Zinc speciation in the suspended particulate matter of an urban river (Orge, France): influence of seasonality and urbanization gradient.

Among trace metal pollutants, zinc is the major one in the rivers from the Paris urban area, such as the Orge River, where Zn concentration in the suspended particulate matter (SPM) can reach 2000 mg/kg in the most urbanized areas. In order to better understand Zn cycling in such urban rivers, we have determined Zn speciation in SPM as a function of both the seasonal water flow variations and the urbanization gradient along the Orge River. Using TEM/SEM-EDX and linear combination fitting (LCF) of EXAFS data at the Zn K-edge, we show that Zn mainly occurs as tetrahedrally coordinated Zn(2+) sorbed to ferrihydrite (37-46%), calcite (0-37%), amorphous SiO2 (0-21%), and organic-P (0-30%) and as octahedrally coordinated Zn(2+) in the octahedral layer of phyllosilicates (18-25%). Moreover, the Zn speciation pattern depends on the river flow rate. At low water flow, Zn speciation changes along the urbanization gradient: geogenic forms of Zn inherited from soil erosion decrease relative to Zn bound to organic-phosphates and amorphous SiO2. At high water flow, Zn speciation is dominated by soil-borne forms of Zn regardless the degree of urbanization, indicating that erosion of Zn-bearing minerals dominates the Zn contribution to SPM under such conditions.

Novel insights into Fukushima nuclear accident from isotopic evidence of plutonium spread along coastal rivers.

The Fukushima Dai-ichi Nuclear Power Plant (FDNPP) accident led to important releases of radionuclides into the environment, and trace levels of plutonium (Pu) were detected in northeastern Japan. However, measurements of Pu isotopic atom and activity ratios are required to differentiate between the contributions of global nuclear test fallout and FDNPP emissions. In this study, we used a double-focusing sector field ICP-MS to measure Pu atom and activity ratios in recently deposited sediment along rivers draining the most contaminated part of the inland radioactive plume. Results showed that plutonium isotopes (i.e., (239)Pu, (240)Pu, (241)Pu, and (242)Pu) were detected in all samples, although in extremely low concentrations. The (241)Pu/(239)Pu atom ratios measured in sediment deposits (0.0017-0.0884) were significantly higher than the corresponding values attributed to the global fallout (0.00113 ± 0.00008 on average for the Northern Hemisphere between 31°-71° N: Kelley, J. M.; Bond, L. A.; Beasley, T. M. Global distribution of Pu isotopes and (237)Np. Sci. Total. Env. 1999, 237/238, 483-500). The results indicated the presence of Pu from FDNPP, in slight excess compared to the Pu background from global fallout that represented up to ca. 60% of Pu in the analyzed samples. These results demonstrate that this radionuclide has been transported relatively long distances (∼45 km) from FDNPP and been deposited in rivers representing a potential source of Pu to the ocean. In future, the high (241)Pu/(239)Pu atom ratio of the Fukushima accident sourced-Pu should be measured to quantify the supply of continental-originating material from Fukushima Prefecture to the Pacific Ocean.

Quantifying diet-borne metal uptake in Gammarus pulex using stable isotope tracers.

Gammarids are aquatic amphipods widely used for water quality monitoring. To investigate the copper and cadmium diet-borne metal uptake in Gammarus pulex, we adapted the pulse-chase stable isotopes-based approach to determine the food ingestion rate (IR), the gut retention time (GRT) and the metal assimilation efficiencies (AE). G. pulex were fed with (65)Cu-, (106)Cd-, and (53)Cr-labeled alder leaves for 7.5h and then with unlabeled leaves for 5d. The metal stable isotope contents in the gammarids, leaves, filtered water and periodically collected feces were determined. Chromium was poorly assimilated by the gammarids; thus, Cr was used as an unassimilated tracer. The first tracer defecation occurred before the first feces harvest, indicating a gut passage time of less than 9h. A 24-h GRT and a 0.69gg(-1)d(-1) IR were estimated. The Cd AE value was estimated as 5-47%, depending on the assimilation determination method applied. The Cu AE value could not be evaluated regardless of the determination method used, most likely because of the rapid Cu regulation in gammarids in addition to analytical uncertainties when determining the Cu content in leaves. Application of the Cd AE value in the framework of the biodynamic bioaccumulation model shows that the diet-borne uptake of Cd significantly contributes (66-95%) to the metal bioaccumulation in G. pulex fed with alder leaves.

Determining the geochemical fingerprint of the lead fallout from the Notre-Dame de Paris fire: Lessons for a better discrimination of chemical signatures.

On 2019, the fire of Notre-Dame de Paris cathedral ("NDdP") spread an unknown amount of lead (Pb) dust from the roof of the cathedral over Paris. No data describing the geochemical fingerprint of the roof lead, as well as no particle collected during the fire, were available: a post-hoc sampling was performed. To discriminate the potential environmental impact of the fire from multiple Pb sources in Paris, it was mandatory to define unequivocally the fire dust geochemical signature. A dedicated and in hindsight geochemistry-based strategy was developed to eliminate any source of potential contamination due to sampling substrates or previously deposited dust. Radiogenic Pb isotopic signatures (206Pb/207Pb and 208Pb/206Pb ratios) and elemental ratios were determined in 23 Pb-rich samples collected inside NDdP. We determined that the dust collected on wood substrates on the first floor was most representative of fire emissions. These samples were the analyzed for the 4 Pb isotopes (204, 206, 207, 208) and the fire dust signature is characterized by ratio values of 206Pb/207Pb: 1.1669-1.1685, 208Pb/206Pb: 2.0981-2.1095, 208Pb/204Pb: 38.307-38.342, 207Pb/204Pb: 15.633-15.639 and 206Pb/204Pb: 18.242-18.275. In addition, the fire dust presents typical element-to-Pb ratio. This fingerprint was compared to the signatures of the known local Pb sources. The geochemical fingerprint of the fire is significantly different from that of the dominant urban Pb source. This will allow future evaluation of the contribution of the fire to Paris Pb pollution and of the real extent of the area affected by the Pb-containing dust plume. Moreover, the geographical origin of Pb used for the roof restauration and the spire building was identified. These findings open new ways to study the Pb sources in historical monuments for environmental impacts evaluation, as well as for historical perspectives.

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.

X-ray absorption fine structure evidence for amorphous zinc sulfide as a major zinc species in suspended matter from the Seine River downstream of Paris, Ile-de-France, France.

Zinc is one of the most widespread trace metals (TMs) in Earth surface environments and is the most concentrated TM in the downstream section of the Seine River (France) due to significant anthropogenic input from the Paris conurbation. In order to better identify the sources and cycling processes of Zn in this River basin, we investigated seasonal and spatial variations of Zn speciation in suspended particulate matter (SPM) in the oxic water column of the Seine River from upstream to downstream of Paris using synchrotron-based extend X-ray absorption fine structure (EXAFS) spectroscopy at the Zn K-edge. First-neighbor contributions to the EXAFS were analyzed in SPM samples, dried and stored under a dry nitrogen atmosphere or under an ambient oxygenated atmosphere. We found a sulfur first coordination environment around Zn (in the form of amorphous zinc sulfide) in the raw SPM samples stored under dry nitrogen vs an oxygen first coordination environment around Zn in the samples stored in an oxygenated atmosphere. These findings are supported by scanning electron microscopy and energy dispersive X-ray spectrometry observations. Linear combination fitting of the EXAFS data for SPM samples, using a large set of EXAFS spectra of Zn model compounds, indicates dramatic changes in the Zn speciation from upstream to downstream of Paris, with amorphous ZnS particles becoming dominant dowstream. In contrast, Zn species associated with calcite (either adsorbed or incorporated in the structure) are dominant upstream. Other Zn species representing about half of the Zn pool in the SPM consist of Zn-sorbed on iron oxyhydroxides (ferrihydrite and goethite) and, to a lesser extent, Zn-Al layered double hydroxides, Zn incorporated in dioctahedral layers of clay minerals and Zn sorbed to amorphous silica. Our results highlight the importance of preserving the oxidation state in TM speciation studies when sampling suspended matter, even in an oxic water column.

The stress sigma factor σS/RpoS counteracts Fur repression of genes involved in iron and manganese metabolism and modulates the ionome of Salmonella enterica serovar Typhimurium.

In many Gram-negative bacteria, the stress sigma factor of RNA polymerase, σS/RpoS, remodels global gene expression to reshape the physiology of quiescent cells and ensure their survival under non-optimal growth conditions. In the foodborne pathogen Salmonella enterica serovar Typhimurium, σS is also required for biofilm formation and virulence. We have previously identified sRNAs genes positively controlled by σS in Salmonella, including the two paralogous sRNA genes, ryhB1 and ryhB2/isrE. Expression of ryhB1 and ryhB2 is repressed by the ferric uptake regulator Fur when iron is available. In this study, we show that σS alleviates Fur-mediated repression of the ryhB genes and of additional Fur target genes. Moreover, σS induces transcription of the manganese transporter genes mntH and sitABCD and prevents their repression, not only by Fur, but also by the manganese-responsive regulator MntR. These findings prompted us to evaluate the impact of a ΔrpoS mutation on the Salmonella ionome. Inductively coupled plasma mass spectrometry analyses revealed a significant effect of the ΔrpoS mutation on the cellular concentration of manganese, magnesium, cobalt and potassium. In addition, transcriptional fusions in several genes involved in the transport of these ions were regulated by σS. This study suggests that σS controls fluxes of ions that might be important for the fitness of quiescent cells. Consistent with this hypothesis, the ΔrpoS mutation extended the lag phase of Salmonella grown in rich medium supplemented with the metal ion chelator EDTA, and this effect was abolished when magnesium, but not manganese or iron, was added back. These findings unravel the importance of σS and magnesium in the regrowth potential of quiescent cells.

Key factors influencing metal concentrations in sediments along Western European Rivers: A long-term monitoring study (1945-2020).

Since 1945, a large amount of heterogeneous data has been acquired to survey river sediment quality, especially concerning regulatory metals such as Cd, Cr, Cu, Hg, Ni, Pb, and Zn. Large-scale syntheses are critical to assess the effectiveness of public regulations and the resiliency of the river systems. Accordingly, this data synthesis proposes a first attempt to decipher spatio-temporal trends of metal contamination along seven major continental rivers in Western Europe (France, Belgium, Germany, and the Netherlands). A large dataset (>12,000 samples) from various sediment matrices (bed and flood deposits - BFD, suspended particulate matter - SPM, dated sediment cores - DSC) was set up based on monitoring and scientific research from the 1950s to the 2010s. This work investigates the impact of analytical protocols (matrix sampling, fractionation, extraction), location and time factors (related to geology and anthropogenic activities) on metal concentration trends. Statistical analyses highlight crossed-interactions in space and time, as well as between sediment matrices (metal concentrations in SPM ≃ DSC > BFD) and extraction procedures (also related to river lithology). Major spatio-temporal trends are found along several rivers such as (i) an increase of metal concentrations downstream of the main urban industrial areas (e.g. Paris-Rouen corridor on the Seine River, Bonn-Duisburg corridor on the Rhine River), (ii) a long-term influence of former mining areas located in crystalline zones, releasing heavily contaminated sediments for decades (Upper Loire River, Middle Meuse section), (iii) a decrease of metal concentrations since the 1970s (except for Cr and Ni, rather low and stable over time). The improvement of sediment quality in the most recent years in Europe reflects a decisive role of environment policies, such as more efficient wastewater treatments, local applications of the Water Framework Directive and urban industrial changes in the river valleys.

Spatio-temporal variability of solid, total dissolved and labile metal: passive vs. discrete sampling evaluation in river metal monitoring.

In order to obtain representative dissolved and solid samples from the aquatic environment, a spectrum of sampling methods are available, each one with different advantages and drawbacks. This article evaluates the use of discrete sampling and time-integrated sampling in illustrating medium-term spatial and temporal variation. Discrete concentration index (CI) calculated as the ratio between dissolved and solid metal concentrations in grab samples are compared with time-integrated concentration index (CI) calculated from suspended particulate matter (SPM) collected in sediment traps and labile metals measured by the diffusive gel in thin films (DGT) method, collected once a month during one year at the Seine River, upstream and downstream of the Greater Paris Region. Discrete CI at Bougival was found to be significantly higher than at Triel for Co, Cu, Mn, Ni and Zn, while discrete metal partitioning at Marnay was found to be similar to Bougival and Triel. However, when using time-integrated CI, not only was Bougival CI significantly higher than Triel CI, CI at Marnay was also found to be significantly higher than CI at Triel which was not observed for discrete CI values. Since values are time-averaged, dramatic fluctuations were smoothed out and significant medium-term trends were enhanced. As a result, time-integrated concentration index (CI) was able to better illustrate urbanization impact between sites when compared to discrete CI. The impact of significant seasonal phenomenon such as winter flood, low flow and redox cycles was also, to a certain extent, visible in time-integrated CI values at the upstream site. The use of time-integrated concentration index may be useful for medium- to long-term metal studies in the aquatic environment.

Heavy metal bioaccumulation by the bryophyte Scleropodium purum at three French sites under various influences: rural conditions, traffic, and industry.

An active biomonitoring of the heavy metals pollution experiment was undertaken by means of the bryophyte species Scleropodium purum transplanted at three different sites exposed to rural, traffic, or industrial influences. Concentrations of about 40 elements in S. purum were determined by instrumental neutron activation analysis and inductively coupled plasma mass spectrometry. Accumulation rates of heavy metals were determined in the three sites. These accumulation rates in polluted sites were matched together and also to those recorded at the rural site. The changes of the accumulation rate of heavy metals in S. purum versus their concentrations in PM(10) particles simultaneously collected above show some different accumulation properties of S. purum according to elements and sites. S. purum has a weak efficiency in the three sites to accumulate elements like V, Cr, Cu, Zn, As, Se, Sb, and Pb originating from atmospheric hot sources generally enriched in particulates matter (PM(10)), whereas it is particularly high for Br, Th, and Rb. For other elements, Co, La, Ce, and Hf, and rare earth elements, Fe, Sr, Nb, Ti, Al, and Sc, the collection efficiency by S. purum is intermediate. In the industrial site Dunkerque, a magnification of the collection efficiency by S. purum for elements originating from steel and aluminum productions and petroleum refinement suggests that these metals could be enriched in coarse particles with a better accumulation by the bryophyte with respect to PM10.

The Isotopic Signature of Lead Emanations during the Fire at Notre Dame Cathedral in Paris, France.

When Notre Dame de Paris cathedral caught fire on 15 April 2019, lead particles were deposited in its surroundings. Our objective was to determine whether the lead plume had a homogeneous isotopic signature (i.e., a set of homogenous isotopic ratios), and whether, if so, this was different from common sources. In January 2020, dust samples were collected from six areas inside the cathedral, downwind of the fire, as well as from eight roof debris fragments. These samples were mineralized and analyzed using ICP-MS. Their isotopic ratios (207Pb/206Pb and 206Pb/204Pb) were determined and then compared both to each other and to previous published ratios measured in home dusts and blood samples collected in France. The isotopic ratios of dust samples collected inside the cathedral were compatible with each other and with the roof fragments. These isotopic ratios are common and differ neither from those of many other dusts collected in France during the period 2008-2009, nor from those of blood samples collected from children in France during the same period. Moreover, the fire's isotopic signature is close to the overall signature for Paris. Indeed, it would be difficult to attribute the fire at the cathedral to either lead poisoning or environmental contamination.

Increasing the power of interpretation for soil metaproteomics data.

BACKGROUND: Soil and sediment microorganisms are highly phylogenetically diverse but are currently largely under-represented in public molecular databases. Their functional characterization by means of metaproteomics is usually performed using metagenomic sequences acquired for the same sample. However, such hugely diverse metagenomic datasets are difficult to assemble; in parallel, theoretical proteomes from isolates available in generic databases are of high quality. Both these factors advocate for the use of theoretical proteomes in metaproteomics interpretation pipelines. Here, we examined a number of database construction strategies with a view to increasing the outputs of metaproteomics studies performed on soil samples. RESULTS: The number of peptide-spectrum matches was found to be of comparable magnitude when using public or sample-specific metagenomics-derived databases. However, numbers were significantly increased when a combination of both types of information was used in a two-step cascaded search. Our data also indicate that the functional annotation of the metaproteomics dataset can be maximized by using a combination of both types of databases. CONCLUSIONS: A two-step strategy combining sample-specific metagenome database and public databases such as the non-redundant NCBI database and a massive soil gene catalog allows maximizing the metaproteomic interpretation both in terms of ratio of assigned spectra and retrieval of function-derived information. Video abstract.

Silver and thallium historical trends in the Seine River basin.

Records on pollution by metals of minor economic importance (e.g. silver and thallium) but which prove to be toxic are rarely documented in river sediment. This study used two sediment cores collected downstream of the Seine River to describe the temporal evolution of Ag and Tl concentrations in an urban catchment. Radionuclide analysis (i.e. Cs-137 and Pb-210) allowed dating sediment deposition within the cores (1933-2003). Ag concentration reached maximum values of 14.3-24.6 mg kg(-1) in the 1960s and 1970s, before gradually decreasing up to values which approximated 4 mg kg(-1) in 2003. In contrast, Tl concentrations remained roughly constant throughout the core (median value of 0.86 mg kg(-1)). Suspended solids was collected at upstream locations in the catchment to derive the background concentrations in Ag and Tl. Very high Ag concentrations were measured in the upstream Seine River sites (0.33-0.59 mg kg(-1)), compared to the values reported in the literature (0.055 mg kg(-1)). This suggests the presence of a widespread and ancient Ag pollution in the Seine River basin, as demonstrated by the very high Ag enrichment ratios recorded in the cores. Annual flux of particulate Ag in the Seine River was estimated at 1.7 t yr(-1) in 2003. In contrast, Tl concentrations remained in the same order of magnitude as the natural background signal (0.3-0.5 mg kg(-1)). This study suggests that the Seine River basin is free of Tl contamination. Future concerns should hence mostly rely on Ag contamination, in a context of increasing Ag uses and possible releases to the environment.

Investigating the relationships between chemical element concentrations and discharge to improve our understanding of their transport patterns in rural catchments under subtropical climate conditions.

Solute and particulate elemental concentrations (C) exhibit different responses to changes in discharge (Q), and those relationships are not well understood in subtropical agricultural environments. The objective is to describe the transport processes of different chemical elements during a set of contrasted rainfall events (2011-2015) that occurred in a small rural catchment under subtropical climate. The study was carried out in the Lajeado Ferreira Creek catchment (1.23 km2), southern Brazil. To this end, the concentrations in dissolved organic carbon (DOC), Cl-, NO3-, SO4-, ten chemical elements (in either dissolved or particulate forms) and suspended sediment concentrations (SSC) were determined. Metric indices were then calculated to characterize their transport patterns: (i) the best fit slope between log-C and log-Q (ß), (ii) the coefficient of variation of C and Q, (iii) shape of the hysteresis loop and hysteresis index, and (iv) the flushing index. All particulate elements along with the dissolved inorganic phosphorus (PO4-3) were shown to be controlled by the sediment dynamics. Geogenic elements (Fe2+, Zn2+, Cu2+, Mn2+, Si4+) showed a dilution effect with increasing Q values, likely because they were mainly transported with subsurface and base flow. Dissolved elements that are mainly supplied with fertilizers (Na+ and Cl-) as well as DOC showed a dilution effect, although they were mainly transported by surface runoff. Finally, a chemostatic behavior was found for those chemical elements (Mg2+, K+, Ca2+, NO3- and SO42-) that are supplied by more than one flow pathways. The results demonstrate that under subtropical climate conditions, the transport of essential nutrients including PO4-3 and metals (in particulate form), are mainly transported with surface runoff. Accordingly, runoff control on cultivated hillslopes should be improved to reduce the potential contaminant supply to the river and to reduce the potentially deleterious impacts that they may cause in downstream regions.

Innovative combination of tracing methods to differentiate between legacy and contemporary PAH sources in the atmosphere-soil-river continuum in an urban catchment (Orge River, France).

Polycyclic aromatic hydrocarbons (PAH) have been released by human activities during more than a century, contaminating the entire atmosphere - soil - river continuum. Due to their ubiquity in the environment and their potential severe biological impacts, PAH became priority pollutants and were targeted by environmental public agencies. To better manage PAH pollution, it is necessary to identify unambiguously the sources and pathways of those compounds at the catchment scale, and to evaluate the persistence of historical PAH pollution in the environment especially in those urban contexts concentrating multiple PAH sources. Accordingly, the current research monitored the contamination in atmospheric fallout, soils and rivers of a 950-km2 catchment (Orge River) characterized by an increasing urban gradient in downstream direction, and located in the Seine River basin characterized by a high level of PAH legacy contamination. A combination of various approaches was used, including the widely used PAH diagnostic ratios, together with innovative methods such as PAH correlations and sediment fingerprinting using fallout radionuclides to clearly identify both the origin of PAH and their main PAH pathways to the river. The results demonstrated the persistence of legacy PAH contamination in the catchment, responsible for the signature of the suspended particulate matter currently transiting in the Orge River. They underlined the conservation of PAH through the soil - river continuum. Finally, urban runoff was demonstrated to provide the main PAH source to the river in the densely urbanized area by both PAH correlations and sediment fingerprinting. These results were used to model PAH concentrations in those particles supplied from urban areas to the river.

Impact of urban pressure on the spatial and temporal dynamics of PAH fluxes in an urban tributary of the Seine River (France).

Polycyclic aromatic hydrocarbons (PAHs) produced by numerous anthropogenic activities are ubiquitous in the environment and have become a priority concern due to their potential severe biological impacts. A better understanding of PAH transfer at the catchment scale is therefore necessary to improve the management of PAH contaminants and protect rivers. Furthermore, the impact of changes in hydrological regimes and land uses on PAH fluxes should be specifically investigated. Accordingly, the current research monitors the contamination in atmospheric fallout, soils and rivers in a 950-km2 catchment (Orge River) characterized by an increasing urban gradient in downstream direction. During an entire hydrological year, river water contamination was quantified through regular sampling of both particulate and dissolved material at four river-monitoring stations, reflecting the increasing urbanization gradient. The significant input of PAHs from urban areas in downstream river sections corresponded to a specific PAH flux that reached 23 g km-2 y-1 despite the low sediment yield. Moreover, the comparison with runoff-specific fluxes reported in the literature underlined the major impact of urban runoff on the Orge River water and sediment quality. Nevertheless, the annual PAH load exported by the river (21 kg y-1) remained lower than the PAH inputs from atmospheric fallout (173 kg y-1), demonstrating the continuous accumulation of PAH from atmospheric fallout in the catchment soils. Consequently, the notably large PAH stock (close to 1000 tons) resulting from historical contamination of this early-industrialized region continues to increase due to ongoing atmospheric inputs.

Tracing the sources of suspended sediment and particle-bound trace metal elements in an urban catchment coupling elemental and isotopic geochemistry, and fallout radionuclides.

The excessive supply of contaminants from urban areas to rivers during the last centuries has led to deleterious impacts on aquatic ecosystems. The sources, the behavior, and the dynamics of these contaminants must be better understood in order to reduce this excessive anthropogenic pollution. Accordingly, the current research investigated the particle-bound trace element (TE) contamination of the 900-km2 Orge River (Seine basin, France) and the potential sources of these particles (agricultural or forest soils, channel banks, road deposited sediments), through the analysis of multiple fallout radionuclides, elemental geochemistry, and lead isotopic composition on suspended particulate matter (SPM) collected during a hydrological year at four stations following an increasing urbanization gradient (300 to 5000 inhab.km-2). Fallout radionuclide measurements showed an increasing contribution of recently eroded particles from urban areas to the SPM in downstream direction. However, this contribution varied depending on hydrological conditions. A greater contribution of particles originating from urban areas was observed during low stage periods. On the contrary, the contribution of agricultural soils and channel banks that are less enriched in contaminants and fallout radionuclides was higher during seasonal floods, which explained the dilution of radionuclide contents in sediment transiting the river during those events. Trace element contamination of SPM in Cu, Zn, Pb, and Sb increased from moderate to significant levels with urban pressure in downstream direction (with corresponding enrichment factors raising from 2 to 6). In addition, Pb isotopic ratios indicated that the main source of Pb corresponded to the "urban" signature found in road deposited sediments. The low variations in lead isotope ratios found in the SPM for contrasting hydrological conditions demonstrated the occurrence of a single source of Pb contamination. These results demonstrate the need to better manage urban runoff during both flood and low precipitation events to prevent the supply of diffuse particle-bound contamination to rivers draining urban areas.

Investigating the metal contamination of sediment transported by the 2016 Seine River flood (Paris, France).

Fine sediment transport in rivers is exacerbated during flood events. These particles may convey various contaminants (i.e. metals, pathogens, industrial chemicals, etc.), and significantly impact water quality. The exceptional June 2016 flood of the Seine River (catchment area: 65 000 km2, France), potentially mobilized and deposited contaminated materials throughout the Paris region. Flood sediment deposits (n = 29) were collected along the Seine River and its main tributaries upstream (Yonne, Loing and Marne Rivers) and downstream of Paris (Oise and Eure Rivers). Fallout radionuclides (137Cs, 7Be) were measured to characterize the sources of the material transiting the river, while trace elements (e.g. Cr, Ni, Zn, Cu, As, Cd, Sb, Pb, Tl, Ag) and stable lead isotopes (206Pb/207Pb) were analyzed to quantify the contamination of sediment transported during the flood. In upper sections of the Seine River, sediment mainly originated from the remobilization of particles with a well-balanced contribution of surface and subsurface sources. In the upstream tributaries, sediment almost exclusively originated from the remobilization of subsurface particles. In Paris and downstream of Paris, recently eroded particles and surface sources dominated, suggesting particles were mainly supplied by urban runoff and the erosion of agricultural soils. The highest metal concentrations and Enrichment Factors (EF) were found in the sediment collected in the Loing, Orge and Yvette upstream tributaries. Although these inputs were diluted in the Seine River, an increase in elemental concentrations was observed, progressing downstream through Paris. However, EFs in sediment collected along the Seine River were lower or in the same range of values sampled over the last several decades, reflecting the progressive decontamination of the urbanized Seine River basin.

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.

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.