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High-altitude Pyrenean lakes are ecosystems far from local pollution sources, and thus they are particularly sensitive to the atmospheric deposition of metals and metalloids. This study aims to quantify the effect of human activity in 18 lakes located in both side of the France-Spain frontier. Sediment cores were collected in summer 2013, sampled at a 1cm resolution and the concentration of 24 elements was measured by ICP-MS. Statistic and chemometric analysis of the results highlights the influence of the geographical position and lithogenic features of each lake basin on trapping pollutants. More than the 80% of the lakes showed values of enrichment factor (EF) above 2 for at least one of the elements investigated in at least one core interval, which corroborates the existence of historical anthropogenic inputs of elements in the studied area. The results demonstrate the natural origin of As and Ti in Pyrenees, together with the significant anthropogenic inputs of Cd, Pb, Sb and Sn from ancient times. The data set points mining activities as the main historical source of pollution and illustrate the large impact of the industrial revolution. The regional variability could reflect also differential long-range transport, followed by dry or wet deposition., (© 2023. The Author(s).)

Concentrations of inorganic tin (Sn), tributyltin (TBT) and its degradation products dibutyltin (DBT) and monobutyltin (MBT) were measured in surface sediments and in two cores from the Toulon Bay, hosting the major French military harbour. Anticipating planned dredging, the aim of the present work is to map and evaluate for the first time the recent and historic contamination of these sediments by inorganic and organic Sn species derived from antifouling paints used for various naval domains including military, trade, tourism and leisure. Tin and butyl-Sn concentrations in the bay varied strongly (4 orders of magnitude), depending on the site, showing maximum values near the shipyards. The concentrations of total Sn (1.3-112 μg g), TBT (<0.5-2,700 ng g), DBT (<0.5-1,800 ng g) and MBT (0.5-1,000 ng g) generally decreased towards the open sea, i.e. as a function of both distance from the presumed main source and bottom currents. Progressive degradation state of the butyl-Sn species according to the same spatial scheme and the enrichment factors support the scenario of a strongly polluted bay with exportation of polluted sediment to the open Mediterranean. Low degradation and the historical records of butyl-Sn species in two Pb-dated sediment cores, representative of the Northern Bay, are consistent with the relatively recent use of TBT by military shipyards and confirm maximum pollution during the 1970s, which will persist in the anoxic sediments for several centuries. The results show that (a) degradation kinetics of butyl-Sn species depend on environmental conditions, (b) the final degradation product Sn is by far the dominant species after 10-12 half-life periods and (c) using recent data to reliably assess former TBT contamination requires the use of a modified butyl-Sn degradation index BDI. Resuspension of extremely contaminated subsurface sediments by the scheduled dredging will probably result in mobilization of important amounts of butyl-Sn species. [ABSTRACT FROM AUTHOR]

Purpose: Quantifying suspended sediment fluxes and dynamics across mountains, and identifying the origin of sediment in severely eroded areas, are of primary importance for the management of water resources. This contribution aims to generalise previous results from suspended sediment fingerprinting obtained during 2007-2009 in a mesoscale Alpine catchment (the Bléone River; 905 km) in France, and to assess variability in sediment sources throughout the second half of the twentieth century. Materials and methods: Sediment fingerprinting, based on elemental geochemistry and radionuclide measurements, was conducted on a sediment core collected in an alluvial floodplain at the basin outlet. This technique was combined with hydro-sedimentary time-series to reconstruct the origin of suspended sediment deposited at this location over the last 50 years. Results and discussion: Interpretation of sedimentation based on historical hydrological databases corroborates core dating obtained with Cs and Pb activity measurements. Black marls and (marly) limestone sources provided the main fraction of sediment throughout the sequence (40 and 22 %, respectively). However, we also found evidence for the occurrence of major floods carrying large quantities of sediment originating from Quaternary deposits and conglomerates (25 and 16 %, respectively). The variability of sediment sources throughout the sequence may reflect the spatial variability of rainfall within the catchment, which in turn reflects its origin. However, the relatively homogeneous sediment composition throughout the sequence confirms that core-derived information is representative of widespread flood events. Conclusions: These results are consistent with those obtained in previous studies. They also outline the need to take into account the entire grain size range of fine sediment in order to provide an overall picture of sediment sources and transfers within highly erosive catchments. This study also emphasizes the importance of using archival data to validate the results of sediment fingerprinting studies conducted during short contemporary monitoring programmes, and to extend fingerprinting of sediment sources over longer time-scales which include large and widespread floods. [ABSTRACT FROM AUTHOR]

Abstract: Despite increasingly strict control of polychlorinated biphenyl (PCB) releases in France since the mid-1970s, PCB contamination of fish recently has emerged as a major concern in the lower Rhône River basin. We measured PCB concentrations in Rhône sediment to evaluate the effects of PCB releases from major urban and industrial areas, sediment redistribution by large floods, and regulatory controls on PCB trends from 1970 to present. Profiles of PCBs (the sum of seven indicator PCB congeners) were reconstructed from sediment cores collected from an off-river rural reference site and from three depositional areas along the Rhône upstream and downstream from the city of Lyon, France. Core chronology was determined from radionuclide profiles and flood deposits. PCB concentrations increased progressively in the downstream direction, and reached a maximum concentration in 1991 of 281μg/kg at the most downstream site. At the rural reference site and at the upstream Rhône site, PCB concentrations peaked in the 1970s (maximum concentration of 13 and 78μg/kg, respectively) and have decreased exponentially since then. PCB concentrations in the middle and downstream cores were elevated into the early 1990s, decreased very rapidly until 2000, and since then have remained relatively stable. Congener profiles for three time windows (1965–80, 1986–93, and 2000–08) were similar in the three sediment cores from the Rhône and different from those at the rural reference site. The results indicate that permitted discharges from a hazardous-waste treatment facility upstream from Lyon might have contributed to high concentrations into the 1980-90s, but that industrial discharges from the greater Lyon area and tributaries to the Rhône near Lyon have had a greater contribution since the 1990s. There is little indication that PCB concentration in sediments downstream from Lyon will decrease over at least the short term. [Copyright &y& Elsevier]

Abstract: During the Late Holocene, the rate of sea level rise decreased and climate changes, hydrodynamic processes or anthropogenic impacts became predominant parameters governing the sedimentary infill of estuarine environments. The aim of this study is to describe the response of past benthic mollusc communities to these forcing factors. Mollusc skeletal remains were sampled from three 8000, 5500 and 2600 year-long sedimentary records in the Marennes–Oléron Bay (Atlantic Coast, France), where environmental changes have previously been identified thanks to a combination of very high resolution seismic profiles and sedimentological data. Molluscan assemblages successfully record environmental changes, even at the smallest temporal scale. They provide relevant information regarding bathymetry, salinity, hydrodynamics, oxygen content and sediment supply. In the 8000 year-long record, the transition from an upper to a lower intertidal mudflat community provides evidence of a transgressive phase that occurred between 8000 and 7600 years BP. In the 5500 year-long record, an oyster bank developed on the slopes of a tidal channel has been recovered. The composition of the fossil community and the careful examination of skeletal remains suggest that the channel was hydraulically inefficient, in response to the sediment infilling of its drainage area. In the 2600 year-long record, a soft-bottom, shallow-water, subtidal mollusc community, similar to that found nowadays in the Marennes–Oléron Bay, has been recovered from both lower mixed sand-mud and upper muddy units separated by a major regional unconformity dated to about 1000 years BP. This sharp transition is recorded by a few rare species, and was responsible for the local extinction of the bivalve Lepton squamosum. However, the abundance of the most common species and the quantity of fragmented shells remain stable, which may indicate that mud drape deposition was related to an increase in mud supply rather than a decrease in water energy. The level of detail of the palaeoenvironmental reconstructions varies, depending on the ecological requirements of the species. Stenotypic indicator species provide accurate, quantitative information, whereas eurytypic species add undesired variability to the assemblages. Since fossil molluscs are easy to collect and to identify and provide long-term, smoothed records of environment variations, this study suggests that they can be used prior to any other biological proxy, as a first step into reconstructions of Holocene coastal environments. [Copyright &y& Elsevier]

Brominated flame retardants (BFRs) are anthropogenic compounds that are ubiquitous in most manufactured goods. Few legacy BFRs have been recognised as persistent organic pollutants (POPs) and have been prohibited since the 2000s. However, most BFRs continue to be used despite growing concerns regarding their toxicity; they are often referred to as novel BFRs (nBFRs). While environmental contamination due to chlorinated POPs has been extensively investigated, the levels and spatiotemporal trends of BFRs are comparatively understudied. This study aims to reconstruct the temporal trends of both legacy and novel BFRs at the scale of a river corridor. To this end, sediment cores were sampled from backwater areas in four reaches along the Rhône River. Age-depth models were established for each of them. Polychlorinated biphenyls (PCBs), legacy BFRs (polybrominated diphenyl ethers - PBDEs, polybrominated biphenyls - PBBs and hexabromocyclododecane - HBCDDs) and seven nBFRs were quantified. Starting from the 1970s, a decreasing contamination trend was observed for PCBs. Temporal trends for legacy BFRs revealed that they reached peak concentrations from the mid-1970s to the mid-2000s, and stable concentrations by the mid-2010s. Additionally, individual concentrations of nBFRs were two to four orders of magnitude lower than those of legacy BFRs. Their temporal trends revealed that they appeared in the environment in the 1970s and 1980s. The concentrations of most of these nBFRs have not decreased in recent years. Thus, there is a need to comprehend the sources, contamination load, repartition in the environment, and toxicity of nBFRs before their concentrations reach hazardous levels. • Time trends of legacy BFRs in sediments along the Rhône River are similar. • Legacy BFRs reached their peak between the 1970s and the 2000s, and are now stable. • nBFRs concentrations are two to four times lower than that of legacy BFRs. • Some nBFRs appeared along the Rhône River as early as the 1970s–1980s. • No decreasing trend in nBFRs concentrations has been observed, so far. [ABSTRACT FROM AUTHOR]

Fluvial suspended particulate matter (SPM) fluxes transport large amounts of contaminants that can affect water quality and river ecosystems. To better manage these inputs in river systems, it is essential to identify SPM and sediment sources. Many studies have applied a fingerprinting method based on using metals integrated into a numerical mixing model to estimate source contributions in a watershed. Most fingerprinting studies use contemporary SPM to trace historical inputs, whereas their metal concentrations were modified over time due to anthropogenic inputs. Moreover, total concentrations of these properties are subject to change due to diagenetic processes occurring in stored sediments. The aim of this study was to assess the relevance of using the non-reactive fraction of metals (i.e. metals and metalloids) in fingerprinting studies to estimate the historical contributions of SPM tributary inputs in a sediment core. To assess metal concentrations in the 'conservative' (i.e. non-reactive) fraction, SPM (samples of sources) and sediment core layers (targeted sediments) were subjected to total mineralization and soft extraction, and the non-reactive fraction was obtained by calculating the difference between the two extractions. This approach was applied on a sediment core from the Upper Rhône River (France), using geochemical signature in contemporary SPM of three major tributaries. We showed that the non-reactive fraction retains a higher number of metals in the range test for the deepest layers, which are characterized by significant anthropogenic inputs. Through apportionment modelling using Monte Carlo simulation, we demonstrated that the tributary contributions computed using the non-reactive fraction are more consistent with historical flood and water flow data and have lower uncertainties than with the total fraction. Working with the non-reactive fraction made it possible to decipher historical inputs of SPM using contemporary SPM samples. This approach enables robust identification of sub-catchment areas liable to provide large quantities of SPM. The non-reactive fraction can be used in a variety of environmental conditions and at various spatial and temporal scales to provide a robust quantification of sediment sources., (Copyright © 2021. Published by Elsevier Ltd.)

Tritium is a radioisotope of hydrogen with a half-life of 12.32 years and was used for its luminescent properties by the watchmaking industry from 1962 to the 2008. Tritiated luminescent salts were integrated in the paints applied on the index and dial of watches and clocks. French and Swiss watchmaking workshops used more than 28 000 TBq of tritium over this period of time and produced almost 350 million watches. Despite the end of tritiated salts use in watchmaking workshops in 1992 in France and 2008 in Switzerland, high level of organically bound tritium (OBT) are still observed in sediments of the Rhône River downstream the Lake Geneva. Contamination of the Rhône River by tritiated hot particles since 1962 up to nowadays remains poorly documented. In order to assess the long term behavior and fate of technogenic tritium in this river and its trajectories in the river system, two sediment cores were collected at the upstream (UC) and downstream (DC) part of the Rhône River in France and OBT contents were determined. For both sedimentary cores, maximum OBT contents were registered over the 1980s when tritium was intensively used by watchmaking industries. These residual OBT contents are 1 000 to 10 000 fold higher than current natural background levels in riverine sediments. The OBT contents progressively decreased since 1989 with close effective half-life in upstream and downstream area (5 ± 2 years). The OBT contents were lower in DC than in UC due to the dilution by uncontaminated sediments delivered by tributaries not affected by the watchmaking industries. Trajectories analysis indicates that the resiliency of the Rhône River system in regards to this contamination would be reached in 14–70 years and in 14–28 years respectively for the upstream and downstream part of the river. • History of tritium used in French and Swiss watchmaking workshops was reviewed. • OBT was analyzed in sediment cores collected upstream and downstream the Rhône River. • Reconstructed time series testimony anthropic pressures over three major periods of time. • Maximum OBT contents were registered over the 1980 with higher levels upstream. • Current background level would be reached in 14–70 years. [ABSTRACT FROM AUTHOR]

Bed sediments and a dated sediment core were collected upstream and downstream from the city of Lyon (France) to assess the spatial and temporal trends of contamination by per- and polyfluoroalkyl substances (PFASs) in this section of the Rhône River. Upstream from Lyon, concentrations of total PFASs (ΣPFASs) in sediments are low (between 0.19 and 2.6 ng g -1 dry weight - dw), being characterized by a high proportion of perfluorooctane sulfonate (PFOS). Downstream from Lyon, and also from a fluoropolymer manufacturing plant, ΣPFASs concentrations reach 48.7 ng g -1 dw. A gradual decrease of concentrations is reported at the coring site further downstream (38 km). Based on a dated sediment core, the temporal evolution of PFASs is reconstructed from 1984 to 2013. Prior to 1987, ΣPFASs concentrations were low (≤2 ng g -1 dw), increasing to a maximum of 51 ng g -1 dw in the 1990s and then decreasing from 2002 to the present day (∼10 ng g -1 dw). In terms of the PFAS pattern, the proportion of perfluoroalkyl sulfonic acids (PFSAs) has remained stable since the 1980s (∼10%), whereas large variations are reported for carboxylic acids (PFCAs). Long chain- (C > 8) PFCAs characterized by an even number of perfluorinated carbons represent about 74% of the total PFAS load until 2005. However, from 2005 to 2013, the relative contribution of long chain- (C > 8) PFCAs with an odd number of perfluorinated carbons reaches 80%. Such changes in the PFAS pattern likely highlight a major shift in the industrial production process. This spatial and retrospective study provides valuable insights into the long-term contamination patterns of PFAS chemicals in river basins impacted by both urban and industrial activities., (Copyright © 2019. Published by Elsevier Ltd.)