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.

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 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.

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.

Health indicators and contaminant levels of a critically endangered species in the Gironde estuary, the European sturgeon.

The European sturgeon, Acipenser sturio, is a highly endangered species that almost disappeared in the last decades. Thanks to yearly restocking of the population, this species is still found in the Gironde estuary (France), where juveniles grow during several years before leaving to the ocean. The aims of this study were to evaluate the pressure exerted on these fish by known organic and inorganic contaminants during their stay at the Gironde estuary, and to get information on the fish's health in this context. Monthly captures over the year 2014 provided 87 fish from the cohorts 2012 and 2013 mainly, and from cohorts 2008, 2009, and 2011, all fish born in hatchery. We report the very first analyses of contaminant levels and of biological markers measured in the blood of these fish. Low inorganic contamination was found, composed of seven metals mainly Zn (< 5 µg mL-1), Fe (< 1.5 µg mL-1), Cu (< 0.8 µg mL-1), Se (< 0.8 µg mL-1), As (< 0.25 µg mL-1), Co (< 0.14 µg mL-1), and Mn (< 0.03 µg mL-1). Concerning persistent organic contaminants, the sum of seven PCBs varied from 1 to 10 ng g-1 plasma, that of eight OCPs from 0.1 to 1 ng g-1, and that of eight PBDEs from 10 to 100 pg g-1. Higher levels of contaminants were measured during spring as compared to summer. The sex steroid hormone plasma levels (estradiol, testosterone, and 11-ketotestosterone) were quite low, which was predictable for juveniles. The transcription of reproduction-involved genes (EstR, AR, LHR, sox9) in blood cells was demonstrated for the first time. Some of them were correlated with organic contaminant levels PCBs and OCPs. Other gene transcriptions (sodCu and bax) were correlated with PCBs and OCPs. However, the DNA damage level measured here as comet tail DNA and micronuclei ratio in red blood cells were in the very low range of the values commonly obtained in fish from pristine areas. The data presented here can serve as a reference base for future monitoring of this population of sturgeons.

Trace elements and persistent organic pollutants in chicks of 13 seabird species from Antarctica to the subtropics.

Seabirds from remote regions are mainly exposed to environmental contaminants from non-point contamination of their food webs. Pre-fledging seabird chicks are fed by their parents with marine prey captured in the vicinity of breeding colonies. Contaminant concentrations in tissues of pre-fledging chicks can thus be mostly related to local dietary sources, and have the potential to unravel spatial patterns of environmental contamination in marine ecosystems. Here, mercury (Hg), 13 other trace elements, and 18 persistent organic pollutants (POPs) were quantified in blood of chicks across four breeding locations that encompass a large latitudinal range in the southern Indian Ocean (from Antarctica, through subantarctic areas, to the subtropics), over a single breeding season. Thirteen species of penguins, albatrosses and petrels were studied, including endangered and near-threatened species, such as Amsterdam albatrosses and emperor penguins. Blood Hg burdens varied widely between species, with a factor of ~50 between the lowest and highest concentrations (mean ±â€¯SD, 0.05 ±â€¯0.01 and 2.66 ±â€¯0.81 µg g-1 dry weight, in thin-billed prions and Amsterdam albatrosses, respectively). Species relying on Antarctic waters for feeding had low Hg exposure. Concentrations of POPs were low in chicks, with the exception of hexachlorobenzene. Contaminant concentrations were mainly explained by species differences, but feeding habitat (inferred from δ13C values) and chicks' body mass also contributed to explain variation. Collectively, our findings call for further toxicological investigations in Amsterdam albatrosses and small petrel species, because they were exposed to high and diverse sources of contaminants, and in macaroni penguins, which specifically showed very high selenium concentrations. CAPSULE: Seabird chicks from four distant sites in the southern Indian Ocean had contrasted blood metallic and organic contaminant patterns depending on species, feeding habitat and body mass.

Biomagnification of perfluoroalkyl acids (PFAAs) in the food web of an urban river: assessment of the trophic transfer of targeted and unknown precursors and implications.

The present work examined the trophic transfer of perfluoroalkyl and polyfluoroalkyl substances (PFASs) in a typical urban river (Orge River, near Paris, France), and aimed to investigate the potential contribution of precursors to the biomagnification of perfluoroalkyl acids (PFAAs). Sixteen PFAAs, twelve of their precursors (pre-PFAAstargeted) and two fluorinated alternatives to long-chain PFASs were analyzed in water, sediments and biota (including biofilm, invertebrates and fish). Twenty two compounds were detected in biological samples (2.0-147 ng g-1 wet weight), perfluorooctane sulfonate (PFOS) and C12-C14 perfluoroalkyl carboxylates (PFCAs) being predominant while ∑pre-PFAAstargeted contributed to 1-18% of ∑PFASs. Trophic magnification factors (TMFs) were >1 (i.e. denoting biomagnification) for C9-C14 PFCAs, C7-C10 perfluoroalkyl sulfonates (PFSAs) and several pre-PFAAs (e.g. 8 : 2 and 10 : 2 fluorotelomer sulfonates). The significant decrease in ∑pre-PFCAs/∑PFCAs concentration ratio with trophic level suggested a likely contribution of selected precursors to the biomagnification of PFCAs through biotransformation, while this was less obvious for PFOS. The total oxidizable precursor assay, applied for the first time to sediment and biota, revealed the presence of substantial proportions of extractable unknown pre-PFAAs in all samples (i.e. 15-80% of ∑PFASs upon oxidation). This proportion significantly decreased from sediments to invertebrates and fish, thereby pointing to the biotransformation of unattributed pre-PFAAs in the trophic web, which likely contributes to the biomagnification of some PFAAs (i.e. C9-C12 PFCAs and C7-C10 PFSAs).

Investigation of the spatial variability of poly- and perfluoroalkyl substance trophic magnification in selected riverine ecosystems.

The occurrence at different trophic levels of 17 poly- and perfluoroalkyl substances (PFASs), including perfluoroalkyl acids (PFAAs) and some of their precursors (e.g., perfluoroalkane sulfonamides, 6:2 fluorotelomer sulfonate (6:2 FTSA)), was investigated in riverine freshwater food webs in Southeastern France. Two fish species (Barbus barbus and Squalius cephalus) and various invertebrate taxa were collected in five rivers to assess the spatial variability of trophic magnification factors (TMFs). Particular attention was devoted to sample and data processing to minimize potential biases associated with the TMF determination. Fish were significantly more contaminated than invertebrates (ΣPFAS = 7-1811 vs. 0.9-213 ng g-1 wet weight (ww)). Those from the Rhône River presented significantly higher levels due to high concentrations of perfluoroundecanoic acid (406 ng g-1 ww) and perfluorotridecanoic acid (566 ng g-1 ww) ascribed to an industrial point source. Perfluorooctane sulfonate (PFOS) was dominant at the other sites (concentration range = 3.6-134 ng g-1 ww). Two linear regression models were compared (i.e., Kendall regression vs. Generalized Linear Mixed-Effect Model, GLMM). Results showed that TMFs calculated using the non-weighted Kendall regression were higher than those obtained using the GLMM approach. GLMM-based TMFs were consistently >1 for C9-C14 perfluorocarboxylic acids (PFCAs), PFOS and perfluorodecane sulfonate (PFDS), indicating their apparent biomagnification in the investigated food webs. Comparatively, 6:2 FTSA and N-ethylperfluorooctane sulfonamidoacetic acid (N-EtFOSAA) were less often detected and were not significantly biomagnified, probably because of metabolization. TMF estimates were generally consistent across sites although some PFASs (in particular C9, C10 and C13 PFCAs) displayed higher variability, due to a unique extreme value that may have resulted from the contribution of unattributed precursor biotransformation.

Temporal variations of perfluoroalkyl substances partitioning between surface water, suspended sediment, and biota in a macrotidal estuary.

A one-year monitoring study was conducted in a macrotidal estuary to assess the temporal variations and partitioning behavior of perfluoroalkyl and polyfluoroalkyl substances (PFASs). Surface water, suspended particulate matter (SPM), and invertebrates including zooplankton (copepods, mysids) and shrimps were sampled on a monthly basis in the Gironde Estuary (SW France). Environmental parameters such as suspended solid loads, salinity, and river water flow rate were highly variable at the study site. However, moderate seasonal variations were observed in terms of PFAS levels and profiles. Summed PFAS (Σ22PFASs) concentrations averaged 6.5 ±â€¯2.7 ng L-1 in the dissolved phase and 3.0 ±â€¯1.2 ng g-1 dry weight in the SPM. The Σ22PFASs was in the range of 1.7-13 ng g-1 wet weight in invertebrates. C5-C8 perfluoroalkyl carboxylates (PFCAs) generally prevailed in the dissolved phase, while perfluorooctane sulfonate (PFOS) was dominant in the SPM and biota. Suspended sediment-water partitioning coefficients Log KD and Log KOC were correlated with the perfluoroalkyl chain length, as were the particle-bound fraction and bioaccumulation factors (Log BAF). Compound-specific Log BAFs varied within a limited range over the period surveyed. Biomagnification factors (mysids/copepods) were consistently >1 for PFOS, perfluorooctane sulfonamide, and long-chain PFCAs (perfluorodecanoate and perfluorododecanoate), suggesting biomagnification at the base of the estuarine 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.

Evidence for the widespread occurrence of short- and medium-chain chlorinated paraffins in fish collected from the Rhône River basin (France).

Chlorinated paraffins (CPs) are high-volume chemicals used in numerous industrial applications. Their quantitative analysis is extremely challenging and this work presents the optimization of an analytical method based on gas chromatography hyphenated with electron capture negative ionization time-of-flight high-resolution mass spectrometry (GC-ECNI-TOF HRMS) for the simultaneous determination of short-chain and medium-chain CPs (SCCPs and MCCPs, respectively) in fish tissues (i.e. dorsal muscle). The resolution of the TOF-MS analyzer reduced or eliminated isobaric interferences and the CP response was optimized through Design of Experiment. A simple clean-up procedure based on adsorption chromatography further removed some potentially interfering organochlorines. Good selectivity, linearity and accuracy were achieved; method detection limits or limits of reporting were compatible with expected levels in wild fish (0.03-0.35 ng g-1 wet weight, ww, depending on the congener). This method was proven suitable for the analysis of CPs in tissues of common barbel Barbus, a fish species frequently used for water quality monitoring purposes in Europe. SCCPs and MCCPs were found to be widespread within the Rhône river basin (France). At all locations, MCCP concentrations (1.3-72.7 ng g-1 ww) were higher than those of SCCPs (0.3-10.6 ng g-1 ww) and levels were systematically lower than the proposed Predicted No Effect Concentrations (PNECs). Spatial variations of SCCP composition profiles largely surpassed those of MCCPs, suggesting the influence of local sources.

Where has the pollution gone? A survey of organic contaminants in Ho Chi Minh city / Saigon River (Vietnam) bed sediments.

A wide range of persistent organic chemicals, including polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), some insecticides, as well as polybrominated diphenyl ethers (PBDEs) and some perfluoroalkyl substances (PFASs) were analyzed in 17 bed sediments collected along the Saigon River and at adjacent canal mouths from upstream to downstream in Ho Chi Minh City (Vietnam). Concentrations were rather low for PAHs, as well as for legacy PCBs and dichloro-diphenyl-trichlorethane and metabolites (DDTs), or below detection limits for several PFASs and all PBDEs measured. Several insecticides (chlorpyrifos-ethyl, and the pyrethroids cypermethrin and λ-cyhalothrin) displayed rather high concentrations at a few sites within the city. There was no distinct upstream - downstream trend for PAHs, (DDTs) or PCBs. Although adjacent canal sediments tended to be more contaminated than Saigon River sediments, the differences were not significant. Emissions are almost certainly substantial for PAHs, and probably also for other contaminants such as PBDEs and some PFASs. During the dry season, contaminants are presumably stored in the city, either in canals or on urban surfaces. Heavy rainfall during the monsoon period carries away contaminated particle flows into the canals and then the Saigon River. The strong tidal influence in the river channel hinders the accumulation of contaminated particles. Contaminated deposits should accordingly be investigated further downstream in depositional environments, such as the mangrove.

EStimating Contaminants tRansfers Over Complex food webs (ESCROC): An innovative Bayesian method for estimating POP's biomagnification in aquatic food webs.

Pollution greatly impacts ecosystems health and associated ecological functions. Persistent Organic Pollutants (POPs) are among the most studied contaminants due to their persistence, bioaccumulation, and toxicity potential. Biomagnification is often described using the estimation of a Trophic Magnification Factor (TMF). This estimate is based on the relationship between contamination levels of the species and their trophic level. However, while the estimation can be significantly biased in relation to multiple sources of uncertainty (e.g. species physiology, measurement errors, food web complexity), usual TMF estimation methods typically do not allow accounting for these potential biases. More accurate and reliable assessment tool of TMFs and their associated uncertainty are therefore needed in order to appropriately guide chemical pollution management. The present work proposes a relevant and innovative TMF estimation method accounting for its many variability sources. The ESCROC model (EStimating Contaminants tRansfers Over Complex food webs), which is implemented in a Bayesian framework, allows for a more reliable and rigorous assessment of contaminants trophic magnification, in addition to accurate estimations of isotopes trophic enrichment factors and their associated uncertainties in food webs. Similar to classical mixing models used in food web investigations, ECSROC computes diet composition matrices using isotopic composition data while accounting for contamination data, leading to more robust food web descriptions. As a demonstration of the practical application of the model, ESCROC was implemented to revisit the trophic biomagnification of 5 polyfluoroalkyl substances (PFAS) in a complex estuarine food web (the Gironde, SW France). In addition to the TMF estimate and 95% confidence intervals, the model provided biomagnification probabilities associated to the investigated contaminants-for instance, 92% in the case of perfluorooctane sulfonate (PFOS)-that can be interpreted in terms of risk assessment in a precautionary approach, which should prove useful to environmental managers.

Application of a multidisciplinary and integrative weight-of-evidence approach to a 1-year monitoring survey of the Seine River.

Quality assessment of environments under high anthropogenic pressures such as the Seine Basin, subjected to complex and chronic inputs, can only be based on combined chemical and biological analyses. The present study integrates and summarizes a multidisciplinary dataset acquired throughout a 1-year monitoring survey conducted at three workshop sites along the Seine River (PIREN-Seine program), upstream and downstream of the Paris conurbation, during four seasonal campaigns using a weight-of-evidence approach. Sediment and water column chemical analyses, bioaccumulation levels and biomarker responses in caged gammarids, and laboratory (eco)toxicity bioassays were integrated into four lines of evidence (LOEs). Results from each LOE clearly reflected an anthropogenic gradient, with contamination levels and biological effects increasing from upstream to downstream of Paris, in good agreement with the variations in the structure and composition of bacterial communities from the water column. Based on annual average data, the global hazard was summarized as "moderate" at the upstream station and as "major" at the two downstream ones. Seasonal variability was also highlighted; the winter campaign was least impacted. The model was notably improved using previously established reference and threshold values from national-scale studies. It undoubtedly represents a powerful practical tool to facilitate the decision-making processes of environment managers within the framework of an environmental risk assessment strategy.

Contamination of soils by metals and organic micropollutants: case study of the Parisian conurbation.

Soils are playing a central role in the transfer and accumulation of anthropogenic pollutants in urbanized regions. Hence, this study aimed at examining the contamination levels of selected soils collected within and around the Paris conurbation (France). This also evaluated factors controlling contamination. Twenty-three trace and major elements as well as 82 organic micropollutants including polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), phthalates (PAEs), polybrominated diphenyl ethers (PBDEs), alkylphenols (APs), and perfluoroalkylated substances (PFASs) were analyzed. Results reinforced the concern raised by the occurrence and levels of metals such as Zn, Pb, Cu, and Hg, identified as metallic markers of anthropogenic activities, but also pointed out the ubiquitous contamination of soils by organic micropollutants in the 0.2-55,000-µg/kg dw range. For well-documented compounds like PAHs, PCBs, and to a lesser extent PBDEs, contents were in the range of background levels worldwide. The pollutant stock in tested soil was compared to the annual atmospheric input. For PAHs; Pb; and to a lesser extent Zn, Cu, Cd, Hg, Sb, PAEs, and APs, a significant stock was observed, far more important than the recent annual atmospheric fluxes. This resulted from both (i) the persistence of a fraction of pollutants in surface soils and (ii) the cumulative atmospheric inputs over several decades. Regarding PBDEs and PFASs, stronger atmospheric input contributions were observed, thereby highlighting their recent dispersal into the environment.

Spatio-temporal dynamics of per and polyfluoroalkyl substances (PFASs) and transfer to periphytic biofilm in an urban river: case-study on the River Seine.

This study addresses the spatio-temporal dynamics of per and polyfluoroalkyl substances (PFASs) in a highly urbanized freshwater hydrosystem, the Seine River (NW France). The distribution of PFASs between water, sediment, and periphytic biofilm was investigated at three sampling sites along a longitudinal gradient upstream and downstream from the Paris urban area. Seasonal variability was assessed through four sampling campaigns performed under contrasting hydrological conditions. In the dissolved phase, ∑PFASs fluctuated between 2 and 9 ng L-1 upstream and 6-105 ng L-1 downstream from Paris. Negative correlations between dissolved PFAS levels and river flow rate were generally observed, corroborating the predominance of point-source PFAS inputs at these sites. 18/19 target PFASs were detected, with a predominance of PFHxS and PFOS (20% of ∑PFASs each), except for the farthest downstream site where 6:2 FTSA was prevalent (35 ± 8% of ∑PFASs), likely reflecting industrial and urban inputs. In biofilms, ∑PFASs fell in the 4-32 ng g-1 dw range, and substantial bioconcentration factors (BCFs) were reported for PFNA, PFDA, and PFOS (log BCF 2.1-4.3), higher than those of PFHxS or PFOA. BCFs varied inversely with dissolved PFAS levels, potentially pointing to concentration-dependent bioaccumulation. Biofilm community characteristics (C/N ratio) may also be an influential determinant of PFAS bioaccumulation. Graphical abstract ᅟ.

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.

Biomonitoring of fluoroalkylated substances in Antarctica seabird plasma: Development and validation of a fast and rugged method using on-line concentration liquid chromatography tandem mass spectrometry.

We report on a fast, accurate and rugged analytical procedure to determine a wide span of perfluoroalkyl and polyfluoroalkyl substances (PFASs) in seabird plasma. The 26 investigated compounds included perfluoroalkyl carboxylates (C5-C14 PFCAs), perfluoroalkyl sulfonates (C4, C6, C7, C8, C10 PFSAs), perfluorooctane sulfonamide (FOSA) and N-alkyl derivatives (MeFOSA, EtFOSA), N-alkyl perfluorooctane sulfonamido acetic acids (MeFOSAA, EtFOSAA), fluorotelomer sulfonates (4:2 FTSA, 6:2 FTSA, 8:2 FTSA), polyfluoroalkyl phosphate diesters (diPAPs) and perfluorooctane sulfonamide phosphate diester (diSAmPAP). The method described herein requires a reduced sample amount (25µL) and involves rapid and simple sample preparation (protein precipitation with acetonitrile but without acidification) prior to analysis by on-line solid phase extraction (Oasis HLB sorbent) coupled to high performance liquid chromatography negative electrospray ionization tandem mass spectrometry. The optimization was conducted using experimental designs to account for potential interactions between variables. Out of the 26 target analytes, 23 compounds showed excellent accuracy (±25% of the expected values). Intermediate precision and matrix effects remained acceptable for most analytes thanks to efficient internal standardization. A human serum standard reference material (NIST SRM 1957) was included in the validation scheme to evaluate method trueness, which proved satisfactory (│Z-scores│<2 for most compounds). Notwithstanding the small initial sample intake, limits of detection as low as 0.003-0.1ngg-1 plasma were obtained. This allowed the determination of 11 target PFASs in Antarctic seabird plasma samples. ΣPFASs in Antarctic seabird plasma ranged from 0.37 to 19ngg-1, with a predominance of PFOS (>54% of ΣPFASs on average). The reduced plasma amount required implies that the present method could also be applied to the analysis of PFASs in the plasma of smaller biological models.