Investigation of Capitella spp. symbionts in the context of varying anthropic pressures: First occurrence of a transient advantageous epibiosis with the giant bacteria Thiomargarita sp. to survive seasonal increases of sulfides in sediments.

Capitella spp. is considered as an important ecological indicator of eutrophication due to its high densities in organic-rich, reduced, and sometimes polluted coastal ecosystems. We investigated whether such ability to cope with adverse ecological contexts might be a response to the microorganisms these worms are associated with. In populations from the French Atlantic coast (Roscoff, Brittany), we observed an epibiotic association covering the tegument of 20-30% specimens from an anthropized site while individuals from a reference, non-anthropized site were devoid of any visible epibionts. Using RNAseq, molecular and microscopic analyses, we described and compared the microbial communities associated with the epibiotic versus the non-epibiotic specimens at both locations. Interestingly, data showed that the epibiosis is characterized by sulfur-oxidizing bacteria among which the giant bacterium Thiomargarita sp., to date only described in deep sea habitats. Survey of Capitella combined with the geochemical analysis of their sediment revealed that epibiotic specimens are always found in muds with the highest concentration of sulfides, mostly during the summer. Concomitantly, tolerance tests demonstrated that the acquisition of epibionts increased survival against toxic level of sulfides. Overall, the present data highlight for the first time a peculiar plastic adaptation to seasonal variations of the habitat based on a transcient epibiosis allowing a coastal species to survive temporary harsher conditions.

Leaching of two northern France slag heaps: Influence on the surrounding aquatic environment.

After the exploitation of coal mines in the 19th and 20th centuries in northern France, many mining slag heaps (SH) were left without any particular management or monitoring. Currently, the influence of these SHs on the quality of surrounding wetlands is hardly known. The purpose of this work is to determine the water quality in the neighbourhood of two SHs located near the city of Douai and its influence on the distribution of aquatic invertebrates in local wetlands. Our approach involves (1) the spatial and temporal characterization of the water composition (anions, major elements, sulphide, DOC and alkalinity) and of the biological diversity (aquatic invertebrates) and (2), based on this chemical and biological screening, the establishment of relationships between water quality and biodiversity distribution through multivariate data analysis. The results clearly indicate that substantial leaching from the slag heaps occurs, given the very high concentrations of dissolved sulphates (in the range of 2 g L-1). While the pH remains weakly basic, indicating that the leaching water has been neutralized by the highly carbonated regional substratum, high levels of biodegradable organic matter and sulphate contents have been noticed. They sporadically cause significant drops in dissolved oxygen and the occurrence of dissolved sulphides that massively reduce biodiversity, qualitatively and quantitatively. In Summer, oxygen saturation is generally lower due to the higher rate of organic matter degradation, and the risk of anoxic episodes therefore increases. Finally, as wetlands are vulnerable environments, these preliminary results suggest that monitoring and management of these sites must be attempted quickly to avoid the degradation of those valuable habitats.

Passive sampler measurements of inorganic arsenic species in environmental waters: A comparison between 3-mercapto-silica, ferrihydrite, Metsorb®, zinc ferrite, and zirconium dioxide binding gels.

The performances of five Diffusive Gradients in Thin Films (DGT) binding gels, namely 3-mercapto-functionalized silica (3MP), ferrihydrite (Fh), Metsorb®, zinc ferrite (ZnFe2O4), and Zirconium oxide (ZrO2), were evaluated for in situ determination of As speciation in water and sediments. A combination of batch experiments at various pH (without addition of buffers) and in the presence of reduced species (Mn2+, Fe2+ and HS-),time-series experiments in oxic waters, and in situ deployment in anoxic river sediments has permitted to evaluate the potential interferences among the binding gels. Firstly, the efficiency of each DGT binding gel dedicated to total As (i.e., Fh, Metsorb®, ZnFe2O4 and ZrO2) or As(III) (i.e., 3MP) determination confirms that the determination of As species is possible in oxic freshwater and seawater over 96 h for a wide range of pH (5-9). Secondly, concerning the deployment in river sediment, high HCO3- concentrations have a little negative effect only on the DGT performances of the iron(III)-binding gels (i.e, Fh and ZnFe2O4). Thirdly, the presence of sulfides does not show any effect on the DGT uptake of As, but strongly affects the elution factor parameter. Discrepancies in elution between the different binding gels potentially result in precipitation of orpiment, especially in 1 mol L-1 HNO3. A correction of the classical elution factor derived from batch experiments was applied to provide more representative results. Finally, this study shows the difficulties to determine As speciation in anoxic sediments, and suggests that corrections of the elution factor may be required as a function of the species present in the deployment matrices.

Understanding the impact of the changes in weather conditions on surface water quality.

The aim of this paper is to better understand the functioning of the River Selle (northern France) during dry weather and storm events, to assess the impact of a town on the surface water quality and to suggest qualitative assumptions on the vulnerability of water quality to weather conditions. Two high-frequency monitoring stations covering the Cateau-Cambrésis town were deployed during 4 months in 2016. River flow, water temperature, pH, dissolved oxygen, turbidity, conductivity, total organic carbon, nitrates and phosphates were monitored every 10 min. The water supply of the River Selle is mainly dominated by groundwater as shown by the behaviour of the river flow, the water temperature and the nitrate concentrations in both surface water and groundwater. The reference station located at the upstream of the river (Saint Souplet) exhibits low anthropogenic pressure during dry weather but is significantly impacted during storm events. At the downstream of the Cateau-Cambrésis town, the water quality is severely impacted by phosphates during dry weather mainly due to wastewater inputs into the river. An additional load of pollution is highlighted during storm events. According to our results, the water quality of the River Selle would degrade if actions to reduce dry-weather and storm events pollution sources are not undertaken rapidly. Moreover, nutrients, particularly phosphates, are clearly in excess in this system. Efforts to combat soil leaching and the revision of sewage systems and urban wastewater treatment in the catchment are two key points to tackle. Finally, this study shows the importance of understanding the current behaviour of a given river towards dry weather and storm events before suggesting local scenarios of the impact of climate change on surface water quality.

Immune failure reveals vulnerability of populations exposed to pollution in the bioindicator species Hediste diversicolor.

Human activities on the shoreline generate a growing pollution, creating deleterious habitats in coastal zones. Some species nevertheless succeed in such harsh milieus, raising the question of their tolerance to environmental stress. The annelid Hediste diversicolor lives buried in the sediments, directly exposed to contaminants trapped in the mud. After verifying the similarity of their genetic contexts, we compared reproductive output and individual immune resistance measures of populations living in polluted vs. 'clean' sediments, and related these assessments with measures of phthalates and metal pollution, and associated toxicity indices. Chemical analyses predicted no toxicity to the local infauna, and phenological studies evidenced no direct cost of living in noxious habitats. However, populations exposed to pollutants showed a significantly reduced survival upon infection with a local pathogen. Surprisingly, physiological studies evidenced a basal overinflammatory state in the most exposed populations. This over-activated baseline immune phenotype likely generates self-damage leading to enhanced immune cell death rate and immune failure. Monitoring the immune status of individual worms living in anthropic areas could thus be used as a reliable source of information regarding the actual health of wild populations.

On the bioavailability of trace metals in surface sediments: a combined geochemical and biological approach.

The bioavailability of metals was estimated in three river sediments (Sensée, Scarpe, and Deûle Rivers) impacted by different levels of Cu, Cd, Pb, and Zn (Northern France). For that, a combination of geochemistry and biological responses (bacteria and chironomids) was used. The results obtained illustrate the complexity of the notion of "bioavailability." Indeed, geochemical indexes suggested a low toxicity, even in surface sediments with high concentrations of total metals and a predicted severe effect levels for the organisms. This was also suggested by the abundance of total bacteria as determined by DAPI counts, with high bacterial cell numbers even in contaminated areas. However, a fraction of metals may be bioavailable as it was shown for chironomid larvae which were able to accumulate an important quantity of metals in surface sediments within just a few days.We concluded that (1) the best approach to estimate bioavailability in the selected sediments is a combination of geochemical and biological approaches and that (2) the sediments in the Deûle and Scarpe Rivers are highly contaminated and may impact bacterial populations but also benthic invertebrates.

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.

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.

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.

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.

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).

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.

Potential risks of metal toxicity in contaminated sediments of Deûle river in northern France.

The aim of this paper was to evaluate the potential sediment cumulative damage and toxicity due to metal contamination in a polluted zone of Deûle river (in northern France) from nearby two smelters. Metal-enrichment factors and geoaccumulation indices measured with sediment depth revealed that--compared to background levels either in local reference soils or in world rivers sediments/suspended particulate matter--Cd contributed to the highest pollution levels, followed by Zn, Pb and to a much lesser extent Cu and Ni. A comparison of the vertical distribution of AVS (acid volatile sulfides), SEM (simultaneously extracted metals), TMC (total metal concentrations), TOC (total organic carbon) and interstitial water-metal concentrations in the sediment allowed us to highlight the extent of toxicity caused by Cd, Pb, Zn, Ni and Cu and to raise the possibility of their association with certain geochemical phases. To assess the actual environmental impacts of these metals in Deûle river, numerical sediment quality guidelines were further used in the present work. Sedimentary Pb, Zn, and Cd contents largely exceeded PEC (probable effect concentration) values reported as consensus-based sediment quality guidelines for freshwater ecosystems. As for risks of toxicity from pore waters, metal concentrations reached their maxima at the surficial layers of the sediment (1-3 cm) and IWCTU (Interstitial Water Criteria Toxicity Unit) observed for Pb and to a lesser extent Cd, violated the corresponding water quality data recommended by USEPA.

Electrochemical properties of silver-copper alloy microelectrodes for use in voltammetric field apparatus.

Microelectrodes of silver-copper alloys have been evaluated for use in voltammetric analyses. Increased overpotential towards the hydrogen overvoltage reaction (HER) was found as a function of increased copper content in the silver. A study of oxidizing products by cyclic voltammetry (CV) in NaOH solution showed ten anodic and eight cathodic peaks which are described in the present paper. The behaviour of these alloy electrodes is somewhere between pure silver and pure copper electrodes. Differential pulse anodic stripping voltammetry (DPASV) was used to measure zinc, cadmium and lead in ultrapure water only (18 MOmegacm), and good linearity was found for all metals (r (2)=0.998) in the range of 0.5 to 5 ppb with a 600- to 1,200-s plating time. It was additionally found that cadmium and lead were better separated on the alloy electrodes compared to pure silver electrodes. Measurements of nickel were carried out on alloy electrodes by use of adsorptive differential pulse cathodic stripping voltammetry (Ad-DPCSV), and good linearity (r (2)=1.000) was found in the range from 0.5 to 5 ppb with an adsorption time of 120 s. The alloy electrodes were also found to be sensitive to nitrate, and good linearity (r (2)=0.997) was found in the range from 1 mg L(-1) to 100 mg L(-1) using differential pulse voltammetry (DPV) scanning from -450 mV to -1,500 mV. Addition of nitrate in ultrapure water afforded two different peaks related to the successive reductions of nitrate and nitrite. In ammonium buffer solution (pH 8.6) only one peak resulting from reduction of nitrate was observed. Furthermore, the use of alloy electrodes containing 17% Cu was tested in real samples, by installing it in a voltammetric system for monitoring of zinc and lead in a polluted river, the river Deûle, near the town of Douai in northern France. Results were found to be in agreement with parallel measurements carried out by ICP-MS.