Nicolas Marmier

Toxicity of TiO2 nanoparticles to cladocerans, algae, rotifers and plants – Effects of size and crystalline structure

With the rapid development of nanotechnology, there is an increasing risk of human and environmental exposure to nanotechnology-based materials. However, the data on the potential environmental effects of nanoparticles are scarce. The aim of this study is to assess the effect of particle size and crystal structure (anatase and rutile) of titanium dioxide on their toxicity. Thus, acute and chronic toxicity tests included a modified acute test (72 h) using daphnies and algae, rotifers and plants as model organisms. Gradient of toxicity varied with the tested biological organisms. Our results revealed that TiO(2) nanoparticles in anatase crystal structure are toxic in the entire set of tests conducted. However, at highconcentration, through their antimicrobial properties, they significantly promoted growth of roots. Because of its lipophilicity, the rutile crystalline structure of TiO(2) NPs form larger aggregates in aqueous medium; then they have less effect on biological organisms, and thus a lower toxicity than the anatase crystalline form of TiO(2). We also demonstrated that exposure duration, aggregation and concentrations are contributing factors in nanoparticles-mediated toxicity.

Sorption of Cr(VI) onto natural iron and aluminum (oxy)hydroxides: effects of pH, ionic strength and initial concentration.

The aim of this work is to study the performances of removal of hexavalent chromium from aqueous solution by three different oxy-hydroxides: hematite, goethite and alpha-alumina. Batch experiments were conducted to measure the effects on adsorption of Cr(VI) of different parameters such as pH of the medium, ionic strength, and initial concentration. Results showed that the adsorption of Cr(VI) depends strongly on the pH, but is independent of ionic strength for hematite and goethite. For alpha-alumina, adsorption is strongly dependent on pH values and ionic strength. Equilibrium studies showed that Cr(VI) had a high affinity in an acidic medium, but decreased as solution pH increased. Equilibrium isotherms were measured experimentally. Results were analyzed by the Langmuir and Freundlich equations using linearized correlation coefficient at room temperature. The characteristic parameters for each isotherm have been determined. Langmuir equation was found to fit the equilibrium data for Cr(VI) adsorption.

Sorption of selenium(IV) onto magnetite in the presence of silicic acid

Sorption of selenium(IV) and silicic acid onto magnetite (Fe(3)O(4)) was investigated in binary systems, with concentrations of silicic acid under the solubility limit of amorphous silica. Using the double diffuse layer model (DDLM), surface complexation constants of selenium(IV) and H(4)SiO(4) onto magnetite were extracted using Fiteql 4.0. Then, prediction curves of the sorption of selenium(IV) in the presence of silicic acid onto magnetite were obtained, using the calculated surface complexation constants. Finally, laboratory experiments were performed and showed a competition between selenium(IV) and silicic acid for the surface sites of magnetite. Experimental results matched the model predictions, confirming its ability to model qualitatively and quantitatively the ternary system.

Structural identification of europium(III) adsorption complexes on montmorillonite

A study of trivalent europium retention onto Na-montmorillonite is presented, combining both macroscopic and microscopic points of view. In order to investigate the metal sorption mechanisms at a molecular level and therefore experimentally identify both clay reactive sites and sorption equilibria, laser-induced fluorescence spectroscopy (LIF) and X-ray photoelectron spectroscopy (XPS) on europium ion loaded montmorillonite have been performed. Moreover, since this clay is an alumino-silicated mineral, we have interpreted our experimental results in terms of interactions between a metal ion and a cation exchange site, and distinct “aluminol” and “silanol” edge sites. Therefore, identical structural investigations have been carried out on both Eu/alumina and Eu/silica systems. These comparisons have allowed us to determine the nature of the europium surface complexes and thus led to an experimental definition of the sorption equilibria involved in the retention process. The obtained lifetime values and the Eu 3d XPS spectra of europium sorbed on the three solids have shown that this metal is sorbed, on the montmorillonite clay, on exchange sites as an outer-sphere complex and onto both “aluminol” and “silanol” edge sites as inner-sphere surface complexes, depending on the pH value and the ionic strength of the suspension.

Influence of uranium on bacterial communities: a comparison of natural uranium-rich soils with controls.

This study investigated the influence of uranium on the indigenous bacterial community structure in natural soils with high uranium content. Radioactive soil samples exhibiting 0.26% - 25.5% U in mass were analyzed and compared with nearby control soils containing trace uranium. EXAFS and XRD analyses of soils revealed the presence of U(VI) and uranium-phosphate mineral phases, identified as sabugalite and meta-autunite. A comparative analysis of bacterial community fingerprints using denaturing gradient gel electrophoresis (DGGE) revealed the presence of a complex population in both control and uranium-rich samples. However, bacterial communities inhabiting uraniferous soils exhibited specific fingerprints that were remarkably stable over time, in contrast to populations from nearby control samples. Representatives of Acidobacteria, Proteobacteria, and seven others phyla were detected in DGGE bands specific to uraniferous samples. In particular, sequences related to iron-reducing bacteria such as Geobacter and Geothrix were identified concomitantly with iron-oxidizing species such as Gallionella and Sideroxydans. All together, our results demonstrate that uranium exerts a permanent high pressure on soil bacterial communities and suggest the existence of a uranium redox cycle mediated by bacteria in the soil.

The toxicity of composted sediments from Mediterranean ports evaluated by several bioassays.

This work investigates the ecotoxicological evaluation of contaminated dredged sediments from French Mediterranean navy harbour (A), commercial port (B) and two composite specimens (C) and (D) coming from the mixture of A and B with other port sediments. The toxicity of elutriates from these sediments is estimated using embryo-toxicity test, Microtox® solid phase test, LuminoTox, phytotoxicity tests and genotoxicity test. Bioassay responses are not clearly correlated with chemical contamination in the whole sediment and vary as a function of tested organisms. The highest contaminated samples (A and C) are almost always more toxic than the less contaminated samples (B and D). Among composite sediments, the mixture effect with other sediments is not efficient to decrease toxicity in sample C, suggesting that other parameters influence toxicity level such as particle size or organic matter content. These parameters should be taken into consideration in order to improve the efficiency of the mixture process and produce composite sediments with low toxicity.

Arsenic in marine sediments from French Mediterranean ports: Geochemical partitioning, bioavailability and ecotoxicology

This work investigates arsenic mobility, bioavailability and toxicity in marine port sediments using chemical sequential extraction and laboratory toxicity tests. Sediment samples were collected from two different Mediterranean ports, one highly polluted with arsenic and other inorganic and organic pollutants (Estaque port (EST)), and the other one, less polluted, with a low arsenic content (Saint Mandrier port (SM)). Arsenic distribution in the solid phase was studied using a sequential extraction procedure specifically developed for appraising arsenic mobility in sediments. Toxicity assessment was performed on sediment elutriates, solid phases and aqueous arsenic species as single substance using the embryo-toxicity test on oyster larvae (Crassostrea gigas) and the Microtox test with Vibrio fischeri. Toxicity results showed that all sediment samples presented acute and sub-chronic toxic effects on oyster larvae and bacteria, respectively. The Microtox solid phase test allow to discriminate As-contaminated samples from the less contaminated ones, suggesting that toxicity of whole sediment samples is related to arsenic content. Toxicity of dissolved arsenic species as single substance showed that Vibrio fischeri and oyster larvae are most sensitive to As(V) than As(III). The distribution coefficient (Kd) of arsenic in sediment samples was estimated using results obtained in chemical sequential extractions. The Kd value is greater in SM (450 Lkg(-1)) than in EST (55 Lkg(-1)), indicating that arsenic availability is higher for the most toxic sediment sample (Estaque port). This study demonstrates that arsenic speciation play an important role on arsenic mobility and its bioavailability in marine port sediments.

Ecotoxicological evaluation of Mediterranean dredged sediment ports based on elutriates with oyster embryotoxicity tests after composting process

The ecotoxicological effect of dredged sediments was estimated by embryo-larval toxicity of the oyster Crassosstrea gigas in sediment elutriates (filtered and unfiltered). The study covers the main ports from the French Mediterranean coast. Composted sediments from a navy harbour (A), a commercial port (B) and two composite specimens (C and D) obtained after mixing various sediments were taken into consideration. Effective concentrations affecting 50% of larvae (EC50) were obtained from different elutriate concentrations (from 0 to 100%). Toxicity results obtained from filtered elutriates decreased according to the following gradient: sample A (5.68%), B (20.50%), C (37.60%) and D (47.17%). Chemical concentrations in whole sediments were in agreement with those in elutriates. Among the measured contaminants in elutriates, Cu and Zn resulted as the main contributors to toxicity. Dissolved organic carbon played an important role by exerting a protective effect against the toxicity of dissolved Cu. Toxicity results were interpreted on the basis of toxicity scores to give indication about sediment quality which provided more severe judgement than risk score based on chemical concentrations in sediments.

Competition between selenium (IV) and silicic acid on the hematite surface.

Competition between selenium (IV) and silicic acid for the hematite (alpha-Fe(2)O(3)) surface has been studied during this work. Single batch experiments have been performed to study separately the sorption of selenium (IV) and silicic acid as a function of the pH. With the help of the 2-pK surface complexation model, experimental data have been fitted using the FITEQL 4.0 program. Two monodentate inner-sphere surface complexes have been used to fit selenite ions retention, triple bond FeSeO(3)(-) and triple bond FeHSeO(3). In order to fit sorption of silicic acid, the two following surface complexes, namely triple bond FeH(3)SiO(4), and triple bond FeH(2)SiO(4)(-), have been used. Using the surface complexation constants coming from these two binary systems, prediction curves of the effect of silicic acid on the retention of selenium (IV) onto hematite have been obtained. Finally, performed experiments showed a competition between selenium (IV) and silicic acid for the surface sites of hematite. Experimental data matched DDLM predictions, confirming the ability of the surface complexation model to predict quantitatively and qualitatively the ternary system selenium (IV)/H(4)SiO(4)/hematite.

Toxicity assessment of silica nanoparticles, functionalised silica nanoparticles, and HASE-grafted silica nanoparticles

Numerous nanomaterials have recently been developed, and numerous practical applications have been found in water treatment, medicine, cosmetics, and engineering. Associative polymers, such as hydrophobically modified alkali-soluble emulsion (HASE) systems are involved in several applications and have been extensively studied due to their ability to form three-dimensional networked gels. However, the data on the potential environmental effects of this polymers are scarce. The aim of this study is to assess the effect of functionalisation of silica nanoparticles, and coupling of functionalised silica nanoparticles to the associative polymer HASE on their toxicity. Thus, acute and chronic toxicity tests included a modified acute test (72 h) using daphnies, algae, and plants as model organisms. Gradient of toxicity varied with the tested organisms. Our results revealed that the functionalised nanoparticules and NP grafted polymer cause a global decrease in toxicity compared to commercial nanoparticule and HASE polymer.