Catherine Noiriel

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.

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.

Experimental evidence for rock layering development by pressure solution

Natural deformation of rocks is commonly associated with development of mineralogical layering, leading to irreversible transformations of their microstructure. The mechanisms of such chemical differentiation processes during diagenesis, tectonics, metamorphism, or fault differentiation remain poorly understood, as they are difficult to reproduce experimentally due to the very slow kinetics involved. This paper shows that development of differentiated layering, similar to that observed in natural deformation, is stress driven and can be obtained from indenter experiments. Samples of (1) gypsum plaster mixed with clay, and (2) natural diatomite loosely interbedded with volcanic ash, saturated with aqueous solutions in equilibrium, were subjected to loading for several months at 40 °C and 150 °C, respectively. X-ray microtomography and scanning electron microscopy observations show that layering develops by a self-organized pressure solution process. Stress-driven dissolution of the soluble minerals (either gypsum or silica) is initiated in the areas initially richer in insoluble species (clay or volcanic ash), as diffusive mass transfer along the interface between soluble and insoluble minerals is much faster than along the healed boundaries of the soluble minerals. The passive concentration of the insoluble minerals amplifies the dissolution along layers oriented perpendicularly to the maximum compressive stress. Conversely, in areas with an initial low content of insoluble minerals and clustered soluble minerals, dissolution is slower. Consequently, these areas are less deformed; they host the re-deposition of the soluble species and act as rigid objects that concentrate both stress and dissolution near their boundaries, thus amplifying the differentiation and the development of layered microstructures.

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.

Three-dimensional morphological and mineralogical characterization of testate amebae.

Testate amebae are unicellular shelled protozoa commonly used as indicators in ecological and paleoecological studies. We explored the potential application of three-dimensional (3D) X-ray micro-tomography used in addition to 2D techniques (environmental scanning electron microscopy, electron probe micro-analysis, and cathodoluminescence) for detailed characterization of agglutinated shells of protozoa. We analyzed four specimens of the aquatic testate ameba Difflugia oblonga (Arcellinida), to test whether size distribution and mineral composition of shell grains diverged from sediment size distribution and mineralogical composition. From the 3D images, the geometry of the specimens (size and mass) and of the individual grains forming the specimen (grain size distribution and volume) were calculated. Based on combined chemical, mineralogical, and morphological analyses we show that D. oblonga is able to selectively pick up the small size fraction of the sediment with a preference for low-density silicates close to quartz density (~2.65). The maximum size of the grains matches the size of the pseudostome (shell aperture), suggesting the existence of a physical limit to grain size used for building the shell. This study illustrates the potential of this combined approach to characterize agglutinated shells of protozoa. This data can be useful for detailed morphological studies with applications in taxonomy and ecology.