Temporal trends of plastic additive contents in sediment cores of three French rivers (Loire, Meuse and Moselle) over the last decades.

Sediment cores from three major French watersheds (Loire, Meuse and Moselle) have been dated by 137Cs and 210Pbxs from 1910 (Loire), 1947 (Meuse) and 1930 (Moselle) until the present in order to reconstruct trajectories of plastic additive contaminants including nine phthalate esters (PAEs) and seven organophosphate esters (OPEs), measured by gas chromatography-mass spectrometer (GC-MS-MS). Historical levels of ∑PAEs were higher than those of ∑OPEs in the Loire and the Moselle sediments, while ∑PAEs and ∑OPEs contents were of the same order of magnitude in the Meuse sediments. Although increases in concentrations do not evolve linearly, our results clearly indicate an increase in OPEs and PAEs concentrations from the 1950-1970 period onwards, compared with the first half of the 20th century. Our results show that, ∑OPE contents increase gradually over time in the Loire and Meuse rivers but evolve more randomly in the Moselle River. Trajectories of ∑PAEs depend on the river and no generality can be established, suggesting sedimentary reworking and/or local contamination. Data from this study allowed comparisons of contents of ∑OPEs and ∑PAEs between rivers, with ∑OPE concentrations in the Moselle River > Meuse River > Loire River, and concentrations of ∑PAEs in the Loire River > Moselle River > Meuse River. Among all PAEs, di(2-ethylhexyl) phthalate (DEHP) was the most abundant in all sediment samples, followed by diisobutyl phthalate (DiBP). Tris (2-chloroisopropyl) phosphate (TCPP) was the most abundant OPE in sediments of the three rivers. In addition, strong positive Pearson correlations were observed between organic matter (OM) parameters and OPE concentrations, and to a lesser extent, between OM parameters and PAE concentrations. This is particularly true for the Moselle River and for the Loire River, but less so for the Meuse River.

Temporal evolution of plastic additive contents over the last decades in two major European rivers (Rhone and Rhine) from sediment cores analyses.

Although global plastic distribution is at the heart of 21st century environmental concerns, little information is available concerning how organic plastic additives contaminate freshwater sediments, which are often subject to strong anthropogenic pressure. Here, sediment core samples were collected in the Rhone and the Rhine watersheds (France), dated using 137Cs and 210Pbxs methods and analysed for nine phthalates (PAEs) and seven organophosphate esters (OPEs). The distribution of these organic contaminants was used to establish a chronological archive of plastic additive pollution from 1860 (Rhine) and 1930 (Rhone) until today. Sediment grain size and parameters related to organic matter (OM) were also measured as potential factors that may affect the temporal distribution of OPEs and PAEs in sediments. Our results show that OPE and PAE levels increased continuously in Rhone and Rhine sediments since the first records. In both rivers, ∑PAEs levels (from 9.1 ± 1.7 to 487.3 ± 27.0 ng g-1 dry weight (dw) ± standard deviation and from 4.6 ± 1.3 to 65.2 ± 11.2 ng g-1 dw, for the Rhine and the Rhone rivers, respectively) were higher than ∑OPEs levels (from 0.1 ± 0.1 to 79.1 ± 13.7 ng g-1 dw and from 0.6 ± 0.1 to 17.8 ± 2.3 ng g-1 dw, for Rhine and Rhone rivers, respectively). In both rivers, di(2-ethylhexyl) phthalate (DEHP) was the most abundant PAE, followed by diisobutyl phthalate (DiBP), while tris (2-chloroisopropyl) phosphate (TCPP) was the most abundant OPE. No relationship was found between granulometry and additives concentrations, while organic matter helps explain the vertical distribution of PAEs and OPEs in the sediment cores. This study thus establishes a temporal trajectory of PAEs and OPEs contents over the last decades, leading to a better understanding of historical pollution in these two Western European rivers.

Effects of climate variability changes on runoff and erosion in the Western European Loess Belt region (NW, France).

Runoff and soil erosion are very pronounced in the Western European Loess Belt. In this study, the distributed physically-based model CLiDE is calibrated, validated, and applied to a catchment of this area (Dun, NW, France) to assess the hydro-sedimentary impacts of climate change scenarios. Despite considerable progress over the last decade in the study of runoff and soil erosion in the context of climate change, the effects of changes in the temporal variability of precipitation remain poorly understood, especially at the scale of a river basin. To examine these relationships more closely, we developed a stochastic weather generator to individually adjust the components that structure the temporal variability of rainfall. The climate scenarios considered represent projections to the year 2100 of the temporal variability of rainfall over NW Europe. The scenarios are based on historical daily rainfall records (1990-2012) and 4 exploratory assumptions: a 50 % decrease in the interannual rainfall regime (scenario 6yD), a 100 % increase in the interannual rainfall regime (scenario 6yI), a 50 % increase in the seasonal rainfall regime (scenario 1yI) and a 50 % increase in the synoptic rainfall regime (scenario 3dI). Simulated daily water and sediment discharges and erosion/deposition maps for each scenario are compared to those simulated for the situation without changes in rainfall. The time series were aggregated over different time intervals to allow for a multi-scale analysis of the differences. The results indicate that the model provides a satisfactory prediction of the catchment's water and sediment discharges, especially over the calibration period. Increased climate variability, whether on a synoptic (3dI), seasonal (1yI) or interannual (6yI) scale, leads to increased runoff and erosion. Increasing the synoptic rainfall variability (3dI) leads to the largest increase in mean annual runoff and erosion. Only the reduction of the interannual rainfall variability (6yD) provokes the decrease of these values.

Shifts in sediment bacterial communities reflect changes in depositional environments in a fluviatile context.

Sediments are complex heterogeneous matrices allowing to some extent the recording of past environmental conditions by integrating sediment characteristics, contamination and the microbial community assembly. In aquatic environments, abiotic environmental filtering is considered the primary deterministic mechanism shaping microbial communities in sediments. However, the number and relative contributions of geochemical and physical factors associated with biotic parameters (reservoir of microorganisms) complicate our understanding of community assembly dynamics. In this study, the sampling of a sedimentary archive in a site alternately subjected to contrasting inputs from the Eure and the Seine Rivers allowed us to study the response of microbial communities to changes in depositional environment over time. The coupling of the quantification and sequencing of the gene encoding the 16S rRNA with analyses of grain size, organic matter and major and trace metal contents demonstrated that microbial communities reflected contrasting sedimentary inputs over time. Total organic carbon (TOC) was the main factor influencing microbial biomass, while the quantity and quality of organic matter (R400, RC/TOC), major elements (i.e. Al, Fe, Ti) and trace metals (i.e. Zn, Pb, Cu, Cr, Ni, As, Co, Ag, Sb) shaped the structure of the microbial community. Besides the effect of geochemical factors, a specific microbial signature was associated with the contrasting sedimentary sources, highlighting the importance of the microbial reservoir in the assembly of microbial communities. Indeed, the main genera identified in the facies influenced by the Eure River were affiliated with the phyla Desulfobacterota (Syntrophus, Syntrophorhabdus, Smithella, Desulfatiglans), Firmicutes (Clostridium_sensu_stricto_1), Proteobacteria (Crenothrix), Verrucomicrobiota (Luteolibacter), while the contributions of the Seine River were characterised by some halophilic genera Salirhabdus (Firmicutes), Haliangium (Myxococcota) and SCGC-AB-539-J10 (Chloroflexi). This study sheds light on the overall processes determining the assembly of microbial communities in sediments and the importance of associating geochemical factors with reservoirs of microorganisms inherited from sediment sources.

Hydrological classification by clustering approach of time-integrated samples at the outlet of the Rhône River: Application to Δ14C-POC.

Within the framework of the Rhône Sediment Observatory, monthly time-integrated samples have been collected by Particle Traps in the last decade to monitor particulate contaminants in the Rhône River and its main tributaries. In this watershed with a contrasted hydrology, a clustering approach is used to classify the samples according to the main hydrological events. This approach has been applied to riverine particulate organic radiocarbon signatures (Δ14C-POC) that are strongly affected by the origin of the material and the occurrence of nuclear power plant releases. Suspended Particulate Matter (SPM) samples were collected near the outlet of the Rhône River and analysed for 14C along with particulate organic carbon (POC), chlorophyll a and tritium contents to confirm Δ14C-POC origins. Cluster Analysis, coupled to Principal Component Analysis, was performed based on monthly average water discharges of the Upper Rhône River and the five main tributaries. The classification obtained by fuzzy C-mean logic of the Rhône River hydrology into 5 clusters is similar to that already observed in the literature with Mediterranean/Cevenol flood, oceanic pluvial flood, nival flood, low-water level and baseflow clusters. The contributions of each cluster among the Δ14C-POC values demonstrate the complexity of hydrological classification of time-integrated samples. First, the samples with a unique and significantly dominant cluster are easily explained with negative Δ14C-POC values observed in the flood clusters due to input of 14C-depleted material from soil or rock weathering, and positive values observed in the low-water level and baseflow clusters due to anthropogenic input by nuclear industry. Second, samples that present a homogeneous mixture between several clusters demonstrate the occurrence of different hydrological events during the sampling periods. This tool appears as a solution to estimate the contribution of each hydrological event in time-integrated samples.

The unravelling of radiocarbon composition of organic carbon in river sediments to document past anthropogenic impacts on river systems.

As carriers of dissolved and particulate loads that connect continental surfaces to oceans, river systems play a major role in the global carbon cycle. Indeed, riverine particulate organic carbon (POC) is a melange of various origins characterized by their own 14C labeling. In addition, civil nuclear activities have brought new 14C source that remains poorly documented. We propose to unravel the Δ14C value of POC stored in a sedimentary archive collected downstream the most nuclearized European rivers (the Loire River). We postulate that riverine POC is a mixture of aquatic POC (which could be impacted by the liquid discharge from nuclear industry), terrestrial and petrogenic POC. With a combination of radiocarbon measurements, POC analyses and the palynofacies method, we assessed the respective Δ14C value of the POC origins. The gaps between the Δ14C values of the sedimentary POC and those of the atmosphere were the result of the dilution from dead-C, the freshwater reservoir effect imprinting the Δ14C of aquatic POC and the age and transit time of terrestrial POC within the catchment. Importantly, we consider that the unravelling of radiocarbon composition of riverine POC could be useful to determine either the transit time of material from source to sink, some past industrial or natural events, the resilience of the river system and milestones of the social and economic trajectory of a catchment. For the last three decades, riverine sediments could also act as a source of radiocarbon for the atmosphere.

Historical and post-ban releases of organochlorine pesticides recorded in sediment deposits in an agricultural watershed, France.

Agricultural use of organochlorine pesticides (OCPs) increased during the twentieth century but many of them have been progressively banned several decades after their introduction. Nevertheless, these lipophilic chemical compounds may persist in soils and sediments. From sediment deposits, it is possible to reconstruct the chronology of OCP releases in relation to former applications through time. Nevertheless, long-term fate of OCPs i.e. source, transfer, and storage through the watershed, is also related to the OCPs-sediment characteristics interactions, and our study showed the significant links between OCPs and labile or refractory organic matter. From sediment cores collected in a mainly agricultural watershed, the Eure River watershed (France), aldrin and lindane widespread applications during the 1950s-1970s have been recorded. While lindane applications declined after that date, according to the temporal trend of the stable isomer of hexachlorocyclohexane (ß-HCH), α-, and γ-HCH have been recorded at significant levels in the 2000s, suggesting first local post-ban applications. Nevertheless, the relationships between these OCPs and labile organic matter resulted in an overestimation of the post-ban releases. Also, the detection of stable metabolites of dichlorodiphenyltrichloroethane (DDT) (i.e. 4,4'-DDE) and heptachlor (i.e. heptachlor epoxide) several decades after their ban, revealed the role of old deep soils erosion in the chronology of OCP releases and thus the reemergence of stable transformation products from historical OCPs.

Flux estimation, temporal trends and source determination of trace metal contamination in a major tributary of the Seine estuary, France.

Anthropogenic impacts on rivers have increased significantly over the past ~150 years, particularly at the beginning of the industrial revolution. Among other signs, this impact is manifested through the addition of trace metals and metalloid elements to rivers. The Eure River watershed in France covers an area of 6017 km2 and is a major tributary of the Seine estuary. It is not exempt from anthropogenic pressures and has been exposed to significant metal discharges over the last 80 years. The average concentrations of metals (i.e., Cr, Co, Ni, Cu, Zn, Ag, Cd, Sb, and Pb), in suspended particulate matter currently transported by the river are high compared to the local geochemical background. Moreover, the lack of correlation between concentration variations and the hydrosedimentary behaviour of the Eure River suggests that the river is currently under anthropogenic pressure. Analysis of sediment cores indicate strong As contamination during the 1940s, Cr, Co, Ni, Cu, Zn, Ag, and Cd contamination during the 1960s and 1970s, and Sb and Pb contamination during the 1990s and 2000s. The enrichment factors calculation suggests that total anthropogenic pressure within the Eure River watershed since the 1940s was comparable or higher than those in many other French watersheds. An estimation of particulate metal flux in 2017 shows that the Eure River watershed contributed to 7, 8, 9, 10 and 16% of total inputs to the Seine estuary in Cr, Cu, Zn, Cd and Pb respectively. Moreover, the estimation of past theoretical flux indicates that during the 1990s the Eure River watershed was the main contributor of particulate Pb to the estuary. The use of Pb isotopes has revealed that this contamination was primarily of industrial origin.

Evidence for tritium persistence as organically bound forms in river sediments since the past nuclear weapon tests.

Tritium of artificial origin was initially introduced to the environment from the global atmospheric fallout after nuclear weapons tests. Its level was increased in rainwaters by a factor 1000 during peak emissions in 1963 within the whole northern hemisphere. Here we demonstrate that tritium from global atmospheric fallout stored in sedimentary reservoir for decades as organically bound forms in recalcitrant organic matter while tritium released by nuclear industries in rivers escape from such storages. Additionally, we highlight that organically bound tritium concentrations in riverine sediments culminate several years after peaking emission in the atmosphere due to the transit time of organic matter from soils to river systems. These results were acquired by measuring both free and bound forms of tritium in a 70 year old sedimentary archive cored in the Loire river basin (France). Such tritium storages, assumed to be formed at the global scale, as well as the decadal time lag of tritium contamination levels between atmosphere and river systems have never been demonstrated until now. Our results bring new lights on tritium persistence and dynamics within the environment and demonstrate that sedimentary reservoir constitute both tritium sinks and potential delayed sources of mobile and bioavailable tritium for freshwaters and living organisms decades after atmospheric contamination.

A brief history of origins and contents of Organically Bound Tritium (OBT) and 14C in the sediments of the Rhône watershed.

Tritium (3H) and Carbon-14 (14C) are radionuclides of natural (cosmogenic) origin that have also been introduced into the environment by humans since the middle of the last century. They are therefore not compounds that have only recently been released into the environment and they do not pose a recognized health threat due to their low radiotoxicity. However, they hold an important place among current concerns because they are being discharged into the environment by the nuclear industry in large quantities compared to other radionuclides. Those both radionuclides partly integrate organic matter during metabolic processes (i.e., photosynthesis) leading to organically bound forms that can be found in sediments. Organically bound tritium (OBT) analyses carried out on the sediments of the Rhône and its tributaries indicate a significant and historical tritium labelling of sedimentary particles all along the Rhône river, as well as in several northern tributaries, in particular the Ognon and the Tille rivers (tributaries of the Saone), the Doubs River and the Loue River (a tributary of the Doubs) and the Arve river. The recorded levels (10 to over 20,000 Bq/L) are very likely to be related to the presence of synthetic tritiated particles (technogenic tritium), which were used in the past in watchmaking workshops. Although overall contamination levels decrease from north to south in the Rhône watershed and fade over time, particularly due to the radioactive decay of tritium, this contamination source of technogenic tritium in the Rhône watersheds is currently still not negligible. Carbon-14 analyses show that the Rhône sediments generally display 14C levels close to the atmospheric reference values (231 Bq·kg-1 of C in 2015) or even lower in most of cases, and show sporadic and weak labelling near nuclear facilities. The low 14C levels in the Rhône sediments are most likely related to the solid contributions from tributaries draining areas that are rich in fossil organic matter, and therefore devoid of 14C. In the Rhône watershed, the presence in solid particles of tritium in a form organically bound to synthetic compounds and of petrogenic (fossil) organic carbon, can potentially alter the apparent assimilation rates to the food chain of these two radionuclides.

Occurrence of 1,1'-dimethyl-4,4'-bipyridinium (Paraquat) in irrigated soil of the Lake Chad Basin, Niger.

Increased use of agrochemical products to improve yields for irrigated crops in sub-Saharan Africa has been accompanied by a significant increase in the risk of environmental contamination. Detailed examples of the fate of pesticides after initial spreading on crop fields are scarce in tropical regions, where safe practices and related health risks are poorly understood by smallholder farmers. In the semi-arid environment of the Lake Chad Basin, SE Niger, both intrinsic properties of pesticides and extrinsic factors such as soil and climate helped to characterize processes leading to an accumulation of pesticides in soils. Analysis by HPLC-UV of a 6 m deep soil profile showed the presence of Paraquat at concentrations from 953 ± 102 µg kg(-1) to 3083 ± 175 µg kg(-1) at depths between 0.80 and 2.75 m below the land surface. Soil analysis revealed that up to approximately 15 % of the total soil matrix consists of smectites, a clay mineral capable of retaining cationic pesticides such as Paraquat, and a very low content of organic matter (<0.15 wt.% TOC). Paraquat could be stored and not bioavailable in a clayey barrier at approximately 2-m depth and therefore does not represent an immediate risk for populations or environment in this form. However, if the Paraquat application rate remains constant, the clayey barrier could reach a saturation limit within 150-200 years and 180-220 years if we consider a DT50 in soil of ~1,000 days (FAO). Consequently, it could lead to a deeper infiltration and so a pollution of groundwater. Such a scenario can represent a health risk for drinking water and for the Lake Chad, which is a major resource for this densely populated region of semi-arid Africa. Further analyses should focus on deeper layers and groundwater Paraquat contents to validate or invalidate the hypothesis of storage in this clay-rich layer.

Nutrient dynamics at the sediment-water interface in a Mediterranean lagoon (Thau, France): influence of biodeposition by shellfish farming activities.

The Thau Lagoon, a French Mediterranean shallow lagoon, is a site where extensive shellfish farming occurs. The aim of the present work is to evaluate the role of this activity on nutrient exchange at the sediment-water interface in relation to organic matter (OM) sedimentation and degradation. Two stations inside (C5) and outside (C4) of the shellfish farming areas were sampled at three seasons. Porewater chemistry surveys and calculated diffusive fluxes were used to evaluate the trophic status of the Thau lagoon. Quantitative (Particulate Organic Carbon) as well as qualitative OM (Hydrogen Index, Carbohydrates) analyses were performed on sediments to assess OM characteristics. Results emphasized that surficial sediments at C5 are always more enriched in OM. Porewater nutrient concentrations are 10-20 times higher at C5 than at C4. In June 2003, the porewater profiles exhibit a sharp gradient at the bottom waters, indicating a hypereutrophic status, leading to an anoxic crisis.