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.

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.

Platinum in sediments and mussels from the northwestern Mediterranean coast: Temporal and spatial aspects.

Platinum (Pt) is considered a Technology Critical Element (TCE) and an emerging metallic contaminant with increasing release into the environment. Gaps in knowledge and understanding of environmental levels, fate and effects of Pt still exist, especially in the marine environment. This work presents Pt concentrations in the northwestern Mediterranean coast including: (i) temporal variability from sediment cores and farmed mussels in the Toulon Bay (historically affected by intense human activities) and (ii) spatial distribution from recent wild mussels collected along ∼ 700 km coastline with contrasting ecosystems (including natural reserves), quantified using voltammetry and inductively coupled plasma-mass spectrometry. The historical (>100 years) record of Pt in sediments from the Toulon Bay suggests the existence of non-negligible Pt sources older than those related to vehicle emission devices, such as petrol industry and coal-fired activities. A strong Pt increase in more recent sediments (from ∼12 to 16 ng g-1) and mussels (8-fold increase from ∼0.12 to 0.80 ng g-1) covering the past 25 years reflect the overall evolution of Pt demand in Europe (∼20-fold increase for vehicle catalysts in 20 years). Spatial biomonitoring of Pt in mussels along the northwestern Mediterranean coast is assumed to reflect inter-site differences of Pt exposure (0.09-0.66 ng g-1) despite seasonal effect on tissue development. This study highlights the need for thorough and regular monitoring of Pt levels in sediments and biota from urbanized coastal areas in order to better assess the environmental impact of this TCE, including potential risks for marine organisms.

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.

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.

Assessment of the effects of Cu and Ag in oysters Crassostrea gigas (Thunberg, 1793) using a battery of cell and tissue level biomarkers.

Oysters are considered sentinel organisms in environmental water quality monitoring programs in which cell and tissue level biomarkers are reliable tools. Copper (Cu) and silver (Ag) are present in relatively high concentrations in several estuaries, potentially affecting environmental and human health. Crassostrea gigas oysters were exposed during 28 days to a range of environmentally relevant concentrations of Cu and Ag alone or in mixture. Effects were studied through cell and tissue level biomarkers approach. Results indicated: changes in the Condition Index (CI), altered digestive gland epithelium and presence of histopathological alterations in the gonad and digestive gland of exposed oysters. A time-dependent increase in lipofuscin contents in exposed oysters and an increase in intralysosomal metal accumulation in digestive cells through the experiment were also recorded. The Integrative Biological Response (IBR) Index showed that even at low exposure levels, Ag and Cu can produce alterations on oysters' health status.

Evidencing the Impact of Coastal Contaminated Sediments on Mussels Through Pb Stable Isotopes Composition.

Heavily contaminated sediments are a serious concern for ecosystem quality, especially in coastal areas, where vulnerability is high due to intense anthropogenic pressure. Surface sediments (54 stations), 50 cm interface cores (five specific stations), river particles, coal and bulk Pb plate from past French Navy activities, seawater and mussels were collected in Toulon Bay (NW Mediterranean Sea). Lead content and Pb stable isotope composition have evidenced the direct impact of sediment pollution stock on both the water column quality and the living organisms, through the specific Pb isotopic signature in these considered compartments. The history of pollution events including past and present contaminant dispersion in Toulon Bay were also demonstrated by historical records of Pb content and Pb isotope ratios in sediment profiles. The sediment resuspension events, as simulated by batch experiments, could be a major factor contributing to the high Pb mobility in the considered ecosystem. A survey of Pb concentrations in surface seawater at 40 stations has revealed poor seawater quality, affecting both the dissolved fraction and suspended particles and points to marina/harbors as additional diffuse sources of dissolved Pb.

Sources and historical record of tin and butyl-tin species in a Mediterranean bay (Toulon Bay, France).

Concentrations of inorganic tin (Sn(inorg)), tributyltin (TBT) and its degradation products dibutyltin (DBT) and monobutyltin (MBT) were measured in surface sediments and in two cores from the Toulon Bay, hosting the major French military harbour. Anticipating planned dredging, the aim of the present work is to map and evaluate for the first time the recent and historic contamination of these sediments by inorganic and organic Sn species derived from antifouling paints used for various naval domains including military, trade, tourism and leisure. Tin and butyl-Sn concentrations in the bay varied strongly (4 orders of magnitude), depending on the site, showing maximum values near the shipyards. The concentrations of total Sn (1.3-112 µg g(-1)), TBT (<0.5-2,700 ng g(-1)), DBT (<0.5-1,800 ng g(-1)) and MBT (0.5-1,000 ng g(-1)) generally decreased towards the open sea, i.e. as a function of both distance from the presumed main source and bottom currents. Progressive degradation state of the butyl-Sn species according to the same spatial scheme and the enrichment factors support the scenario of a strongly polluted bay with exportation of polluted sediment to the open Mediterranean. Low degradation and the historical records of butyl-Sn species in two (210)Pb-dated sediment cores, representative of the Northern Bay, are consistent with the relatively recent use of TBT by military shipyards and confirm maximum pollution during the 1970s, which will persist in the anoxic sediments for several centuries. The results show that (a) degradation kinetics of butyl-Sn species depend on environmental conditions, (b) the final degradation product Sn(inorgBT) is by far the dominant species after 10-12 half-life periods and (c) using recent data to reliably assess former TBT contamination requires the use of a modified butyl-Sn degradation index BDI(mod). Resuspension of extremely contaminated subsurface sediments by the scheduled dredging will probably result in mobilization of important amounts of butyl-Sn species.

Silver behaviour along the salinity gradient of the Gironde Estuary.

Dissolved and particulate Ag concentrations (Ag(D) and Ag(P), respectively) were measured in surface water and suspended particulate matter (SPM) along the salinity gradient of the Gironde Estuary, South West France, during three cruises (2008-2009) covering contrasting hydrological conditions, i.e. two cruises during intermediate and one during high freshwater discharge (~740 and ~2,300 m(3)/s). Silver distribution reflected non-conservative behaviour with 60-70 % of Ag(P) in freshwater particles being desorbed by chlorocomplexation. The amount of Ag(P) desorbed was similar to the so-called reactive, potentially bioavailable Ag(P) fraction (60 ± 4 %) extracted from river SPM by 1 M HCl. Both Ag(P) (0.22 ± 0.05 mg/kg) and Ag(P)/Th(P) (0.025-0.028) in the residual fraction of fluvial and estuarine SPM were similar to those in SPM from the estuary mouth and in coastal sediments from the shelf off the Gironde Estuary, indicating that chlorocomplexation desorbs the reactive Ag(P). The data show that desorption of reactive Ag(P) mainly occurs inside the estuary during low and intermediate discharge, whereas expulsion of partially Ag(P)-depleted SPM (Ag(P)/Th(P) ~0.040) during the flood implies ongoing desorption in the coastal ocean, e.g. in the nearby oyster production areas (Marennes-Oléron Bay). The highest Ag(D) levels (6-8 ng/L) occurred in the mid-salinity range (15-20) of the Gironde Estuary and were decoupled from freshwater discharge. In the maximum turbidity zone, Ag(D) were at minimum, showing that high SPM concentrations (a) induce Ag(D) adsorption in estuarine freshwater and (b) counterbalance Ag(P) desorption in the low salinity range (1-3). Accordingly, Ag behaviour in turbid estuaries appears to be controlled by the balance between salinity and SPM levels. The first estimates of daily Ag(D) net fluxes for the Gironde Estuary (Boyle's method) showed relatively stable theoretical Ag(D) at zero salinity (Ag (D) (0) = 25-30 ng/L) for the contrasting hydrological situations. Accordingly, Ag(D) net fluxes were very similar for the situations with intermediate discharge (1.7 and 1.6 g/day) and clearly higher during the flood (5.0 g/day) despite incomplete desorption. Applying Ag (D) (0) to the annual freshwater inputs provided an annual net Ag(D) flux (0.64-0.89 t/year in 2008 and 0.56-0.77 t/year in 2009) that was 12-50 times greater than the Ag(D) gross flux. This estimate was consistent with net Ag(D) flux estimates obtained from gross Ag(P) flux considering 60 % desorption in the estuarine salinity gradient.

Comparison of periphytic biofilm and filter-feeding bivalve metal bioaccumulation (Cd and Zn) to monitor hydrosystem restoration after industrial remediation: a year of biomonitoring.

Despite a significant decrease in the metallic waste emissions from an industrial site and a remediation process initiated in 2007, the Riou-Mort watershed (southwest France) still exhibits high Cd and Zn concentrations. Metal wastes have long been proven to significantly disturb aquatic communities. In this study, bioaccumulation capacities and responses to the chemical improvement of the hydrosystem were assessed for a year along the contamination gradient through the comparison of two biological models: Corbicula fluminea and periphytic biofilms, both considered as good bioindicators. Bioaccumulation results confirmed the persistence of water contamination in Corbicula fluminea and biofilms with, respectively, maximum Cd concentrations reaching 80.6 and 861.2 µg gDW(-1), and Zn concentrations 2.0 and 21.3 mg gDW(-1). Biofilms exhibited bioaccumulation in close correlation with water contamination, while Corbicula fluminea presented Cd bioaccumulation clearly regulated by water temperature and metal concentrations, affecting the ventilatory activity, as revealed by condition indices measurements. Also, a linear regression using Cd bioaccumulation and temperature () showed that below approximately 6 °C Corbicula fluminea did not appear to accumulate metals. Bioconcentration factors (BCFs) were higher in biofilms in comparison with Corbicula fluminea and showed the great accumulation capacity of suspended particulate matter in biofilms. However, bioaccumulation capacities are known to be influenced by many factors other than metal concentrations, such as temperature, water oxygenation or plankton and nutrient concentrations. Thus, this study demonstrates the power of a combined assessment using both Corbicula fluminea and biofilms as bioindicators to give a more integrated view of water quality assessment. Finally, when comparing our results with previous studies, the start of hydrosystem restoration could be shown by decreasing bioaccumulation in organisms.

Long-term records of cadmium and silver contamination in sediments and oysters from the Gironde fluvial-estuarine continuum - evidence of changing silver sources.

The Gironde fluvial estuarine system is impacted by historic metal pollution (e.g. Cd, Zn, Hg) and oysters (Crassostrea gigas) from the estuary mouth have shown extremely high Cd concentrations for decades. Based on recent work (Chiffoleau et al., 2005) revealing anomalously high Ag concentrations (up to 65 mg kg(-1); dry weight) in Gironde oysters, we compared long-term (~1955-2001) records of Ag and Cd concentrations in reservoir sediment with the respective concentrations in oysters collected between 1979 and 2010 to identify the origin and historical trend of the recently discovered Ag anomaly. Sediment cores from two reservoirs upstream and downstream from the main metal pollution source provided information on (i) geochemical background (upstream; Ag: ~0.3 mg kg(-1); Cd: ~0.8 mg kg(-1)) and (ii) historical trends in Ag and Cd pollution. The results showed parallel concentration-depth profiles of Ag and Cd supporting a common source and transport. Decreasing concentrations since 1986 (Cd: from 300 to 11 mg kg(-1); Ag: from 6.7 to 0.43 mg kg(-1)) reflected the termination of Zn ore treatment in the Decazeville basin followed by remediation actions. Accordingly, Cd concentrations in oysters decreased after 1988 (from 109 to 26 mg kg(-1), dry weight (dw)), while Ag bioaccumulation increased from 38 up to 116 mg kg(-1), dw after 1993. Based on the Cd/Ag ratio (Cd/Ag~2) in oysters sampled before the termination of zinc ore treatment (1981-1985) and assuming that nearly all Cd in oysters originated from the metal point source, we estimated the respective contribution of Ag from this source to Ag concentrations in oysters. The evolution over the past 30 years clearly suggested that the recent, unexplained Ag concentrations in oysters are due to increasing contributions (>70% after 1999) by other sources, such as photography, electronics and emerging Ag applications/materials.

Roles of regional hydrodynamic and trophic contamination in cadmium bioaccumulation by Pacific oysters in the Marennes-Oléron Bay (France).

The Marennes-Oléron Bay, hosting the largest oyster production in France, is influenced by the historic polymetallic pollution of the Gironde Estuary. Despite management efforts and decreasing emissions in the Gironde watershed, cadmium levels in oysters from the bay are close to the consumption limit (5 µg g(-1) dw, EC). From mid April to mid July 2009, we investigated the role of tidal resuspension and regional hydrodynamics on Cd speciation (seawater, SPM, phytoplankton, sediment, microphytobenthos) and bioaccumulation in 18 month-old oysters (gills, digestive glands, rests of tissues) reared under natural conditions (i) at ∼60 cm above the sediment and (ii) on the sediment surface. Dissolved and particulate Cd concentrations in surface and bottom waters were similar and constant over tidal cycle suggesting the absence of Cd release during sediment resuspension. Temporal dissolved and particulate Cd concentrations were closely related to Gironde Estuary water discharges, showing increasing concentrations during flood situations and decreasing concentrations afterwards. Cd depletion in the water column was associated with increasing Cd in the [20-100 µm] plankton fraction, suggesting Cd bioaccumulation. After 3 months, enrichment factors of Cd in tissues of oysters exposed in the water column and directly on the sediment were respectively 3.0 and 2.2 in gills, 4.7 and 3.2 in digestive glands and 4.9 and 3.4 in remaining tissues. Increasing Cd bioaccumulation in gills, digestive glands and remaining tissues can be related to elevated dissolved Cd in the bay, suggesting gill contamination via the direct pathway and subsequent internal redistribution of Cd to other organs and tissues. Elevated Cd contents in oysters reared on tables could be attributed to different trophic Cd transfer (phytoplankton versus microphytobenthos) or to different oyster metabolisms between the rearing conditions as suggested by metallothionein concentrations.

Copper addition by organic matter degradation in the freshwater reaches of a turbid estuary.

This study reports on the relationship between copper (Cu) behavior and organic matter (OM) transformation along the turbidity gradient in the freshwater reaches of the Gironde Estuary. During a one-year survey, surface water and suspended particulate matter (SPM) were sampled at least monthly at three sites along the Garonne Branch, representing the main fluvial branch of the Gironde Estuary. Additionally, a longitudinal high resolution profile was sampled along the Garonne Branch, covering the turbidity gradient from the river water endmember to the maximum turbidity zone (MTZ). Seasonal variability and spatial distribution of Cu in both the dissolved phases (<0.2 µm, Cu(0.2) and <0.02 µm, Cu(0.02)) and particulate Cu (Cu(P)) clearly suggested Cu(0.2) addition during summer, that increased the Cu(0.2) concentrations by a factor ~2, mainly manifested by an increase in the Cu(0.02) fraction. At the annual timescale (2004), this internal Cu reactivity increased Cu(0.02) fluxes in the Garonne Branch by ~20% (3.6 t year(-1)), with the equivalent of ~2.9 t year(-1) derived from the Cu(P) fraction and ~0.7 t year(-1) from the colloidal (0.02-0.2 µm) fraction, without involving and/or affecting the Cu(C18) (hydrophobic metal-organic complexes) fraction. Combining data on Cu speciation with the results obtained by several independent techniques (DOC and POC measurements, 3D-fluorescence, and TEM) suggested close relationships between Cu behavior and OM transformation/restructuration along the turbidity gradient in the Garonne Branch. The observed Cu(0.02) addition was related to increasing humification (humification index HIX increased from 9 to 12, network formation) and labile OM degradation (Iγ/Iα ratio decreased from 0.70 to 0.44), going along with decreasing DOC and POC concentrations. Mass-balances suggest that in the studied system, degradation of OM may account for the release of ~25 µmol potentially bioaccessible Cu(0.02) per mole of particulate organic carbon mineralized.

Tracing cadmium contamination kinetics and pathways in oysters (Crassostrea gigas) by multiple stable Cd isotope spike experiments.

Laboratory experiments using stable Cd isotopes ((110)Cd and (112)Cd) were conducted to separately and simultaneously characterize Cd accumulation in different tissues of Pacific oysters (Crassostrea gigas) via the (i) trophic and (ii) direct pathways. For this, we exposed juvenile oysters to (110)Cd-spiked seawater ((110)Cd: 2 µg l(-1); constant level) and (112)Cd-spiked food (Thalassiossera weissflogii, (112)Cd: 2 µg l(-1) in 35×10(3) cells/oyster/L) in four experimental treatment groups, each containing 6 oysters, for 21 days with constant trophic feeding. These Cd contamination levels were ∼10 times lower than those typically used in experimental accumulation studies. Three oysters per treatment group were dissected every 7 days with separate sampling of the gills, digestive gland and the rest of the body. Metallothioneins were analysed in the digestive gland and gills. Cadmium concentrations and isotope ratios were measured in water (daily) and tissues (weekly) by GF-AAS and ICP-MS. The observed time-dependant evolution in Cd concentrations and (110)Cd/(114)Cd and (112)Cd/(114)Cd isotope ratios clearly revealed the bio-accumulation short-term kinetics and pathways of Cd contamination in the different tissues. Under the experimental conditions, significantly changed isotope ratios in gills and the digestive gland of oysters suggested rapid and efficient contamination by (110)Cd derived from direct exposure followed by internal Cd transfer between organs. Trophic contamination became measurable after 14 days of exposure corresponding to a trophic transfer rate of 1%. Constant metallothionein levels during the experiment suggested that the initially present metallothionein levels were sufficient to deal with the experimental Cd exposure.

Long-term monitoring (1960-2008) of the river-sediment transport in the Red River Watershed (Vietnam): temporal variability and dam-reservoir impact.

The Red River (China/Vietnam, A=155,000 km(2)) is a typical humid tropics river originating from the mountainous area of Yunnan Province in China. Based on information on daily discharge (Q) and suspended particulate matter (SPM) concentration between 1960-2008 for the SonTay gauging station (outlet of the River and entry to the Delta) provided by the National Institute IMHE-MONRE, the mean annual SPM flux was estimated at 90 Mt/yr, corresponding to a sediment yield of 600 t/km(2)/yr. The temporal variability of annual SPM fluxes (ranging from 24 to 200 Mt/yr) is strongly related to the interannual hydrological conditions. However, some years of high water flow were not associated with high sediment fluxes, especially after 1989 when the HoaBinh dam came into operation. Therefore, the median discharge pre- (3389 m(3)/s) and post 1989 (3495 m(3)/s) are similar indicating there was little or no change between both periods. Sediment rating curves (power law-type; SPM=aQ(b)) were fitted for both periods (1960-1989; 1990-2008). The analysis of the pre- and post-1989 sediment rating parameters (a, b) suggests a downshift of b-parameter values after 1989, attributed to a decrease of the sediment supply due to the commissioning of the HoaBinh dam. A single sediment rating curve derived from 1960-1989 data was used to simulate the annual variability of former sediment delivery, generating excellent cumulative flux estimates (error ~1%). In contrast, applying the same rating curve to the 1990-2008 data resulted in systematic and substantial (up to 109%) overestimation. This suggests that the HoaBinh dam reduces annual SPM delivery to the delta by half, implying important metal/metalloid storage behind the HoaBinh dam.

The particulate 7Be/210Pbxs and 234Th/210Pbxs activity ratios as tracers for tidal-to-seasonal particle dynamics in the Gironde estuary (France): implications for the budget of particle-associated contaminants.

The short-lived natural radionuclides (7)Be (T(1/2)=53 days), (234)Th(xs) (T(1/2)=24.1 days) and (210)Pb(xs) (T(1/2)=22.3 years), i.e. (234)Th and (210)Pb in excesses of that supported within particles by the decay of their parent isotopes, were analysed in suspended particulate matter (SPM) to study the particle dynamics in the Gironde fluvial estuarine system (France), strongly impacted by heavy metal pollution. From surveys of this land-ocean interface in 2006 and 2007, we established a times series of these radioisotopes and of their activity ratios ((7)Be/(210)Pb(xs) and (234)Th/(210)Pb(xs) ARs) in particles sampled under different hydrological conditions. The particulate (7)Be/(210)Pb(xs) AR varies along the fluvial estuarine system mainly due to variations in (7)Be activities, controlled by riverine, oceanic and atmospheric inputs and by resuspension of old (7)Be-deficient sediments. These processes vary with river discharge, tidal cycle and season. Therefore, seasonal particle transport processes can be described using variations of the SPM (7)Be/(210)Pb(xs) ARs. During high river discharge, the SPM (7)Be/(210)Pb(x) ARs decrease from river to the ocean. The turbidity maximum zone (TMZ) is dispersed and the particles, and the associated contaminants, are rapidly transported from river to coastal waters, without significant retention within the TMZ. During low river discharge, the TMZ intrudes into the fluvial estuary, and the lowest (7)Be/(210)Pb(x) ARs are observed there due to resuspension of (7)Be-deficient sediments. Away from the TMZ, from the middle to lower estuary, SPM (7)Be/(210)Pb(x) ARs increase, indicating that the particles have been recently tagged with (7)Be. We explain this trend as being caused by marine input of dissolved radionuclides, as traced by SPM (234)Th/(210)Pb(xs) ARs, followed by scavenging in the estuary. This result indicates that particle transport models based on (7)Be and trace-metal budgets must consider oceanic dissolved inputs as an additional source of (7)Be and, possibly, of contaminants to estuaries.

Assessment of metal contamination in a small mining- and smelting-affected watershed: high resolution monitoring coupled with spatial analysis by GIS.

The Riou Mort River watershed (SW France), representative of a heavily polluted, small, heterogeneous watershed, represents a major source for the polymetallic pollution of the Lot-Garonne-Gironde fluvial-estuarine system due to former mining and ore-treatment activities. In order to assess spatial distribution of the metal/metalloid contamination in the watershed, a high resolution hydrological and geochemical monitoring were performed during one year at four permanent observation stations. Additionally, thirty-five stream sediment samples were collected at representative key sites and analyzed for metal/metalloid (Cd, Zn, Cu, Pb, As, Sb, Mo, V, Cr, Co, Ni, Th, U and Hg) concentrations. The particulate concentrations in water and stream sediments show high spatial differences for most of the studied elements suggesting strong anthropogenic and/or lithogenic influences; for stream sediments, the sequence of the highest variability, ranging from 100% to 300%, is the following: Mo < Cu < Hg < As < Sb < Cd < Zn < Pb. Multidimensional statistical analyses combined with metal/metalloid maps generated by GIS tool were used to establish relationships between elements, to identify metal/metalloid sources and localize geochemical anomalies attributed to local geochemical background, urban and industrial activities. Finally, this study presents an approach to assess anthropogenic trace metal inputs within this watershed by combining lithology-dependent geochemical background values, metal/metalloid concentrations in stream sediments and mass balances of element fluxes at four key sites. The strongest anthropogenic contributions to particulate element fluxes are 90-95% for Cd, Zn and Hg in downstream sub-catchments. The localisation of anthropogenic metal/metalloid sources in restricted areas offers a great opportunity to further significantly reduce metal emissions and restore the Lot-Garonne-Gironde fluvial-estuarine ecosystem.

Potential impact of former Zn ore extraction activities on dissolved uranium distribution in the Riou-Mort watershed (France).

The industrial basin of Decazeville (Riou-Mort watershed, South-West France) is well known for its heavy metal pollution and its subsequent environmental effects on the Lot-Garonne River system. The source of this pollution is the Riou-Mort River, which drains smelting waste areas. A first survey after remediation works has revealed elevated dissolved uranium (U(D)) concentrations in the outlet of the Riou-Mort River. The objective of this research is to identify the origin of U(D) in the Riou-Mort watershed and to evaluate the impact of industrial activities on this element. Uranium was measured at 10 water sampling sites, located upstream and downstream the industrial basin, and in three smelting waste deposits. Uranium concentrations in the smelting waste deposits reach up to 14.4 mg kg(-1) and (234U/238U) activity ratios (AR) are near unity. Dissolved U concentrations in the Riou-Mort River and its main tributaries ranges over two orders of magnitude from 0.02 to 6.1 microg L(-1). The highest levels were measured in a site with no anthropogenic pollution, upstream from the industrial area. This observation suggests that U(D) is mainly linked to weathering; the elevated U concentrations originate from the naturally occurring radioactive materials (NORM) located in the Permian bedrock and no significant U pollution exists, at present, in the Riou-Mort watershed. This work demonstrates that spatial monitoring coupled with a long time-series are an essential prerequisite in assessment of spatiotemporal variations of U(D), prior to a diagnostic of pollution in a small watershed.