Reactivity and bioconcentration of stable cesium in a hyperturbid fluvial-estuarine continuum: A combination of field observations and geochemical modeling.

Effective, post-accidental management needs an accurate understanding of the biogeochemical behavior of radionuclides in surface environments at a regional scale. Studies on stable isotopes (element homologs) can improve this knowledge. This work focuses on the biogeochemical behavior of stable cesium (Cs) along a major European fluvial-estuarine system, the Gironde Estuary (SW France). We present results obtained from (i) a long-term monitoring (2014-2017) of dissolved (Csd) and particulate (Csp) Cs concentrations at five sites along the freshwater continuum of the Garonne watershed, (ii) Csd and Csp concentrations during four oceanographic campaigns at contrasting hydrological conditions along longitudinal profiles of the estuarine system, (iii) a 24 h cycle of Csp at the estuary mouth, and (iv) a historical trend of Cs bioconcentration in wild oysters at the estuary mouth (RNO/ROCCH, 1984-2017). In addition, we model the partitioning of Cs within the estuarine environment for clay mineral interactions via PhreeqC. At fluvial sites, we observe a geogenic dependence of the Csp and a seasonal variability of Csd, with a downstream increase of the solid-liquid partitioning (log10 Kd values from 3.64 to 6.75 L kg-1) for suspended particulate matter (SPM) < 200 mg L-1. Along the estuarine salinity gradients, Cs shows a non-conservative behavior where fresh SPM (defined as Cs-depleted particles recently put in contact with Csd) act as a Cs sink during both flood and low discharge (drought) conditions. This sorption behavior was explained by the geochemical model, highlighting the relevance of ionic strength, water and SPM residence times. However, at high salinities, the overall log10 Kd value decreases from 6.02 to 5.20 for SPM ∼300-350 mg L-1 due to the Csd oceanic endmember. Despite wild oysters showing low bioconcentration factors (∼1220 L kg-1) at the estuary mouth, they are sensitive organisms to Cs fluxes.

Contrasting platinum trajectories in three major French rivers using dated sediment cores (1910-2021): From geochemical baseline to emerging source signals.

Platinum (Pt) is a Technology Critical Element (TCE) which, since the 1990s, has been mainly used in the industry in catalytic converters for automobile emission control. Previous studies have shown Pt contamination of road-side sediments and surface sediments in urban rivers and lakes but few of them have addressed temporal variations. The present work presents historical Pt concentration trends in 137Cs-dated sediment cores from floodplains or secondary channels at the outlets of three major French watersheds (Loire, Rhone, and Seine Rivers) covering the past ∼110 years, i.e., from the 1910s to 2021. Platinum baseline levels in the sediment were estimated for the Loire River (0.76 ± 0.22 µg kg-1 for the period ∼1910-∼1955) and the Rhone River (1.64 ± 0.41 µg kg-1), and historical Pt variations seem to reflect variations in hydrodynamics and grain size composition. Since the early 2000s, Pt concentrations in the Loire and the Rhone River sediments tend to increase (>2.5 µg kg-1) and were attributed to the use of car catalytic converters, an emerging technology since the 1990s using >50 % of European Pt demand. High and variable historical Pt concentrations (up to 14.6 µg kg-1) in the Seine River sediments may reflect legacy Pt sources due to former anthropogenic activities in this watershed, such as the use of Pt-based catalysts for petroleum refinery since the end of the 1940s, coal handling and precious metals refining, probably concealing the likely presence of an emerging traffic-related Pt signal. This first comparison of historical Pt concentration trends in sediments from contrasting watersheds allows to distinguish signals originating from different natural and anthropogenic sources (background level, historical sources, road traffic).

Global natural concentrations of Rare Earth Elements in aquatic organisms: Progress and lessons from fifty years of studies.

Rare Earth Elements (REEs) consist of a coherent group of elements with similar physicochemical properties and exhibit comparable geochemical behaviors in the environment, making them excellent tracers of environmental processes. For the past 50 years, scientific communities investigated the REE concentrations in biota through various types of research (e.g. exploratory studies, environmental proxies). The extensive development of new technologies over the past two decades has led to the increased exploitation and use of REEs, resulting in their release into aquatic ecosystems. The bioaccumulation of these emerging contaminants has prompted scientific communities to explore the fate of anthropogenic REEs within aquatic ecosystems. To achieve this, it is necessary to determine the natural concentration levels of REEs in aquatic organisms and the factors controlling REE dynamics. However, knowledge gaps still exist, and no comprehensive approach currently exists to assess the REE concentrations at the ecosystem scale or the factors controlling these concentrations in aquatic organisms. Based on a database comprising 102 articles, this study aimed to: i) provide a retrospective analysis of research topics over a 50-year period; ii) establish reference REE concentrations in several representative phyla of aquatic ecosystems; and iii) examine the global-scale influences of habitat and trophic position as controlling factors of REE concentrations in organisms. This study provides reference concentrations for 16 phyla of freshwater or marine organisms. An influence of habitat REE concentrations on organisms has been observed on a global scale. A trophic dilution of REE concentrations was highlighted, indicating the absence of biomagnification. Lastly, the retrospective approach of this study revealed several research gaps and proposed corresponding perspectives to address them. Embracing these perspectives in the coming years will lead to a better understanding of the risks of anthropogenic REE exposure for aquatic organisms.

First assessment of Rare Earth Element organotropism in Solea solea in a coastal area: The West Gironde Mud Patch (France).

Few studies exist on concentration and internal distribution of Rare Earth Elements (REEs) in marine fishes. REEs organotropism was determined in common sole (Solea solea) from the West Gironde Mud Patch (WGMP; N-E Atlantic Coast, France). The highest ∑REEs concentrations occurred in liver (213 ± 49.9 µg kg-1 DW) and gills (119 ± 77.5 µg kg-1 DW) followed by kidneys (57.7 ± 25.5 µg kg-1 DW), whereas the lowest levels were in muscles (4.53 ± 1.36 µg kg-1 DW) of Solea solea. No significant age- or sex-related differences were observed. The organotropism varied among groups of REEs. Light and heavy REEs preferentially accumulated in liver and gills, respectively. All considered organs showed different normalized REEs patterns, suggesting differences in internal distribution processes between organs. Further work should address: (1) baseline levels worldwide, and (2) factors controlling uptake and organ-specific concentration of REEs.

European fluxes of medical gadolinium to the ocean: A model based on healthcare databases.

Marine ecosystems are exposed to a multitude of stresses, including emerging metals as Rare Earth Elements. The management of these emerging contaminants represents a significant environmental issue. For the past three decades, the increasing medical use of gadolinium-based contrast agents (GBCAs) has contributed to their widespread dispersion in hydrosystems, raising concerns for ocean conservation. In order to control GBCA contamination pathways, a better understanding of the cycle of these elements is needed, based on the reliable characterization of fluxes from watersheds. Our study proposes an unprecedented annual flux model for anthropogenic gadolinium (Gdanth) based on GBCA consumption, demographics and medical uses. This model enabled the mapping of Gdanth fluxes for 48 European countries. The results show that 43 % of Gdanth is exported to the Atlantic Ocean, 24 % to the Black Sea, 23 % to the Mediterranean Sea and 9 % to the Baltic Sea. Together, Germany, France and Italy contribute 40 % of Europe's annual flux. Our study was therefore able to identify the current and future major contributors to Gdanth flux in Europe and identify abrupt changes related to the COVID-19 pandemic.

Historical mass balance of cadmium decontamination trends in a major European continent-ocean transition system: Case study of the Gironde Estuary.

Despite the effective remediation efforts following the end of the metallurgic activity thirty years ago upstream the Lot River watershed, the levels of cadmium (Cd) accumulated in wild oysters from the downstream Gironde Estuary still exceed nowadays the admissible human consumption limit (5 mg/kg, d.w.). The main goal of this work is to quantify the role of sediments as long-term intra-estuarine sources or sinks of Cd and the transport of this contaminant towards the estuary mouth taking as case study the example of the highly turbid Gironde Estuary. The original estimation for the annual net fluxes of the suspended particulate matter ( [Formula: see text] and particulate Cd ( [Formula: see text] ) presented in this work between 1990 and 2020 indicates that 80% of the Cd discharged into the ocean is in dissolved form (Cdd). The values of [Formula: see text] vary proportionally to those of [Formula: see text] and ranged between 0.1 and 1.4 t/y, with a ten-year average decreasing from 0.8 to 0.6 t/y for the past 30 years. The differences between ten-year total (Cdp + Cdd) gross and net fluxes show that Cd has effectively been stored in estuarine sediments. This Cd storage was of about 43, 22 and 13 t for the 1990s, 2000s and 2010s, respectively. However, during years of low gross fluxes, estuarine sediments act as additional, secondary sources of bio-available/dissolved Cd into the water column, potentially relating to the continued observations of high Cd concentrations in wild oysters at the estuary mouth. In addition to the natural solubility of Cdp along the salinity and turbidity gradients of the estuary, natural and anthropogenic remobilization of bottom sediment particles further contribute to its mobilization from the particle phase, along with other numerous inorganic/organic pollutants. The mass balances presented in this work could support a new sediment management policy potentially more beneficial to the estuarine ecosystem.

Impact of metallurgy tailings in a major European fluvial-estuarine system: Trajectories and resilience over seven decades.

Tailings containing mining and ore treatment waste, accumulated over long time periods are major contaminant sources at the watershed scale and may seriously impair environmental quality of river-sea continuums. A critical review of existing work in different disciplines addressing the multi-metal contamination of the Gironde Watershed, a major fluvial-estuarine model system representative of many other systems worldwide, has provided a condensed, yet pertinent overview on various aspects of this environmental problem. Combining long-term observation and contamination records from different environmental archives, there is a clear trend towards resilience for the main historical contaminants (Cd, Zn, Pb and Cu), yet suggesting that resilience needs appropriate management of both, tailings as the initial source and contaminated sediments acting as temporary metal traps which may transform into delayed sources. Contaminated sediment management is an increasingly important challenge due to (i) successful remediation at the contamination source itself (ii) global-change induced factors and strategies and (iii) lacking coordination of actions between upstream and downstream parts of the fluvial-estuarine continuum. Less studied and emerging metallic contaminants show recent trends in sediments and biota that are decoupled from the legacy contaminant trajectories due to recent sources and applications, suggesting that further work is needed to assess their potential impact on the environmental quality of the Gironde fluvial-estuarine system and that of other systems, especially in a context of worldwide rapidly growing mining activity and metal use.

Impacts of Highway Runoff on Metal Contamination Including Rare Earth Elements in a Small Urban Watershed: Case Study of Bordeaux Metropole (SW France).

High temporal resolution sampling of runoff (15 samples/4 h) and river water (24 samples/24 h) was performed during a major rainstorm (41 mm/4 h) in the Bordeaux Metropole, after a dry and high vehicle-density period. Runoff was sampled at the outlet of one collector draining Northern Bordeaux Highway (NBH; 80,000-93,000 vehicles/day) and river water in the downstream Jalle River. The studied metals, including priority and emergent (Rare Earth Elements [REEs]) contaminants, showed major temporal and spatial variations in the dissolved and particulate concentrations. Hierarchical cluster analyses distinguished metal groups, reflecting different: (i) sources (i.e., automotive traffic: Zn-Cu-Ce and wastewater treatment plant: Cd-Ag-Gd) and/or (ii) processes (i.e., groundwater dilution by rainwater and sorption processes). The contribution of the particulate fraction to total metal fluxes was predominant in the NBH collector (except for Sr and Mo) and highly variable in the Jalle River, where the highest particulate metal loads were due to the export of road dusts exported by the NBH collector. Metal fluxes from the NBH collector represented highly variable fractions of daily fluxes into the Gironde Estuary at the outlet of the Jalle River, depending on elements and partitioning. The resulting relative contributions ranged from: 5% (Sr) to 40% (Cu) for dissolved phases and 30% (As) to 88% (Cu) for particulate phases. The first 40 min of the event accounted for 65% of the suspended particulate matter flux (and associated particulate metals) exported by the NBH collector, whereas the respective water flux contribution was 35%. This finding clearly demonstrates the importance of monitoring the first minutes of rainy events when establishing mass balances in urban systems.

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.

Metal pollution trajectories and mixture risk assessed by combining dated cores and subsurface sediments along a major European river (Rhône River, France).

In European rivers, research and monitoring programmes have targeted metal pollution from bed and floodplain sediments since the mid-20th century by using various sampling and analysis protocols. We propose to characterise metal contamination trajectories since the 1960s based on the joint use of a large amount of data from dated cores and subsurface sediments along the Rhône River (ca. 512 km, Switzerland-France). For the reconstruction of spatio-temporal trends, enrichment factors (EF) and geo-accumulation (Igeo) approaches were compared. The latter index was preferred due to the recurrent lack of grain-size and lithogenic elements in the dataset. Local geochemical backgrounds were established near (1) the Subalps and (2) the Massif Central to consider the geological variability of the watershed. A high contamination (Igeo = 3-5) was found for Cd, Cu and Zn from upstream to downstream over the period 1980-2000. This pattern is consistent with long-term emissions from major cities and the nearby industrial areas of the Upper Rhône (Geneva, Arve Valley), and Middle Rhône (Lyon, Chemical Corridor, Gier Valley). Hotspots due to Cu and Zn leaching from vineyards, mining, and highway runoff were also identified, while Pb was especially driven by industrial sources. The recovery time of pollution in sediment varied according to the metals and was shorter upstream of Lyon (15-20 years) than downstream (30-40 years). More widely, it was faster on the Rhône than along other European rivers (e.g. Seine and Rhine). Finally, the ecotoxicological mixture risk of metal with Persistent Organic Pollutants (POPs) for sediment-dwelling organisms showed a medium "cocktail risk" dominated by metals upstream of Lyon, although it is enhanced due to POPs downstream, and southward to the delta and the Mediterranean Sea. Overall, this study demonstrates the heterogeneity of the contamination trends along large fluvial corridors such as the Rhône River.

Corbicula fluminea: A sentinel species for urban Rare Earth Element origin.

The increase in the global population, coupled with growing consumption of Rare Earth Elements (REEs), has led to increasing transfer of these emerging contaminants into the environment, particularly through the effluents from wastewater treatment plants (WWTP). The objectives of this study were to determine the geochemical quality of a French river subject to strong urban pressure (the Jalle River in the Bordeaux area) and to examine the bioavailability of natural and anthropogenic REEs in a model species of freshwater bivalve, the Asian clam Corbicula fluminea. To this end, two fractions (dissolved and total) of the water from the Jalle River were sampled and the bivalves were exposed by in situ caging during a three-month monitoring period. The REE patterns obtained showed the presence of Gadolinium (Gd) anomalies in the dissolved and total fractions as well as in Corbicula fluminea. The apparent bioavailability of natural REEs was in the following order for the dissolved fraction: Medium REEs (MREEs) > Light REEs (LREEs) > Heavy REEs (HREEs) and for the particulate fraction: MREEs > LREEs = HREEs. These results highlight the importance of the particulate fraction in the study of the bioavailability of REEs in bivalves. An increase of anthropogenic Gd (Gdanth) was observed in the dissolved fraction between the upstream site (3.4 ng.L-1) and the WWTP Downstream site (48.4 ng.L-1). The Gd anomaly observed in the water was also observed in Corbicula fluminea with a significant increase in the bioaccumulation of Gdanth, from 1.5 ± 1 ng.gDW-1 upstream to 4.1 ± 0.7 ng.gDW-1 downstream of the WWTP effluents, thus confirming the enhanced bioavailability of medical-origin Gd to freshwater bivalves. This study strongly suggests that Corbicula fluminea can be used as a sentinel species in the monitoring of Gd contamination of medical origin. It would thus appear important to consider the potential entry of this contaminant into the human food chain via other, commercially exploited bivalve species.

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.

Organotropism and biomarker response in oyster Crassostrea gigas exposed to platinum in seawater.

Platinum (Pt) is a technology critical element (TCE) for which biogeochemical cycles are still poorly understood. This lack of knowledge includes Pt effects on marine organisms, which proved to be able to bioconcentrate this trace element. Oysters Crassostrea gigas were exposed to stable Pt isotope spiked daily in seawater for 35 days. Seawater was renewed daily and spiked (with Pt(IV)) to three nominal Pt concentrations (50, 100, and 10,000 ng L-1) for two replicate series. Organotropism study revealed that gills, and to a lesser extent mantle, are the key organs regarding Pt accumulation, although a time- and concentration-dependent linear increase in Pt levels occurred in all the organs investigated (i.e., digestive gland, gonads, gills, mantle, and muscle). In oysters exposed to Pt concentrations of 10,000 ng L-1, significant biomarker impairments occurred, especially at cellular levels. They reflect altered lipofuscin and neutral lipid contents, as well as intralysosomal metal accumulation. These observations were attributed to activation of excretion/detoxification mechanisms, including Pt elimination through feces and clearly support the importance of the digestive gland in the response to direct Pt exposure. Despite relatively constant condition index, the integrative biological response (IBR) index suggests a generally decreasing health status of oysters.

Rare Earth Element fluxes over 15 years into a major European Estuary (Garonne-Gironde, SW France): Hospital effluents as a source of increasing gadolinium anomalies.

New and rapidly developing technologies imply the emission of emerging potentially toxic contaminants such as Rare Earth Elements (REEs). Yet, the lithology-derived quantities and anthropogenic contributions, especially from urban areas, to annual REE fluxes into fluvial-estuarine systems remain widely unknown. The Garonne River drains water from ~20% of the French land surface hosting about 5,200,000 inhabitants and two large cities. Based on long-term monitoring (2003-2017) of water discharges and dissolved REEs concentrations at the outlet of the Garonne Watershed upstream from Bordeaux, this study aims at assessing REE anomalies and evaluating temporal evolution of annual dissolved REE fluxes into the Gironde Estuary. Additionally, potential urban sources (e.g. domestic, medical) in the urban area of Bordeaux (1,190,000 inhab.) were analyzed to evaluate respective signatures and contributions. Gadolinium (Gd) showed clear anomalies in all samples, with annual average anthropogenic concentrations ranging from 1.8 to 7.2 ng·L-1 (0.011 to 0.046 nmol·L-1) in the Garonne River. If variations in annual Gd fluxes depend on hydrology, anthropogenic Gd fluxes have shown an overall increasing trend from 32 kg·year-1 (204 mol·year-1) in 2003 to 75 kg·year-1 (475 mol·year-1) in 2017. Sewer waters from the third largest hospital complex of France, the hospital group Pellegrin, contributed 25% to the incoming daily Gd flux into Bordeaux major Waste Water Treatment Plant (WWTP), owed to Gd use as contrast agent for Magnetic Resonance Imaging (MRI). Due to weak removal efficiency in the WWTP, the Bordeaux Metropole significantly contributes (>27 kg·year-1; 172 mol·year-1) to Gd fluxes in the Gironde Estuary. The temporal evolution of anthropogenic Gd fluxes in the Garonne River may be related with the growing regional population and the increasing number of MRI instruments, highlighting the importance of new high-tech applications in urban areas on contaminant fluxes and their potential harmful effects in fluvial-estuarine systems in the future.

Whole-transcriptome response to wastewater treatment plant and stormwater effluents in the Asian clam, Corbicula fluminea.

The increase in human population and urbanization are resulting in an increase in the volume of wastewater and urban runoff effluents entering natural ecosystems. These effluents may contain multiple pollutants to which the biological response of aquatic organisms is still poorly understood mainly due to mixture toxicity and interactions with other environmental factors. In this context, RNA sequencing was used to assess the impact of a chronic exposure to wastewater treatment plant and stormwater effluents at the whole-transcriptome level and evaluate the potential physiological outcomes in the Asian clam Corbicula fluminea. We de-novo assembled a transcriptome from C. fluminea digestive gland and identified a set of 3,181 transcripts with altered abundance in response to water quality. The largest differences in transcriptomic profiles were observed between C. fluminea from the reference site and those exposed to wastewater treatment plant effluents. On both anthropogenically impacted sites, most differentially expressed transcripts were involved in signaling pathways in relation to energy metabolism such as mTOR and FoxO, suggesting an energy/nutrient deficit and hypoxic conditions. These conditions were likely responsible for damages to proteins and transcripts in response to wastewater treatment effluents whereas exposure to urban runoff might result in immune and endocrine disruptions. In absence of comprehensive chemical characterization, the RNAseq approach could provide information regarding the mode of action of pollutants and then be useful for the identification of which parameters must be studied at higher integration level in order to diagnose sites where the presence of complex and variable mixtures of chemicals is suspected.

How can water quality be improved when the urban waste water directive has been fulfilled? A case study of the Lot river (France).

The Lot river, a major tributary of the downstream Garonne river, the largest river on the Northern side of the Pyrenees Mountains, was intensively studied in the 1970s. A pioneering program called "Lot Rivière Claire" provided a diagnosis of water quality at the scale of the whole watershed and proposed an ambitious program to manage nutrient pollution and eutrophication largely caused by urban wastewater releases. Later on, the implementation of European directives from 1991 to 2000 resulted in the nearly complete treatment of point sources of pollution in spite of a doubling of the basin's population. At the outlet of the Lot river, ammonium and phosphate contamination which respectively peaked to 1 mg N-NH4 L-1 and 0.3 mg P-PO4 L-1 in the 1980s returned to much lower levels in recent years (0.06 mg N-NH4 L-1 and 0.02 mg P-PO4 L-1), a reduction by a factor 15. However, during this time, nitrate contamination has regularly increased since the 1980s, from 0.5 to 1.2 mg N-NO3 L-1 in average, owing to the intensification of agriculture and livestock farming. Application of the Riverstrahler model allowed us to simulate the water quality of the Lot drainage network for the 2002-2014 period. We showed that, with respect to algal requirements, phosphorus and silica are well balanced, but nitrogen remains largely in excess over phosphorus and silica. This imbalance can be problematic for the ecological status of the water bodies. Using the model, for simulating various scenarios of watershed management, we showed that improvement of urban wastewater treatment would not result in any significant change in the river's water quality. Even though arable land occupies a rather limited fraction of the watershed area, only the adoption of better farming practices or more radical changes in the agro-food system could reverse the trend of increasing nitrate contamination.

Tracing platinum accumulation kinetics in oyster Crassostrea gigas, a sentinel species in coastal marine environments.

Platinum Group Elements (PGEs) are extremely scarce in the Earth's Crust and of strong interest for high-end technologies due to their specific properties. They belong to the Technology Critical Elements (TCEs) for which use is forecast to increase, implying growing emissions into the environment in the following years. In particular, with the intensive use of platinum (Pt) in car catalytic converters, the anthropogenic geochemical cycle of this element has surpassed the natural cycle. Yet, environmental Pt levels are still in the sub picomolar range, making its analytical detection a challenge. Few studies cover the behavior of Pt in marine waters in terms of speciation, reactivity and possible transfer to the biota. In this study, oysters (Crassostrea gigas) from an unpolluted estuary were exposed to the stable isotope 194Pt in seawater at a range of concentrations during 35days. Seawater was renewed daily and spiked to three nominal Pt concentrations (50, 100, and 10,000ng·L-1) for two replicate series. In addition, control conditions were monitored. Five oysters from each tank were dissected after 3, 7, 14, 21, 28, 35days of Pt exposure, and analyzed by ICP-MS. Accuracy of this analytical method applied to biological matrix was checked by an inter-method comparison with a voltammetrical technique. A concentration-dependent accumulation of Pt in oysters increasing with exposure time occurred. After 28days, oyster Pt accumulation from low and intermediate exposure conditions reached a plateau. This was not the case of the highest exposure condition for which oyster tissues showed increasing concentrations until the last day of the experiment. A linear correlation exists between seawater concentrations and Pt content in oysters for low and intermediate exposure concentrations i.e. closer to environmental concentrations. By showing high Pt accumulation potential, oysters may serve as sentinels, ensuring biomonitoring of Pt concentrations in marine coastal waters.

Inputs, dynamics and potential impacts of silver (Ag) from urban wastewater to a highly turbid estuary (SW France).

Although silver (Ag) has been listed as a priority pollutant for the aquatic environment by the European Union (Directive 2006/11/EC), the use of Ag-based products with antimicrobial effects is increasing in Europe, as well as North America and Asia. This study investigates personal care products (PCP) as a potential source of Ag in wastewater, as well as the dynamics and fate of Ag in the influent and effluent of a major urban wastewater treatment plant (WWTP) located on the fluvial part of the Gironde Estuary. Typical household PCPs marked as using Ag contained concentrations of up to 0.4 mg kg-1 making them likely contributors to urban Ag released into the aquatic environment. Silver concentrations in influent wastewater generally occurred during mid-week working hours and decreased during the night and on weekends clearly indicating the dominance of urban sources. Up to 90% of the total Ag in wastewater was bound to particles and efficiently (>80%) removed by the treatment process, whereas 20% of Ag was released into the fluvial estuary. Silver concentrations in wastewater effluents clearly exceeded estuarine concentrations and may strongly amplify the local Ag concentrations and fluxes, especially during summer rainstorms in low river discharge conditions. Further work should focus on environmental effects and fate of urban Ag release due to immediate localized outfall and/or the adsorption on estuarine particles and subsequent release as dissolved Ag chloro-complexes within the estuarine salinity gradient.

Modeling water quality in an urban river using hydrological factors--data driven approaches.

Contrasting seasonal variations occur in river flow and water quality as a result of short duration, severe intensity storms and typhoons in Taiwan. Sudden changes in river flow caused by impending extreme events may impose serious degradation on river water quality and fateful impacts on ecosystems. Water quality is measured in a monthly/quarterly scale, and therefore an estimation of water quality in a daily scale would be of good help for timely river pollution management. This study proposes a systematic analysis scheme (SAS) to assess the spatio-temporal interrelation of water quality in an urban river and construct water quality estimation models using two static and one dynamic artificial neural networks (ANNs) coupled with the Gamma test (GT) based on water quality, hydrological and economic data. The Dahan River basin in Taiwan is the study area. Ammonia nitrogen (NH3-N) is considered as the representative parameter, a correlative indicator in judging the contamination level over the study. Key factors the most closely related to the representative parameter (NH3-N) are extracted by the Gamma test for modeling NH3-N concentration, and as a result, four hydrological factors (discharge, days w/o discharge, water temperature and rainfall) are identified as model inputs. The modeling results demonstrate that the nonlinear autoregressive with exogenous input (NARX) network furnished with recurrent connections can accurately estimate NH3-N concentration with a very high coefficient of efficiency value (0.926) and a low RMSE value (0.386 mg/l). Besides, the NARX network can suitably catch peak values that mainly occur in dry periods (September-April in the study area), which is particularly important to water pollution treatment. The proposed SAS suggests a promising approach to reliably modeling the spatio-temporal NH3-N concentration based solely on hydrological data, without using water quality sampling data. It is worth noticing that such estimation can be made in a much shorter time interval of interest (span from a monthly scale to a daily scale) because hydrological data are long-term collected in a daily scale. The proposed SAS favorably makes NH3-N concentration estimation much easier (with only hydrological field sampling) and more efficient (in shorter time intervals), which can substantially help river managers interpret and estimate water quality responses to natural and/or manmade pollution in a more effective and timely way for river pollution management.