Blood Kinetics of Lipophilic and Proteinophilic Pollutants during Two Types of Long-Term Fast in King Penguins.

In vertebrates, fasting is an intricate physiological process associated with strong metabolic changes, yet its effect on pollutant residue variation is poorly understood. Here, we quantified long-term changes in plasma concentrations of 20 organochlorine and 16 perfluoroalkyl pollutants in king penguins Aptenodytes patagonicus during the breeding and molting fasts, which are marked by low and high levels of protein catabolism, respectively, and by strong lipid use. The profile of measured pollutants in plasma was dominated by perfluorooctanesulfonic acid (PFOS, initial relative contribution of 60%). Initial total pollutant concentrations were similar in molting (3.3-5.7 ng g-1 ww) and breeding penguins (range of 4.2-7.3 ng g-1 wet weight, ww). Long-term fasting (25 days) for molting and breeding led, respectively, to a 1.8- and 2.2-fold increase in total plasma pollutant concentrations, although the rate and direction of change were compound-specific. Hexachlorbenzene (HCB) and PFOS concentrations increased in plasma (net mobilization) during both types of fasting, likely due to lipid use. Plasma perfluoroundecanoate (PFUnDA) and perfluorotridecanoate (PFTrDA) concentrations increased in breeders (net mobilization) but decreased in molting individuals (net excretion), suggesting a significant incorporation of these pollutants into feathers. This study is a key contribution to our understanding of pollutant variation in blood during long-term fasting in wildlife.

Trophic Transfer of Micropollutants and Their Metabolites in an Urban Riverine Food Web.

Trophic magnification factors (TMFs, i.e., the average change in the log-concentration of a pollutant per trophic level) have been extensively assessed for the so-called persistent organic pollutants, especially organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs), which are biomagnified along the food web. In contrast, trophic dilution was documented for pollutants with a high metabolic conversion rate, such as phthalate plasticizers and polycyclic aromatic hydrocarbons (PAHs). However, the fate of their metabolites across the food web has been rarely investigated. In this comparative study, the trophodynamics of 104 micropollutants and 25 of their metabolites were investigated in a freshwater food web from the urban Orge River, France. Trophic levels were determined using stable isotopes. Pyrethroid pesticides and their metabolites were not detected. As predicted, PCBs and OCPs biomagnified (TMF >1), while all chlorinated paraffins (CPs), PAHs, and phthalates underwent a trophic dilution (TMF <1). TMFs significantly decreased with a metabolic transformation rate and increased with hydrophobicity. The levels of PAH or phthalate metabolites were not significantly correlated with trophic levels or underwent a trophic dilution. This study highlighted that the relative contribution of metabolite levels in TMF values calculated for both parent compound and its metabolite(s) is weak compared to TMF values of the parent compound only in a riverine food web.

A Bayesian framework for estimating parameters of a generic toxicokinetic model for the bioaccumulation of organic chemicals by benthic invertebrates: Proof of concept with PCB153 and two freshwater species.

Toxicokinetic (TK) models are relevant and widely used to predict chemical concentrations in biological organisms. The importance of dietary uptake for aquatic invertebrates has been increasingly assessed in recent years. However, the model parameters are estimated on limited specific laboratory data sets that are bounded by several uncertainties. The aim of this study was to implement a Bayesian framework for simultaneously estimating the parameters of a generic TK model for benthic invertebrate species from all data collected. We illustrate our approach on the bioaccumulation of PCB153 by two species with different life traits and therefore exposure routes: Chironomus riparius larvae exposed to spiked sediment for 7 days and Gammarus fossarum exposed to spiked sediment and/or leaves for 7 days and then transferred to a clean media for 7 more days. The TK models assuming first-order kinetics were fitted to the data using Bayesian inference. The median model predictions and their 95% credibility intervals showed that the model fit the data well. From a methodological point of view, this paper illustrates that simultaneously estimating all model parameters from all available data by Bayesian inference, while considering the correlation between parameters and different types of data, is a real added value for TK modeling. Moreover, we demonstrated the ability of a generic TK model considering uptake and elimination routes as modules to add according to the availability of the data measured. From an ecotoxicological point of view, we show differences in PCB153 bioaccumulation between chironomids and gammarids, explained by the different life traits of these two organisms.

Refining uptake and depuration constants for fluoroalkyl chemicals in Chironomus riparius larvae on the basis of experimental results and modelling.

The aims of this study were to determine depuration rates for a range of per- and polyfluoroalkyl substances (PFASs) using Chironomus riparius, and to test a concentration-dependency hypothesis for the long-chain perfluorotridecanoic acid (PFTrDA) for this species. Midge larvae were exposed to field sediments collected downstream of a fluorotelomer plant, and to the same sediment spiked with PFTrDA. Elimination kinetics results indicated complete elimination of all PFASs by chironomids after 42h. These data were used to develop two PFTrDA bioaccumulation models accounting for chironomid growth and for compound concentration dependency or not. There was much better agreement between observed and simulated data under the concentration-dependency hypothesis than under the alternative one (passive diffusion). The PFTrDA uptake rate derived from the concentration-dependency model equaled 0.013 ± 0.008gocgwwh-1, and the depuration rate 0.032 ± 0.009h-1.

Influence of Environmental Factors on the Fate of Legacy and Emerging Per- and Polyfluoroalkyl Substances along the Salinity/Turbidity Gradient of a Macrotidal Estuary.

This study aimed at bridging knowledge gaps regarding the land-sea transport of per- and polyfluoroalkyl substances (PFASs) through riverine discharge into coastal waters. The present survey was conducted in the Gironde estuary (southwestern France) where PFASs were ubiquitously detected albeit at low levels. Emerging PFASs such as fluorotelomer sulfonates or polyfluoroalkyl phosphate diesters accounted for a relatively minor proportion of ∑PFASs, while perfluorooctanesulfonate, perfluorohexanesulfonate, and perfluorohexanoate were the predominant congeners. Multiple linear regressions provided insights into the relative influence of factors controlling PFAS sediment levels. In that respect, the organic carbon fraction (strongly correlated to sediment grain size) appeared as a more important controlling factor than black carbon or distance from upstream sources for long-chain perfluoroalkyl acids. In the maximum turbidity zone (suspended solids up to 2600 mg L-1), the particle-associated fraction was almost consistently >50% for long-chain perfluoroalkyl carboxylates and sulfonates (≥C8 and ≥ C6, respectively). Empirical models of KD partitioning coefficients were derived by integrating, for the first time, both particle-concentration and salting-out effects. These results represent significant progress toward the development of numerical transport models integrating both PFAS partitioning and 3D-hydrosedimentary dynamics, with a view to estimate PFAS mass budgets at the land-sea interface.

Environmental Occurrence of Perfluoroalkyl Acids and Novel Fluorotelomer Surfactants in the Freshwater Fish Catostomus commersonii and Sediments Following Firefighting Foam Deployment at the Lac-Mégantic Railway Accident.

On July 6th 2013, an unmanned train laden with almost 8 million liters of crude oil careened off the rails downtown Lac-Mégantic (Québec, Canada). In the aftermath of the derailment accident, the emergency response entailed the deployment of 33 000 L of aqueous film forming foam (AFFF) concentrate that contained proprietary fluorosurfactants. The present study examines the environmental occurrence of perfluoroalkyl acids (PFAAs) and newly identified per and polyfluoroalkyl substances (PFASs) in the benthic fish white sucker (Catostomus commersonii) and sediments from Lake Mégantic and Chaudière River. In sediments, PFAAs displayed relatively low concentrations (∑PFAAs = 0.06-0.5 ng g-1 dw) while the sum of fluorotelomer-based PFASs was in the range < LOD-6.2 ng g-1 dw. Notably, fluorotelomer sulfonamide betaines (8:2-FTAB and 10:2-FTAB), fluorotelomer betaines (9:3-FTB, 11:3-FTB and 9:1:2 FTB) and 6:2 fluorotelomer sulfonate (6:2-FTSA) were ubiquitously identified in the sediment samples surveyed. Levels of PFAAs remained moderate in fish muscle (e.g. , PFOS: 0.28-2.1 ng g-1 wet-weight), with little or no differences when comparing 2013 or 2014 fish samples with 2011 archived samples. In contrast, n:2-FTSAs emerged in the immediate weeks or months that followed the accident, as did several betaine-based PFASs (8:2-FTAB, 10:2-FTAB, 9:3-FTB, 11:3-FTB, 7:1:2 FTB and 9:1:2 FTB), observed for the first time in situ. Fluorotelomer thioether amido sulfonate (10:2-FTSAS) and fluorotelomer sulfoxide amido sulfonate (10:2-FTSAS-sulfoxide) were also occasionally reported after the AFFF spill. With time, levels of betaine-based PFASs gradually decreased in fish, possibly indicating attenuation by biodegradation of the fluorine-free moiety, supported by the observation of likely metabolites such as n:3-fluorotelomer carboxylates and n:2-fluorotelomer sulfonamides.

Evidence for the Trophic Transfer of Perfluoroalkylated Substances in a Temperate Macrotidal Estuary.

The present survey examines the trophodynamics of a suite of 19 perfluoroalkyl substances (PFASs) in a temperate macrotidal estuary (Gironde, SW France). Across the 147 biota samples (18 taxa) collected, perfluorooctane sulfonate (PFOS), perfluorooctane sulfonamide (FOSA), and C8-C14 perfluoroalkyl carboxylates (PFCAs) were the most-recurrent analytes. ΣPFASs ranged between 0.66-45 ng per g of wet weight of the whole body. Benthic organisms had relatively high ΣPFASs compared to demersal organisms and displayed specific composition profiles with higher relative abundances of C8 and C9 PFCAs. Trophic magnification factors (TMFs) were determined through the use of linear mixed effect models including censored data, thereby considering data below detection limits as well as the interspecific variability of δ15N and PFAS levels (random effects). TMFs were almost consistently >1 in the benthic food web as well as when considering all data pooled together, providing evidence for the biomagnification of several PFASs in estuarine environments. In addition, in contrast with previous observations, TMFs determined in the estuarine benthic web were found to significantly decrease with increasing chain length for C8-C14 PFCAs and C6-C8 perfluoroalkyl sulfonates. This suggests that PFAS chemical structure might not be necessarily predictive of TMFs, which are also influenced by the trophic web characteristics.

Transcriptome profile analysis reveals specific signatures of pollutants in Atlantic eels.

Identifying specific effects of contaminants in a multi-stress field context remain a challenge in ecotoxicology. In this context, "omics" technologies, by allowing the simultaneous measurement of numerous biological endpoints, could help unravel the in situ toxicity of contaminants. In this study, wild Atlantic eels were sampled in 8 sites presenting a broad contamination gradient in France and Canada. The global hepatic transcriptome of animals was determined by RNA-Seq. In parallel, the contamination level of fish to 8 metals and 25 organic pollutants was determined. Factor analysis for multiple testing was used to identify genes that are most likely to be related to a single factor. Among the variables analyzed, arsenic (As), cadmium (Cd), lindane (γ-HCH) and the hepato-somatic index (HSI) were found to be the main factors affecting eel's transcriptome. Genes associated with As exposure were involved in the mechanisms that have been described during As vasculotoxicity in mammals. Genes correlated with Cd were involved in cell cycle and energy metabolism. For γ-HCH, genes were involved in lipolysis and cell growth. Genes associated with HSI were involved in protein, lipid and iron metabolisms. Our study proposes specific gene signatures of pollutants and their impacts in fish exposed to multi-stress conditions.

Demographic consequences of heavy metals and persistent organic pollutants in a vulnerable long-lived bird, the wandering albatross.

Seabirds are top predators of the marine environment that accumulate contaminants over a long life-span. Chronic exposure to pollutants is thought to compromise survival rate and long-term reproductive outputs in these long-lived organisms, thus inducing population decline. However, the demographic consequences of contaminant exposure are largely theoretical because of the dearth of long-term datasets. This study aims to test whether adult survival rate, return to the colony and long-term breeding performance were related to blood mercury (Hg), cadmium (Cd) and persistent organic pollutants (POPs), by using a capture-mark-recapture dataset on the vulnerable wandering albatross Diomedea exulans. We did not find evidence for any effect of contaminants on adult survival probability. However, blood Hg and POPs negatively impacted long-term breeding probability, hatching and fledging probabilities. The proximate mechanisms underlying these deleterious effects are likely multifaceted, through physiological perturbations and interactions with reproductive costs. Using matrix population models, we projected a demographic decline in response to an increase in Hg or POPs concentrations. This decline in population growth rate could be exacerbated by other anthropogenic perturbations, such as climate change, disease and fishery bycatch. This study gives a new dimension to the overall picture of environmental threats to wildlife populations.

Wandering albatrosses document latitudinal variations in the transfer of persistent organic pollutants and mercury to Southern Ocean predators.

Top marine predators are effective tools to monitor bioaccumulative contaminants in remote oceanic environments. Here, we used the wide-ranging wandering albatross Diomedea exulans to investigate potential geographical variations of contaminant transfer to predators in the Southern Ocean. Blood concentrations of 19 persistent organic pollutants and 14 trace elements were measured in a large number of individuals (N = 180) of known age, sex and breeding status from the subantarctic Crozet Islands. Wandering albatrosses were exposed to a wide range of contaminants, with notably high blood mercury concentrations. Contaminant burden was markedly influenced by latitudinal foraging habitats (inferred from blood δ(13)C values), with individuals feeding in warmer subtropical waters having lower concentrations of pesticides, but higher concentrations of mercury, than those feeding in colder subantarctic waters. Sexual differences in contaminant burden seemed to be driven by gender specialization in feeding habitats, rather than physiological characteristics, with females foraging further north than males. Other individual traits, such as adult age and reproductive status, had little effect on blood contaminant concentrations. Our study provides further evidence of the critical role of global distillation on organic contaminant exposure to Southern Ocean avian predators. In addition, we document an unexpected high transfer of mercury to predators in subtropical waters, which merits further investigation.

Abnormal ovarian DNA methylation programming during gonad maturation in wild contaminated fish.

There is increasing evidence that pollutants may cause diseases via epigenetic modifications. Epigenetic mechanisms such as DNA methylation participate in the regulation of gene transcription. Surprisingly, epigenetics research is still limited in ecotoxicology. In this study, we investigated whether chronic exposure to contaminants experienced by wild female fish (Anguilla anguilla) throughout their juvenile phase can affect the DNA methylation status of their oocytes during gonad maturation. Thus, fish were sampled in two locations presenting a low or a high contamination level. Then, fish were transferred to the laboratory and artificially matured. Before hormonal treatment, the DNA methylation levels of the genes encoding for the aromatase and the receptor of the follicle stimulating hormone were higher in contaminated fish than in fish from the clean site. For the hormone receptor, this hypermethylation was positively correlated with the contamination level of fish and was associated with a decrease in its transcription level. In addition, whereas gonad growth was associated with an increase in DNA methylation in fish from the clean site, no changes were observed in contaminated fish in response to hormonal treatment. Finally, a higher gonad growth was observed in fish from the reference site in comparison to contaminated fish.

Oxidative stress in relation to reproduction, contaminants, gender and age in a long-lived seabird.

Reproduction is a demanding activity for animals, since they must produce, and in some cases protect and provision, their young. It is often overlooked that demands of reproduction may also be exacerbated by exposure to contaminants. In this study, we make use of an exceptional long-term dataset to perform a cross-sectional study on the long-lived wandering albatross (Diomedea exulans) in order to test the effects of reproduction, persistent organic pollutants [POPs: pesticides and polychlorinated biphenyls (PCBs)], mercury, individual age (3-47 years), and sex on the levels of plasma oxidative damage and inflammation. The results of our study support the hypothesis that oxidative damage may be a physiological cost of reproduction and that individuals carrying higher levels of organic or non-organic contaminants have higher oxidative damage. Levels of the inflammatory protein haptoglobin were similar between breeding and non-breeding birds, with the exception of breeding males which had the lowest levels of haptoglobin. Our data also show an effect of age and of organic contaminants on the plasma oxidative damage level, but not on plasma haptoglobin. In addition, plasma oxidative damage level increased with red blood cell mercury concentration in females but not in males. Hence, our study highlights that the harmful effects of contaminants may come through interaction with factors like life stage or gender, suggesting potential for high variation in susceptibility to contamination among individuals.

Polychlorinated biphenyls, polybrominated diphenyl ethers, and phthalates in roach from the Seine River basin (France): impact of densely urbanized areas.

Endocrine disruptors (EDs) from three chemical classes-polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), and phthalates-were investigated in the Seine River and one tributary, the Orge River, upstream and downstream of urban areas. The impact of urban areas was characterized by a concentration increase of all compounds in the Seine River and for phthalates and PBDEs in the Orge River. In the Seine River, from upstream (Marnay) to downstream (Triel) of urban areas, water concentration increases were greater for diethylhexyl phthalate (DEHP) (6 times, p < 0.05) and ∑tri-hexa BDE (5 times [p < 0.05]) than for ∑7PCBi (2.6 times). Simultaneously, sediments displayed a strong accumulation of contaminants downstream and compared with upstream values, their concentrations increased greatly: 202-fold for DEHP, 69-fold for BDE209, 25-fold for ∑tri-hexa-BDE, and 11-fold for ∑7PCBi. Variations of fish ED concentrations gave an indication of their habitat contamination increase observed downstream of densely urbanized areas of the Seine River, especially for PBDEs (∑tri-hexa-PBDEs = 14-fold increase ≤15.7 ± 6.9 ng g(-1) dry weight [dw; p < 0.001]) and for PCBs (∑7PCBi eightfold increase ≤211 ± 55 ng g(-1) dw [p < 0.01]). PCA results highlighted relationships between the different ED classes. A correlation (p < 0.05) was observed between PCB and PBDE fish concentrations, suggesting common sources and similar absorption mechanisms. For PCBs, which were poorly biodegraded, the bioaccumulation factor was strongly correlated (p < 0.001) to molecular hydrophobicity, whereas for PBDEs a negative correlation (p < 0.05) was observed related active debromination processes. This multichemical study investigates for the first time the occurrence of a wide range of EDs in roach, which was chosen as a sentinel species for this survey of surface water contamination.

Relevance of flounder caging and proteomics to explore the impact of a major industrial accident caused by fire on the Seine estuarine water quality.

On September 26th 2019, a major fire occurred in the Lubrizol factory located near the Seine estuary, in Rouen-France. Juvenile flounders were captured in the Canche estuary (a reference system) and caged one month in the Canche and in the Seine downstream the accident site. No significant increases of PAHs, PCBs and PFAS was detected in Seine vs Canche sediments after the accident, but a significant increase of dioxins and furans was observed in water and sewage sludge in the Rouen wastewater treatment plant. The proteomics approach highlighted a dysregulation of proteins associated with cholesterol synthesis and lipid metabolism, in fish caged in the Seine. The overall results suggested that the fire produced air borne dioxins and furans that got deposited on soil and subsequently entered in the Seine estuarine waters via runoff; thus contaminating fish preys and caged flounders in the Seine estuary.

Per- and polyfluoroalkyl substances (PFAS) in surface sediments: Occurrence, patterns, spatial distribution and contribution of unattributed precursors in French aquatic environments.

While perfluoroalkyl sulfonic acids (PFSAs) and perfluoroalkyl carboxylic acids (PFCAs) are ubiquitous in aquatic environments, non-targeted methods have recently revealed the presence of numerous unidentified per- and polyfluoroalkyl substances (PFAS). Besides those methods, the total oxidizable precursor (TOP) assay has proved useful to estimate the contribution of unattributed perfluoroalkyl acids precursors (pre-PFAAs). In this study, an optimized extraction method was developed to examine the spatial distribution of 36 targeted PFAS in surface sediments collected at French nationwide scale (n = 43), including neutral, anionic and zwitterionic molecules. In addition, a TOP assay procedure was implemented to estimate the contribution of unattributed pre-PFAAs in these samples. Conversion yields of targeted pre-PFAAs were determined for the first time under realistic conditions and led to differences in oxidation profiles compared to the common spiked ultra-pure water method. PFAS were detected in 86 % of samples and ∑PFAStargeted was in the range < Limit of Detection - 23 ng g-1 dry weight (dw) (median: 1.3 ng g-1 dw), with ∑pre-PFAAstargeted representing on average 29 ± 26 % of ∑PFAS. Among pre-PFAAs, compounds of emerging interest such as the fluorotelomer sulfonamidoalkyl betaines 6:2 FTAB and 8:2 FTAB were respectively detected in 38 % and 24 % of samples, with levels similar to those of L-PFOS (<0.36-2.2, <0.50-6.8 and < 0.08-5.1 ng g-1 dw, respectively). A hierarchical cluster analysis coupled with a geographic information system-based approach revealed similarities between groups of sampling sites. For instance, elevated contribution of FTABs were associated with the proximity to airport activities where betaine-based aqueous film-forming foam (AFFFs) might have been used. In addition, unattributed pre-PFAAs were strongly correlated with ∑PFAStargeted and they accounted for 58 % of ∑PFAS (median value); they were generally found in larger quantity near industrial and urban areas where the highest ∑PFAStargeted were also observed.

Bioaccumulation of polybrominated diphenyl ethers by the freshwater benthic amphipod Gammarus pulex.

This study reports on the relationship between polybrominated diphenyl ether (PBDE) levels in water, sediment, and the benthic macroinvertebrate Gammarus pulex, which plays a major ecological role in freshwater ecosystems. Samples were taken in a periurban watershed (near Paris, France), and PBDEs were systematically detected in sediment (≤727 ng g(-1) OC) and G. pulex (≤264 ng g(-1) lipids). PBDEs were also occasionally detected in the water column at low levels (∑ PBDEs < 1.5 ng L(-1)). The log values of bioaccumulation factors were in the range 7.8 ± 0.1-8.3 ± 0.4 L kg(-1) for tetra- and penta-BDEs, which were the only ones quantified in the dissolved phase of river water. Meanwhile, levels of individual tri- to hepta-PBDE congeners in G. pulex generally positively correlated with sediment levels, suggesting an equilibrium situation. Biota-to-sediment accumulation factors (BSAFs) of tri-hepta BDEs were congener specific and were in the range 0.5 ± 0.3-2.6 ± 1.2. For several PBDEs, BSAF values deviated from the expected range, likely because of in vivo metabolism.

Occurrence of polybrominated diphenyl ethers, polychlorinated biphenyls, and phthalates in freshwater fish from the Orge river (Ile-de France).

Polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs), and phthalates were investigated from July 2009 to April 2010 in three fish species from the Orge river, which flows in a densely populated area of Ile-de-France. In two Cyprinidae (roach and chub) and one Percidae (perch), muscle contents in increasing order ranged as follows: 12-18 ng g(-1) dw for PBDEs (Σtri-hepta), 120-170 ng g(-1) dw for PCBs (Σ7), and 2,250-5,125 ng g(-1) dw for phthalates (Σ7). No variation was observed between contaminant contents and lipid levels. No biomagnification was found according to the trophic level for PBDEs and PCBs, whereas for phthalates the highest contents were found in perch. Seasonal variations were observed with the lowest PBDE and PCB contents occurring in July after spawning in roach and perch (p < 0.001). PBDE content followed a decreasing trend-gonad > liver > muscle-whatever the period. For PCBs, gonad and liver contents remained greater than that of muscle (p < 0.05). Our results indicate a preferential accumulation of halogenated compounds in gonad and liver outside the reproduction period. Bioaccumulation factors for PCBs in muscle were significantly correlated to their chlorination degree in perch (p < 0.01) and roach (p < 0.01). In roach, that correlation slope was by decreasing importance order as follows: gonad > liver > muscle. The biota-sediment accumulation factors varied from 0.1 to 29.2, from 1.6 to 4.8, and from 1 to 123.5 for PBDEs, PCBs, and phthalates, respectively. These results contribute to document the use of freshwater fish as bioindicators of river quality.

Influence of hydrological parameters on organohalogenated micropollutant (polybrominated diphenyl ethers and polychlorinated biphenyls) behaviour in the Seine (France).

The temporal dynamics of polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) were investigated in a heavily urbanized river (Seine River, Paris, France) from November 2009 to May 2010. Pollutant concentrations were in the range of 0.2 to 3.8 ng l(-1) (median 1.1) and 0.4 to 3.6 ng l(-1) (median 1.1) for ∑ tri-deca BDEs and ∑ 7PCBs, respectively. In addition, for both PBDEs and PCBs, the partitioning between the particulate and dissolved phases was investigated. Due to their low water solubility, PBDEs were mainly (>70%) bound to particles. In contrast, only 54% of ∑ 7PCBs occurred in the particulate phase, and their partitioning was influenced by the degree of chlorination. During the sampling period, PBDE/PCB fluxes were quite similar and ranged from 3 to 128 and from 6 to 125 g day(-1), respectively. The annual mass flow of PBDEs and PCBs was estimated to 10 kg for both. Contrary to PCBs and BDE-209, the temporal evolution of ∑ tri-hepta BDEs was related to particulate organic matter content, which is controlled by river flow variations. This suggests that they exhibit different sources or behavior in the Seine River.

Bioaccumulation of per- and polyfluoroalkyl substance in fish from an urban river: Occurrence, patterns and investigation of potential ecological drivers.

Per- and polyfluoroalkyl substances (PFAS) are ubiquitous in aquatic environments and a recent shift toward emerging PFAS is calling for new data on their occurrence and fate. In particular, understanding the determinants of their bioaccumulation is fundamental for risk assessment purposes. However, very few studies have addressed the combined influence of potential ecological drivers of PFAS bioaccumulation in fish such as age, sex or trophic ecology. Thus, this work aimed to fill these knowledge gaps by performing a field study in the Seine River basin (France). Composite sediment and fish (European chub, Squalius Cephalus) samples were collected from four sites along a longitudinal transect to investigate the occurrence of 36 PFAS. Sediment molecular patterns were dominated by fluorotelomer sulfonamidoalkyl betaines (i.e. 6:2 and 8:2 FTAB, 46% of ∑PFAS on average), highlighting the non-negligible contribution of PFAS of emerging concern. C9-C14 perfluoroalkyl carboxylic acids, perfluorooctane sulfonic acid (PFOS), perfluorooctane sulfonamide (FOSA) and 10:2 fluorotelomer sulfonate (10:2 FTSA) were detected in all fish samples. Conversely, 8:2 FTAB was detected in a few fish from the furthest downstream station only, suggesting the low bioaccessibility or the biotransformation of FTABs. ∑PFAS in fish was in the range 0.22-3.8 ng g-1 wet weight (ww) and 11-140 ng g-1 ww for muscle and liver, respectively. Fish collected upstream of Paris were significantly less contaminated than those collected downstream, pointing to urban and industrial inputs. The influence of trophic ecology and biometry on the interindividual variability of PFAS burden in fish was examined through analyses of covariance (ANCOVAs), with sampling site considered as a categorical variable. While the latter was highly significant, diet was also influential; carbon sources and trophic level (i.e. estimated using C and N stable isotope ratios, respectively) equally explained the variability of PFAS levels in fish.

Development of analytical procedures for trace-level determination of polybrominated diphenyl ethers and tetrabromobisphenol A in river water and sediment.

The aim of this work was to develop procedures for the simultaneous determination of selected brominated flame retardants (BFRs) in river water and in river bed sediment. The target analytes were polybrominated diphenyl ethers (PBDEs) and tetrabromobisphenol A (TBBPA). To determine dissolved BFRs, a novel mixed-mode solid-phase extraction procedure was developed by combining a hydrophobic sorbent (C(18)) with a silica-based anion exchange sorbent, so as to overcome the negative artefact induced by dissolved organic carbon. Extraction recoveries exceeded 73% for most analytes, except for BDE-183 and BDE-209 (57%). As regards suspended sediment and river bed sediment, extraction was carried out by means of ultrasonication (recoveries: 73-94%). These procedures, combined to gas chromatography coupled to negative chemical ionisation mass spectrometry (GC-NCI-MS), enabled the determination of BFRs at trace level: 3-160 pg L(-1) in river water, 5-145 pg g(-1) in bed sediment. These methods were applied to the determination of PBDEs and TBBPA in a suburban river (near Paris, France). PBDEs were systematically detected in the water column (SigmaBDEs, 2,300-4,300 pg L(-1)); they partitioned between the dissolved and particulate phases and BDE-209 was the dominant congener, followed by BDE-99 and BDE-47. TBBPA was detected in the dissolved phase only (<35-68 pg L(-1)). All selected BFRs were ubiquitous in bed sediments and levels ranged from 3,100 to 15,100 pg g(-1) and from 70 to 280 pg g(-1) (dry weight), for SigmaBDEs and TBBPA, respectively.