Ludovic Lesven

Arsenic behavior in river sediments under redox gradient: A review

The fate of arsenic - a redox sensitive metalloid - in surface sediments is closely linked to early diagenetic processes. The review presents the main redox mechanisms and final products of As that have been evidenced over the last years. Oxidation of organic matter and concomitant reduction of oxidants by bacterial activity result in redox transformations of As species. The evolution of the sediment reactivity will also induce secondary abiotic reactions like complexation/de-complexation, sorption, precipitation/dissolution and biotic reactions that could, for instance, lead to the detoxification of some As species. Overall, abiotic redox reactions that govern the speciation of As mostly involve manganese (hydr)-oxides and reduced sulfur species produced by the sulfate-reducing bacteria. Bacterial activity is also responsible for the inter-conversion between As(V) and As(III), as well as for the production of methylated arsenic species. In surficial sediments, sorption processes also control the fate of inorganic As(V), through the formation of inner sphere complexes with iron (hydr)-oxides, that are biologically reduced in buried sediment. Arsenic species can also be bound to organic matter, either directly to functional groups or indirectly through metal complexes. Finally, even if the role of reduced sulfur species in the cycling of arsenic in sediments has been evidenced, some of the transformations remain hypothetical and deserve further investigation.

Daily variations of Zn and Pb concentrations in the Deûle River in relation to the resuspension of heavily polluted sediments

Sediments in the Deûle River (northern France) are severely polluted by metals in the vicinity of several metallurgical plants. The aim of this paper is to identify the role played by the recurrent resuspension of these polluted sediments by boat traffic on the dissolved Pb and Zn concentrations in the river. For that purpose, several high-frequency on-line monitoring campaigns were performed. Our results clearly suggest that the resuspension of sedimentary particles into the overlying water significantly increased the dissolved electrolabile Pb and Zn contents. This increase does not persist for a long time because at night and during weekends and holidays, when the boat traffic strongly slows down, Pb and Zn concentrations drop again quickly. Our data also indicate that the biological processes (such as photosynthetic and respiration activities), diffusive and benthic fluxes, as well as dilution of pore water into the overlying water during sediment remobilization do not contribute significantly to the sharp increase of dissolved Pb and Zn concentrations in the river during the day. The good correlation between turbidity and electrolabile metal concentration allows us to discard slow AVS (Acid Volatile Sulfides) oxidation as well. Desorption of metals from sediment particles was clearly the most relevant process, responsible for the increase of dissolved Pb and Zn concentrations in the water column.

Early diagenetic processes aspects controlling the mobility of dissolved trace metals in three riverine sediment columns.

The behaviour of Mn, Fe, Co, Zn, Cd, Pb and Ni has been studied during early diagenesis in three different riverine sediments (Spierre, Lys and Sheldt). For that purpose (1) pore waters were extracted from sediment cores by centrifugation under nitrogen and further analyzed for the determination of total dissolved metal concentrations and (2) DET and DGT probes have been deployed in situ for the determination of high resolution profiles of labile and total dissolved metal concentrations. Furthermore, sulfidization processes have been examined; they revealed a production of pyrite near the water-sediment interface at Helkijn and Wervik sampling sites, probably due to a partial re-oxidation of reduced sulphur species. In Spierre sediments, where Eh values are the most negative, pyrite production should be mainly due to strict anaerobic processes. Concentrations of AVS in Spierre sediments are also very high and result in low TI values and low trace metal concentrations in the pore waters. Otherwise, in Wervik sediments, the low pH values combined to a TI value close to 0 results in the highest observed dissolved trace metal levels. DOS remains low at the three sites, since it does not exceed 0.4. In Wervik and Helkijn, the limitation is probably due to low sedimentary inputs of sulphate. In Spierre, sulphate is never exhausted in the pore water, suggesting a limitation of the DOS by a lack of bio-degradable organic matter. Values of Cd, Cu and Pb DGT concentrations remain low in pore waters whatever the site, due to their strong affinity with the reduced sulphur pool. It has also been demonstrated that the labile fractions of Pb and Cd are the lowest and do not exceed 0.5, while Co and Ni are the most available metals.

Bacterial metal resistance genes and metal bioavailability in contaminated sediments.

In bacteria a metal may be defined as bioavailable if it crosses the cytoplasmic membrane to reach the cytoplasm. Once inside the cell, specific metal resistance systems may be triggered. In this research, specific metal resistance genes were used to estimate metal bioavailability in sediment microbial communities. Gene levels were measured by quantitative PCR and correlated to metals in sediments using five different protocols to estimate dissolved, particle-adsorbed and occluded metals. The best correlations were obtained with czcA (a Cd/Zn/Co efflux pump) and Cd/Zn adsorbed or occluded in particles. Only adsorbed Co was correlated to czcA levels. We concluded that the measurement of czcA gene levels by quantitative PCR is a promising tool which may complement the classical approaches used to estimate Cd/Zn/Co bioavailability in sediment compartments.

Links between bacterial communities in marine sediments and trace metal geochemistry as measured by in situ DET/DGT approaches

Our current view about the relationship between metals and bacteria in marine sediments might be biased because most studies only use ex situ approaches to quantify metals. The aim of the present research was to compare ex situ and in situ methods of metal measurement (DET and DGT--diffusive equilibration or diffusive gradients in thin-films) and relate the results with two commonly used microbiological variables (bacterial biomass and bacterial diversity as revealed by DGGE). No previous studies have used such in situ approaches in microbial ecology. For biomass and most of the investigated trace metals (Ag, Cd, Sn, Cr, Ni, Cu, Pb, and Al) no significant correlations were found. The exceptions were Fe, Mn, Co, and As which behave like micronutrients. For bacterial diversity, no relevant relationships were found. We conclude that in situ methods are more adapted tools for microbial ecologists but that ex situ approaches are still necessary.

Development and application of a HPIC-ICP-MS method for the redox arsenic speciation in river sediment pore waters

A new sensitive chromatographic method has been developed for As speciation determination in anoxic pore waters. Starting from aliquots of 25 μL, the different As species As(III), As(V), MMAAV and DMAAV were separated in less than 4 min by HPIC-ICP-MS using the IonPac® AG7-AS7 anion-exchange column set and dilute HNO3 as mobile phase. The detection limits were below or equal to 0.25 μg L−1 for each As species, which makes the method efficient to determine As speciation in poorly-contaminated sediments. In addition, no precipitation of iron and manganese (hydr)-oxides was observed since the anoxic samples were systematically carefully manipulated under nitrogen atmosphere. Chlorides were eliminated by the chromatographic separation, thus making possible speciation analysis in estuarine or seawater samples. The use of internal standard was not necessary due to good signal stability (<10%) at m/z 75 over 4 h of analysis. An environmental application has also been successfully performed in the Marque River (Northern France). Inorganic As species were detected in pore waters at low concentrations [below 1 and 10 μg L−1, for As(V) and As(III) respectively]. Others As species, identified as thioarsenic species, were also detected.

Monthly variation of trace metals in North Sea sediments: from experimental data to modeling calculations

Seasonal variation in trace metal contamination in surface sediments was studied through high resolution profiles assessed monthly by DGT probes in muddy sediments of the North Sea. General parameters such as pH, temperature, dissolved oxygen and sulfides were also recorded to estimate their role in the speciation of trace metals. Experimental data were included in a thermodynamic equilibrium model to calculate major (geo)chemical processes at the water-sediment interface and to predict the fate of the trace metals in case of (physico-)chemical changes. Results showed lowest Fe, Co, Ni and Cd concentrations in summer, which are most probably due to the very high sulfide concentrations according to our theoretical calculations. Cu and Pb behavior were found to be less influenced by sulfides, since they are also strongly associated to organic matter. The whole set of results clearly indicated that metal speciation in these sediments is controlled by sulfides and OM contents.

Benthic exchange of sedimentary metals (Cd, Cu, Fe, Mn, Ni and Zn) in the Deûle River (Northern France)

Environmental context Exchange processes at the water–sediment interface can release metals to riverine waters, having negative effects on organisms in the water column. We investigate the geochemical processes and metal exchange between the surface sediment and the overlying water under metal contamination conditions. Results suggest that the sediment can be a significant source of metal pollution in aquatic systems, particularly during anoxic events. Abstract Experiments were performed on the Deule River (Northern France), which is strongly polluted by smelting plants, in the aim to investigate the influence of diagenetic processes and benthic macro-faunal activity on trace metal (Cd, Cu, Ni and Zn) and major metal (Fe, Mn) exchanges occurring at the water–sediment interface. Diffusive metal fluxes were determined from pore water metal concentration gradients measured in sediment cores. Benthic metal fluxes were evaluated using incubation chambers under dark conditions, and by further examining key variables (O2, CO2, redox potential and pH) affecting metal release and sequestration processes. As a whole, it was demonstrated that benthic fluxes were strongly dependent upon medium oxygenation and generation of colloidal iron oxides and hydroxides at the overlying water–sediment interface, raising the possibility of trace-metal adsorption and (co)precipitation.

Determination of total arsenic using a novel Zn-ferrite binding gel for DGT techniques: Application to the redox speciation of arsenic in river sediments.

A new laboratory-made Zn-ferrite (ZnFe2O4) binding gel is fully tested using Diffusive Gradient in Thin films (DGT) probes to measure total As [including inorganic As(III) and As(V), as well as MonoMethyl Arsenic Acid (MMAA(V)) and DiMethyl Arsenic Acid (DMAA(V))] in river waters and sediment pore waters. The synthesis of the binding gel is easy, cheap and its insertion into the acrylamide gel is not problematic. An important series of triplicate tests have been carried out to validate the use of the Zn-ferrite binding gel in routine for several environmental matrixes studies, in order to test: (i) the effect of pH on the accumulation efficiency of inorganic As species; (ii) the reproducibility of the results; (iii) the accumulation efficiency of As species; (iv) the effects of the ionic strength and possible competitive anions; and (v) the uptake and the elution efficiency of As species after accumulation in the binding gel. All experimental conditions have been reproduced using two other existing binding gels for comparison: ferrihydrite and Metsorb® HMRP 50. We clearly demonstrate that the Zn-ferrite binding gel is at least as good as the two other binding gels, especially for pH values higher than 8. In addition, by taking into consideration the diffusion rates of As(III) and As(V) in the gel, combining the 3-mercaptopropyl [accumulating only As(III)] with the Zn-ferrite binding gels allows for performing speciation studies. An environmental study along the Marque River finally illustrates the ability of the new binding gel to be used for field studies.

Reagentless and calibrationless silicate measurement in oceanic waters.

Determination of silicate concentration in seawater without addition of liquid reagents was the key prerequisite for developing an autonomous in situ electrochemical silicate sensor (Lacombe et al., 2007) [11]. The present challenge is to address the issue of calibrationless determination. To achieve such an objective, we chose chronoamperometry performed successively on planar microelectrode (ME) and ultramicroelectrode (UME) among the various possibilities. This analytical method allows estimating simultaneously the diffusion coefficient and the concentration of the studied species. Results obtained with ferrocyanide are in excellent agreement with values of the imposed concentration and diffusion coefficient found in the literature. For the silicate reagentless method, successive chronoamperometric measurements have been performed using a pair of gold disk electrodes for both UME and ME. Our calibrationless method was tested with different concentrations of silicate in artificial seawater from 55 to 140×10(-6) mol L(-1). The average value obtained for the diffusion coefficient of the silicomolybdic complex is 2.2±0.4×10(-6) cm(2) s(-1), consistent with diffusion coefficient values of molecules in liquid media. Good results were observed when comparing known concentration of silicate with experimentally derived ones. Further work is underway to explore silicate determination within the lower range of oceanic silicate concentration, down to 0.1×10(-6) mol L(-1).