiental; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. | Fil: Aronzon, Carolina Mariel. Universidad Nacional de San Martín (UNSAM). Instituto de Investigación e Ingeniería Ambiental; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET); Argentina. | Fil: Ríos de Molina, María del Carmen. Instituto Nacional de Tecnología Agropecuaria (INTA). Instituto Tecnología de Alimentos; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. | Fil: Rojas, Dante Emanuel. Instituto Nacional de Tecnología Agropecuaria (INTA). Instituto Tecnología de Alimentos; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Biológica. Instituto de Química Biológica; Argentina. | Fil: Cristos, Diego Sebastian. Instituto Nacional de Tecnología Agropecuaria (INTA). Instituto Tecnología de Alimentos; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Biológica. Instituto de Química Biológica; Argentina. | Fil: Pérez Coll, Cristina Silvia. Universidad Nacional de San Martín (UNSAM). Instituto de Investigación e Ingeniería Ambiental; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET); Argentina.

Marine diatoms have been identified among the most abundant taxa of microorganisms associated with plastic waste collected at sea. However, the impact of nano-sized plastic fragments (nanoplastics) at single cell and population level is almost unknown. We exposed the marine diatom Skeletonema marinoi to model polystyrene nanoparticles with carboxylic acid groups (PS–COOH NPs, 90 nm) for 15 days (1, 10, 50 μg/mL). Growth, reactive oxygen species (ROS) production, and nano-bio-interactions were investigated. No effect on diatom growth was observed, however Dynamic light scattering (DLS) demonstrated the formation of large PS aggregates which were localized at the diatoms’ fultoportula process (FPP), as shown by TEM images. Increase production of ROS and reduction in chain length were also observed upon PS NPs exposure (p < 0.005). The observed PS-diatom interaction could have serious consequences on diatoms ecological role on the biogeochemical cycle of carbon, by impairing the formation of fast-sinking aggregates responsible for atmospheric carbon fixation and sequestration in the ocean sea floor.S. marinoi exposure to PS NPs caused an increase of intracellular and extracellular oxidative stress, the reduction of diatom’s chain length and the adhesion of PS NPs onto the algal surface.

Marine diatoms have been identified among the most abundant taxa of microorganisms associated with plastic waste collected at sea. However, the impact of nano-sized plastic fragments (nanoplastics) at single cell and population level is almost unknown. We exposed the marine diatom Skeletonema marinoi to model polystyrene nanoparticles with carboxylic acid groups (PS–COOH NPs, 90 nm) for 15 days (1, 10, 50 μg/mL). Growth, reactive oxygen species (ROS) production, and nano-bio-interactions were investigated. No effect on diatom growth was observed, however Dynamic light scattering (DLS) demonstrated the formation of large PS aggregates which were localized at the diatoms’ fultoportula process (FPP), as shown by TEM images. Increase production of ROS and reduction in chain length were also observed upon PS NPs exposure (p < 0.005). The observed PS-diatom interaction could have serious consequences on diatoms ecological role on the biogeochemical cycle of carbon, by impairing the formation of fast-sinking aggregates responsible for atmospheric carbon fixation and sequestration in the ocean sea floor. S. marinoi exposure to PS NPs caused an increase of intracellular and extracellular oxidative stress, the reduction of diatom's chain length and the adhesion of PS NPs onto the algal surface.

Endometriosis is a gynaecological disease characterised by the presence of endometriotic tissue outside of the uterus impacting a significant fraction of women of childbearing age. Evidence from epidemiological studies suggests a relationship between risk of endometriosis and exposure to some organochlorine persistent organic pollutants (POPs). However, these chemicals are numerous and occur in complex and highly correlated mixtures, and to date, most studies have not accounted for this simultaneous exposure. Linear and logistic regression models are constrained to adjusting for multiple exposures when variables are highly intercorrelated, resulting in unstable coefficients and arbitrary findings. Advanced machine learning models, of emerging use in epidemiology, today appear as a promising option to address these limitations. In this study, different machine learning techniques were compared on a dataset from a case-control study conducted in France to explore associations between mixtures of POPs and deep endometriosis. The battery of models encompassed regularised logistic regression, artificial neural network, support vector machine, adaptive boosting, and partial least-squares discriminant analysis with some additional sparsity constraints. These techniques were applied to identify the biomarkers of internal exposure in adipose tissue most associated with endometriosis and to compare model classification performance. The five tested models revealed a consistent selection of most associated POPs with deep endometriosis, including octachlorodibenzofuran, cis-heptachlor epoxide, polychlorinated biphenyl 77 or trans-nonachlor, among others. The high classification performance of all five models confirmed that machine learning may be a promising complementary approach in modelling highly correlated exposure biomarkers and their associations with health outcomes. Regularised logistic regression provided a good compromise between the interpretability of traditional statistical approaches and the classification capacity of machine learning approaches. Applying a battery of complementary algorithms may be a strategic approach to decipher complex exposome-health associations when the underlying structure is unknown.

International audience

Microplastic pollution is becoming a major challenge with the growing use of plastic. In recent years, research about microplastic pollution in the environment has become a field of study with increased interest, with ever expanding findings on sources, sinks and pathways of microplastics. Wastewater treatment plants effectively remove microplastics from wastewater and concentrate them in sewage sludge which is often used to fertilise agricultural fields. Despite this, quantification of microplastic pollution in agricultural fields through the application of sewage sludge is largely unknown. In light of this issue, four wastewater treatment plants and 16 agricultural fields (0–8 sewage sludge applications of 20–22 tons ha⁻¹ per application), located in the east of Spain, were sampled. Microplastics were extracted using a floatation and filtration method, making a distinction between light density microplastics (ρ < 1 g cm⁻³) and heavy density microplastics (ρ > 1 g cm⁻³). Sewage sludge, on average, had a light density plastic load of 18,000 ± 15,940 microplastics kg⁻¹ and a heavy density plastic load of 32,070 ± 19,080 microplastics kg⁻¹. Soils without addition of sewage sludge had an average light density plastic load of 930 ± 740 microplastics kg⁻¹ and a heavy density plastic load of 1100 ± 570 microplastics kg⁻¹. Soils with addition of sewage sludge had an average light density plastic load of 2130 ± 950 microplastics kg⁻¹ and a heavy density plastic load of 3060 ± 1680 microplastics kg⁻¹. On average, soils’ plastic loads increased by 280 light density microplastics kg⁻¹ and 430 heavy density microplastics kg⁻¹ with each successive application of sewage sludge, indicating that sewage sludge application results in accumulation of microplastics in agricultural soils.

Microplastic pollution is becoming a major challenge with the growing use of plastic. In recent years, research about microplastic pollution in the environment has become a field of study with increased interest, with ever expanding findings on sources, sinks and pathways of microplastics. Wastewater treatment plants effectively remove microplastics from wastewater and concentrate them in sewage sludge which is often used to fertilise agricultural fields. Despite this, quantification of microplastic pollution in agricultural fields through the application of sewage sludge is largely unknown. In light of this issue, four wastewater treatment plants and 16 agricultural fields (0–8 sewage sludge applications of 20–22 tons ha−1 per application), located in the east of Spain, were sampled. Microplastics were extracted using a floatation and filtration method, making a distinction between light density microplastics (ρ < 1 g cm−3) and heavy density microplastics (ρ > 1 g cm−3). Sewage sludge, on average, had a light density plastic load of 18,000 ± 15,940 microplastics kg−1 and a heavy density plastic load of 32,070 ± 19,080 microplastics kg−1. Soils without addition of sewage sludge had an average light density plastic load of 930 ± 740 microplastics kg−1 and a heavy density plastic load of 1100 ± 570 microplastics kg−1. Soils with addition of sewage sludge had an average light density plastic load of 2130 ± 950 microplastics kg−1 and a heavy density plastic load of 3060 ± 1680 microplastics kg−1. On average, soils’ plastic loads increased by 280 light density microplastics kg−1 and 430 heavy density microplastics kg−1 with each successive application of sewage sludge, indicating that sewage sludge application results in accumulation of microplastics in agricultural soils. Microplastics concentrations in soils are highly proportional to the number of sludge applications.

Harmful algal blooms (HABs) of toxic species of the dinoflagellate genus Dinophysis are a threat to human health as they are mainly responsible for diarrheic shellfish poisoning (DSP) in the consumers of contaminated shellfish. Such contamination leads to shellfish farm closures causing major economic and social issues. The direct effects of numerous HAB species have been demonstrated on adult bivalves, whereas the effects on critical early life stages remain relatively unexplored. The present study aimed to determine the in vitro effects of either cultivated strains of D. sacculus and D. acuminata isolated from France or their associated toxins (i.e. okadaic acid (OA) and pectenotoxin 2 (PTX2)) on the quality of the gametes of the Pacific oyster Crassostrea gigas. This was performed by assessing the ROS production and viability of the gametes using flow cytometry, and fertilization success using microscopic counts. Oocytes were more affected than spermatozoa and their mortality and ROS production increased in the presence of D. sacculus and PTX2, respectively. A decrease in fertilization success was observed at concentrations as low as 0.5 cell mL⁻¹ of Dinophysis spp. and 5 nM of PTX2, whereas no effect of OA could be observed. The effect on fertilization success was higher when both gamete types were concomitantly exposed compared to separate exposures, suggesting a synergistic effect. Our results also suggest that the effects could be due to cell-to-cell contact. These results highlight a potential effect of Dinophysis spp. and PTX2 on reproduction and recruitment of the Pacific oyster.

Harmful algal blooms (HABs) of toxic species of the dinoflagellate genus Dinophysis are a threat to human health as they are mainly responsible for diarrheic shellfish poisoning (DSP) in the consumers of contaminated shellfish. Such contamination leads to shellfish farm closures causing major economic and social issues. The direct effects of numerous HAB species have been demonstrated on adult bivalves, whereas the effects on critical early life stages remain relatively unexplored. The present study aimed to determine the in vitro effects of either cultivated strains of D. sacculus and D. acuminata isolated from France or their associated toxins (i.e. okadaic acid (OA) and pectenotoxin 2 (PTX2)) on the quality of the gametes of the Pacific oyster Crassostrea gigas. This was performed by assessing the ROS production and viability of the gametes using flow cytometry, and fertilization success using microscopic counts. Oocytes were more affected than spermatozoa and their mortality and ROS production increased in the presence of D. sacculus and PTX2, respectively. A decrease in fertilization success was observed at concentrations as low as 0.5 cell mL−1 of Dinophysis spp. and 5 nM of PTX2, whereas no effect of OA could be observed. The effect on fertilization success was higher when both gamete types were concomitantly exposed compared to separate exposures, suggesting a synergistic effect. Our results also suggest that the effects could be due to cell-to-cell contact. These results highlight a potential effect of Dinophysis spp. and PTX2 on reproduction and recruitment of the Pacific oyster.

Myctophids are the most abundant fish group in the Southern Ocean pelagic ecosystem and are an important link in the Antarctic marine food web. Due to their major ecological role, evaluating the level of mercury (Hg) contamination in myctophids is important as a step towards understanding the trophic pathway of this contaminant. The concentrations of total Hg were determined in muscle, gill, heart and liver tissue of 9 myctophid species to quantify tissue partitioning variability between species. Organic Hg concentration and proportion in muscle was also determined. Hg concentrations were higher in the liver and heart than in muscle and gills, but the proportion of organic Hg was almost 100% in muscle, indicating that the main uptake route for Hg is through the diet. Most of the species analysed have similar vertical and horizontal distributions, and similar feeding modes and prey. Geographical and temporal variability of Hg concentrations was examined using samples from 3 different sampling cruise (2007/08, 2015/16 and 2016/17) and 2 locations (South Georgia and South Orkneys Islands). Our results appear to indicate a decreasing trend in Hg contamination over the last decade, particularly gill tissue, which is in agreement with a previous study on squid from the same region. There was no significant variability in Hg concentration between the different sampling locations. Hg levels were consistent with values reported previously for myctophids around the world, indicating low global-scale geographic variability. A positive relationship between fish size and Hg concentration was found for most species, with the exception of Electrona antarctica females, which may be explained through Hg elimination by egg laying. We estimate that myctophids collectively comprise a Southern Ocean mercury ‘reserve’ of ≈1.82 metric tonnes.

Myctophids are the most abundant fish group in the Southern Ocean pelagic ecosystem and are an important link in the Antarctic marine food web. Due to their major ecological role, evaluating the level of mercury (Hg) contamination in myctophids is important as a step towards understanding the trophic pathway of this contaminant. The concentrations of total Hg were determined in muscle, gill, heart and liver tissue of 9 myctophid species to quantify tissue partitioning variability between species. Organic Hg concentration and proportion in muscle was also determined. Hg concentrations were higher in the liver and heart than in muscle and gills, but the proportion of organic Hg was almost 100% in muscle, indicating that the main uptake route for Hg is through the diet. Most of the species analysed have similar vertical and horizontal distributions, and similar feeding modes and prey. Geographical and temporal variability of Hg concentrations was examined using samples from 3 different sampling cruise (2007/08, 2015/16 and 2016/17) and 2 locations (South Georgia and South Orkneys Islands). Our results appear to indicate a decreasing trend in Hg contamination over the last decade, particularly gill tissue, which is in agreement with a previous study on squid from the same region. There was no significant variability in Hg concentration between the different sampling locations. Hg levels were consistent with values reported previously for myctophids around the world, indicating low global-scale geographic variability. A positive relationship between fish size and Hg concentration was found for most species, with the exception of Electrona antarctica females, which may be explained through Hg elimination by egg laying. We estimate that myctophids collectively comprise a Southern Ocean mercury 'reserve' of ≈1.82 metric tonnes. | published

The bioaccessibility of arsenic and its speciation are two important factors in assessing human health risks exposure to contaminated soils. However, the effects of human gut microbiota on arsenic bioaccessibility and its speciation are not well characterized. In this study, an improved in vitro model was utilized to investigate the bioaccessibility of arsenic in the digestive tract and the role of human gut microbiota in the regulation of arsenic speciation. For all soils, arsenic bioaccessibility from the combined in vitro model showed that it was <40% in the gastric, small intestinal and colon phases. This finding demonstrated that the common bioaccessibility approach assuming 100% bioaccessibility would overestimate the human health risks posed by contaminated soils. Further to this, the study showed that arsenic bioaccessibility was 22% higher in the active colon phase than that in the sterile colon phase indicating that human colon microorganisms could induce arsenic release from the solid phase. Only inorganic arsenic was detected in the gastric and small intestinal phases, with arsenate [As(V)] being the dominant arsenic species (74%–87% of total arsenic). Arsenic speciation was significantly altered by the active colon microbiota, which resulted in the formation of methylated arsenic species, including monomethylarsonic acid [MMA(V)] and dimethylarsinic acid [DMA(V)] with low toxicity, and a highly toxic arsenic species monomethylarsonous acid [MMA(III)]. Additionally, a high level of monomethylmonothioarsonic acid [MMMTA(V)] (up to 17% of total arsenic in the extraction solution) with unknown toxicological properties was also detected in the active colon phase. The formation of various organic arsenic species demonstrated that human colon microorganisms could actively metabolize inorganic arsenic into methylated arsenicals and methylated thioarsenicals. Such transformation should be considered when assessing the human health risks associated with oral exposure to soil.

The bioaccessibility of arsenic and its speciation are two important factors in assessing human health risks exposure to contaminated soils. However, the effects of human gut microbiota on arsenic bioaccessibility and its speciation are not well characterized. In this study, an improved in vitro model was utilized to investigate the bioaccessibility of arsenic in the digestive tract and the role of human gut microbiota in the regulation of arsenic speciation. For all soils, arsenic bioaccessibility from the combined in vitro model showed that it was <40% in the gastric, small intestinal and colon phases. This finding demonstrated that the common bioaccessibility approach assuming 100% bioaccessibility would overestimate the human health risks posed by contaminated soils. Further to this, the study showed that arsenic bioaccessibility was 22% higher in the active colon phase than that in the sterile colon phase indicating that human colon microorganisms could induce arsenic release from the solid phase. Only inorganic arsenic was detected in the gastric and small intestinal phases, with arsenate [As(V)] being the dominant arsenic species (74%–87% of total arsenic). Arsenic speciation was significantly altered by the active colon microbiota, which resulted in the formation of methylated arsenic species, including monomethylarsonic acid [MMA(V)] and dimethylarsinic acid [DMA(V)] with low toxicity, and a highly toxic arsenic species monomethylarsonous acid [MMA(III)]. Additionally, a high level of monomethylmonothioarsonic acid [MMMTA(V)] (up to 17% of total arsenic in the extraction solution) with unknown toxicological properties was also detected in the active colon phase. The formation of various organic arsenic species demonstrated that human colon microorganisms could actively metabolize inorganic arsenic into methylated arsenicals and methylated thioarsenicals. Such transformation should be considered when assessing the human health risks associated with oral exposure to soil.

Despite the now well recognised impact of diclofenac on vultures across the Indian subcontinent, this non-steroidal anti-inflammatory drug (NSAID) was registered in 2013 for livestock treatment in Spain, Europe’s main vulture stronghold. We assessed the risk of exposure to diclofenac and nine other NSAIDs in avian scavengers in the Iberian Peninsula (Spain and Portugal) after the onset of diclofenac commercialization. We sampled 228 livestock carcasses from vulture feeding sites, primarily pig (n = 156) and sheep (n = 45). We also sampled tissues of 389 avian scavenger carcasses (306 Eurasian griffon vultures, 15 cinereous vultures, 11 Egyptian vultures, 12 bearded vultures and 45 other facultative scavengers). Samples were analysed by liquid chromatography with mass spectrometry (LCMS). Seven livestock carcasses (3.07%) contained NSAID residues: flunixin (1.75%), ketoprofen, diclofenac and meloxicam (0.44% each). NSAID residues were only detected in sheep (4.44%) and pig (3.21%) carcasses. Fourteen dead avian scavengers (3.60%) had NSAID residues in kidney and liver, specifically flunixin (1.03%) and meloxicam (2.57%). Flunixin was associated with visceral gout and/or kidney damage in three (0.98%) dead Eurasian griffons. To date, diclofenac poisoning has not been observed in Spain and Portugal, however, flunixin would appear to pose an immediate and clear risk. This work supports the need for well managed carrion disposal, alongside appropriate risk labelling on veterinary NSAIDs and other pharmaceuticals potentially toxic to avian scavengers.

Despite the now well recognised impact of diclofenac on vultures across the Indian subcontinent, this non-steroidal anti-inflammatory drug (NSAID) was registered in 2013 for livestock treatment in Spain, Europe's main vulture stronghold. We assessed the risk of exposure to diclofenac and nine other NSAIDs in avian scavengers in the Iberian Peninsula (Spain and Portugal) after the onset of diclofenac commercialization. We sampled 228 livestock carcasses from vulture feeding sites, primarily pig (n = 156) and sheep (n = 45). We also sampled tissues of 389 avian scavenger carcasses (306 Eurasian griffon vultures, 15 cinereous vultures, 11 Egyptian vultures, 12 bearded vultures and 45 other facultative scavengers). Samples were analysed by liquid chromatography with mass spectrometry (LCMS). Seven livestock carcasses (3.07%) contained NSAID residues: flunixin (1.75%), ketoprofen, diclofenac and meloxicam (0.44% each). NSAID residues were only detected in sheep (4.44%) and pig (3.21%) carcasses. Fourteen dead avian scavengers (3.60%) had NSAID residues in kidney and liver, specifically flunixin (1.03%) and meloxicam (2.57%). Flunixin was associated with visceral gout and/or kidney damage in three (0.98%) dead Eurasian griffons. To date, diclofenac poisoning has not been observed in Spain and Portugal, however, flunixin would appear to pose an immediate and clear risk. This work supports the need for well managed carrion disposal, alongside appropriate risk labelling on veterinary NSAIDs and other pharmaceuticals potentially toxic to avian scavengers. | published

Evaluating speciation of arsenic (As) is essential to assess its risk in paddy soils. In this study, effects of phosphate on speciation of As in six paddy soils differing in redox status were studied over a range of pH (pH 3-9) and different background calcium (Ca) levels by batch adsorption experiments and speciation modeling. Contrasting effects of phosphate on As speciation were observed in suboxic and anoxic soils. Under suboxic conditions, phosphate inhibited Fe and As reduction probably due to stabilization of Fe-(hydr)oxides, but increased soluble As(V) concentration as a result of competitive adsorption between As(V) and phosphate. In anoxic soils, phosphate stimulated Fe and As reduction and caused increases of As(III) in soil solution under both acidic and neutral/alkaline pH. The LCD (Ligand and Charge Distribution) and NOM-CD (Natural Organic Matter-Charge Distribution) model can describe effects of pH, calcium and phosphate on As speciation in these paddy soils. The results suggest that phosphate fertilization may decrease (at low pH) or increase (at neutral/alkaline pH) As mobility in paddy soils under (sub)oxic conditions, but under anoxic conditions and in phosphorus deficient soils phosphate fertilization may strongly mobilize As by promoting microbial activities.

Evaluating speciation of arsenic (As) is essential to assess its risk in paddy soils. In this study, effects of phosphate on speciation of As in six paddy soils differing in redox status were studied over a range of pH (pH 3-9) and different background calcium (Ca) levels by batch adsorption experiments and speciation modeling. Contrasting effects of phosphate on As speciation were observed in suboxic and anoxic soils. Under suboxic conditions, phosphate inhibited Fe and As reduction probably due to stabilization of Fe-(hydr)oxides, but increased soluble As(V) concentration as a result of competitive adsorption between As(V) and phosphate. In anoxic soils, phosphate stimulated Fe and As reduction and caused increases of As(III) in soil solution under both acidic and neutral/alkaline pH. The LCD (Ligand and Charge Distribution) and NOM-CD (Natural Organic Matter-Charge Distribution) model can describe effects of pH, calcium and phosphate on As speciation in these paddy soils. The results suggest that phosphatefertilization may decrease (at low pH) or increase (at neutral/alkaline pH) As mobility in paddy soils under (sub)oxic conditions, but under anoxic conditions and in phosphorus deficient soils phosphate fertilization may strongly mobilize As by promoting microbial activities.