Estuarine dissolved speciation and partitioning of trace metals: a novel approach to study biogeochemical processes.

Estuaries are complex systems involving numerous biogeochemical gradients and processes that influence the behavior of trace metals. Lead (Pb), cadmium (Cd), and copper (Cu) speciation and partitioning were studied in the Gironde Estuary (SW France), using a multi-method approach in which data from innovative sensors and laboratory-based techniques were combined. For the first time in this system, the so-called dynamic fractions of the target metals (dissolved forms that are potentially bioavailable) were recorded on-board through voltammetry using unique antifouling gel-integrated microelectrode arrays (GIME) incorporated in a submersible sensing probe (TracMetal). Trace metals in the operationally defined dissolved <0.2 µm and <0.02 µm fractions, as well as complexed with suspended particles (collected after centrifugation) were quantified through sampling/laboratory-based techniques. High spatial resolution trace metal concentrations were monitored along the salinity gradient (S = 0.10 to S = 34.0) together with master bio-physicochemical parameters providing robust cruise-specific information on how well-known abiotic and biotic processes control the Gironde estuarine trace element partitioning, (i.e. conservative behavior, addition/removal). Combining conventional methods with GIME measurements showed: (i) the dominance of Cd dynamic species in the intra-estuarine total dissolved fraction (up to 90%), (ii) the importance of small colloids as trace metal carrier phases, desorbing and complexing dynamic fractions of Pb and Cu, and (iii) the potential influence of photo-redox processes remobilizing Pb under their dynamic forms (up to 80%). Data also suggest trace metal release/sorption by phytoplankton with an increase of dissolved Cu concentrations in the riverine branch, as well as Cu and Cd particulate concentrations showing higher levels towards productive coastal waters. This complete approach allowed to monitor key estuarine biogeochemical processes and highlighted the valuable use of the TracMetal to record subtle variations of potentially bioavailable dissolved metal fractions.

Effects of metals and persistent organic pollutants on the fitness and health of juveniles of the endangered european sturgeon Acipenser sturio Exposed to W1ater and sediments of the garonne and dordogne rivers.

The last remaining population of European sturgeon (Acipenser sturio) lives in the Gironde-Garonne-Dordogne (France) catchment (GGD). Captive young individuals are released into the GGD hydrosystem each year, as part of a restocking programme. This study aims to assess the health status of juveniles A. sturio to current conditions in the GGD hydrosystem, to evaluate their capacity to survive and grow in a moderately anthropized ecosystems. 3-month-old farmed sturgeons were exposed for one month in experimental conditions that mimic the environmental conditions in the Garonne and Dordogne rivers, followed by five months of depuration. After one month of exposure, fish exposed to Dordogne and Garonne waters bioaccumulated higher levels of metals and persistent organic pollutants, displayed a reduced hepato-somatic index, and had depleted levels of lipids and glycogen content in their liver, when compared with the Reference group. However, metabolic and swimming performance, as well as the costs of swimming were not impaired. After the 5 months depuration, a significant decrease of K was observed for all exposure conditions. HSI also decreased with time. The overall health status and adaptive capacity of juvenile A. sturio appeared to be maintained over the experimental 6 months' period. Juveniles of A. sturio seem to have the adaptive capacity to survive and grow in the GGD hydrosystem, after being released as part of a restocking programme.

Using recent high-frequency surveys to reconstitute 35 years of organic carbon variations in a eutrophic lowland river.

Concentrations of dissolved and particulate organic carbon (DOC and POC), total suspended solids (TSS), were measured daily, and phytoplankton pigments (chlorophyll-a and pheopigments) were measured every 3 days at three strategic stations along the eutrophic Loire River between November 2011 and November 2013 marked by a high annual and seasonal variability in hydrological regimes. This unique high-frequency dataset allowed to determine the POC origin (autochthonous or allochthonous). Some strong relationships were evidenced between POC, total pigments and TSS and were tested on a long-term database with a lower frequency (monthly data) to reconstitute unmeasured algal and detrital POC concentrations and estimate annual total organic carbon (TOC) fluxes from 1980 onwards. The results were subjected to only ≈25 % uncertainty and showed that the annual TOC fluxes at the outlet of the Loire River decreased from 520 10(3) tC year(-1) (i.e. 4.7 t km(-2) year(-1)) in the early 1990s to 150 10(3) tC year(-1) (i.e. 1.4 t km(-2) year(-1)) in 2012. Although DOC always dominates, the autochthonous POC represented 35 % of the TOC load at the basin outlet by the end of the 1980s and declined to finally represent 15 % only of the TOC. The control of phosphorus direct inputs and the invasion by Corbicula clams spp. which both occurred since the early 1990s probably highly reduced the development of phytoplankton. Consequently, the autochthonous POC contribution declined and TSS concentrations in summertime significantly decreased as well as a result of both less phytoplankton and less calcite precipitation. At the present time, at least 75 % of the POC has allochthonous origins in the upper Middle Loire but downstream, autochthonous POC dominates during summer phytoplanktonic blooms when total pigments concentrations reach up to 70 µg L(-1) (equivalent to 75 % of the total POC).

Long-term survey of heavy-metal pollution, biofilm contamination and diatom community structure in the Riou Mort watershed, South-West France.

In a metal-polluted stream in the Riou Mort watershed in SW France, periphytic biofilm was analyzed for diatom cell densities and taxonomic composition, dry weight and metal bio-accumulation (cadmium and zinc). Periphytic diatom communities were affected by the metal but displayed induced tolerance, seen through structural impact (dominance of small, adnate species) as well as morphological abnormalities particularly in the genera Ulnaria and Fragilaria. Species assemblages were characterized by taxa known to occur in metal-polluted environments, and shifts in the community structure expressed seasonal patterns: high numbers of Eolimna minima, Nitzschia palea and Pinnularia parvulissima were recorded in Summer and Autumn, whereas the species Surirella brebissonii, Achnanthidium minutissimum, Navicula lanceolata and Surirella angusta were dominant in Winter and Spring. Commonly used indices such as the Shannon diversity index and Specific Pollution Sensitivity Index reflected the level of pollution and suggest seasonal periodicity, the lowest diversities being observed in Summer.

Effects of storage method and duration on the toxicity of marine sediments to embryos of Crassostrea gigas oysters.

The objective of laboratory sediment bioassays is to estimate in situ toxicity. This goal is difficult to achieve, as one of the main limitations of sediment toxicity tests is disruption of sediment geochemistry during sampling, handling and preservation. The effects of storage on the estimation of marine sediment toxicity to Crassostrea gigas embryos and larvae were investigated. Three storage methods and four storage periods were compared with three different sediment types contaminated by heavy metals, polycyclic aromatic hydrocarbons (PAHs) and both contaminants. Freezing and freeze-drying considerably increased the toxicity of decanted sediments and their elutriates as compared to the toxicity obtained with fresh sediments. Concerning the elutriates, the toxicity found with frozen and freeze-dried sediments was correlated with DOC, ammonia and PAH contents. However, the toxicity of fresh sediments kept at 4 degrees C increased with increasing duration of storage and was also correlated with the amount of ammonia in the elutriates.