Fabrizio Bardelli

Reactivities of Fe(II) on calcite: selenium reduction.

The reductive immobilization of Se(IV) by micrometer-sized (100-200 microm) calcite containing sorbed or coprecipitated Fe(II) was investigated at pH 7 under anoxic conditions (O(2) < 1 ppmv) using X-ray absorption near-edge structure (XANES) spectroscopy. The Se(IV) sorption on calcite increased in the presence of sorbed Fe(II) compared to that of Fe-free pure calcite. XANES spectra of Se K-edge shows that nearly half of the total sorbed Se(IV) is reduced to Se(0) by Fe(II) sorbed on calcite within 24 h. The extent of reduction decreases with increasing equilibration time of calcite with Fe(II) solution before Se(IV) addition. The combined results of field emission scanning electron microscopy and X-ray diffraction have shown that needle-shaped red monoclinic elemental Se with diameters of 30-50 nm and lengths of up to 100 nm is precipitated on the calcite surface. Fe(II) coprecipitated calcite does not contribute to Se(IV) reduction within 72 h. Therefore, the reduction capacity of Fe(II) linked to calcite critically depends on its location (either on the surface or in the bulk solid), and less extensively on the pre-equilibration time of calcite with Fe(II) solution. Such understanding is important to predict the transport, transformation, and attenuation of Se in subsurface and in nuclear waste repositories.

The impact of oscillating redox conditions: Arsenic immobilisation in contaminated calcareous floodplain soils

Arsenic contamination of floodplain soils is extensive and additional fresh arsenic inputs to the pedosphere from human activities are ongoing. We investigate the cumulative effects of repetitive soil redox cycles, which occur naturally during flooding and draining, on a calcareous fluvisol, the native microbial community and arsenic mobility following a simulated contamination event. We show through bioreactor experiments, spectroscopic techniques and modelling that repetitive redox cycling can decrease arsenic mobility during reducing conditions by up to 45%. Phylogenetic and functional analyses of the microbial community indicate that iron cycling is a key driver of observed changes to solution chemistry. We discuss probable mechanisms responsible for the arsenic immobilisation observed in-situ. The proposed mechanisms include, decreased heterotrophic iron reduction due to the depletion of labile particulate organic matter (POM), increases to the proportion of co-precipitated vs. aqueous or sorbed arsenic with α-FeOOH/Fe(OH)3 and potential precipitation of amorphous ferric arsenate.

Nanocomposite pyrite-greigite reactivity toward Se(IV)/Se(VI).

A nanopyrite/greigite composite was synthesized by reacting FeCl(3) and NaHS in a ratio of 1:2 (Wei et al. 1996). Following this procedure, the obtained solid phases consisted of 30-50 nm sized particles containing 28% of greigite (Fe(2+)Fe(3+)(2)S(4)) and 72% pyrite (FeS(2)). Batch reactor experiments were performed with selenite or selenate by equilibrating suspensions containing the nanosized pyrite-greigite solid phase at different pH-values and with or without the addition of extra Fe(2+). XANES-EXAFS spectroscopic techniques revealed, for the first time, the formation of ferroselite (FeSe(2)) as the predominant reaction product, along with elemental Se. In the present experimental conditions, at pH 6 and in equilibrium with Se(0), the solution is oversaturated with respect to ferrosilite. Furthermore, thermodynamic computations show that reaction kinetics likely played a significant role in our experimental system.

Arsenic uptake by gypsum and calcite: Modelling and probing by neutron and X-ray scattering

Uptaking of contaminants by solid phases is relevant to many issues in environmental science as this process can remove them from solutions and retard their transport into the hydrosphere. Here we report on two structural studies performed on As-doped gypsum (CaSO4 2H2O) and calcite (CaCO3), using neutron (D20-ILL) and xray (ID11-ESRF) diffraction data and EXAFS (BM8-ESRF). The aim of this study is to determine whether As gets into the bulk of gypsum and calcite structures or is simply adsorbed on the surface. Different mechanisms of substitution are used as hypotheses. The combined Rietveld analysis of neutron and x-ray diffraction data shows an expansion of the unit cell volume proportional to the As concentration within the samples. DFT-based simulations confirm the increase of the unit cell volume proportional to the amount of carbonate or sulphate groups substituted. Interpolation of the experimental Rietveld data allows us to distinguish As substituted within the structure from that adsorbed on the surface of both minerals. Results obtained by EXAFS analysis from calcite samples show good agreement with the hypothesis of replacement of As into the C crystallographic site.

Arsenate incorporation in gypsum probed by neutron, X-ray scattering and density functional theory modeling.

The ability of gypsum, a common sulfate mineral, to host arsenic atoms in its crystalline structure, is demonstrated through experimental structural studies of the solid solutions formed upon synthetic coprecipitation of gypsum (CaSO4 x 2 H2O) and arsenic. Neutron and X-ray diffraction methods show an enlargement of the gypsum unit cell proportional to the concentration of arsenic in the solids and to the pH solution value. The substitution of sulfate ions (SO4(2-)) by arsenate ions is shown to be more likely under alkaline conditions, where the HAsO4(2-) species predominates. A theoretical Density Functional Theory model of the arsenic-doped gypsum structure reproduces the experimental volume expansion. Extended X-ray Absorption Fine Structure (EXAFS) measurements of the local structure around the arsenic atom in the coprecipitated solids confirm solid state substitution and allow some refinement of the local structure, corroborating the theoretical structure found in the simulations. The charge redistribution within the structure upon substitutions of either the protonated or the unprotonated arsenate species studied by means of Mulliken Population Analyses demonstrates an increase in the covalency in the interaction between Ca(2+) and AsO4(3-), whereas the interaction between Ca(2+) and HAsO4(2-) remains predominantly ionic.

Combined non-destructive XRF and SR-XAS study of archaeological artefacts

AbstractWe report on a non-destructive study of Sicilian ceramic fragments of cultural heritage interest, classified as “proto-majolica” pottery and dating back to the twelfth to thirteen centuries AD. The analytical approach used is based on the employment of two totally non-invasive spectroscopic techniques: X-ray fluorescence (XRF), using a portable energy-dispersive XRF analyser, and X-ray absorption spectroscopy, using synchrotron radiation as a probe (SR-XAS). XRF measurements allowed us to collect elemental and spatially resolved information on major and minor constituents of the decorated coating of archaeological pottery fragments, so providing preliminary results on the main components characterizing the surface. In particular, we assigned to Fe and Mn the role of key elements of the colouring agent. With the aim of obtaining more detailed information, we performed SR-XAS measurements at the Fe and Mn K-edges at the Italian BM08 beamline at the European Synchrotron Radiation Facility (Grenoble, France). The experimental data were analysed by applying principal component analysis and least-squares fitting to the near-edge part of the spectra (X-ray absorption near-edge structure) to determine the samples’ speciation. From the overall results, umber, a class of brownish pigments characterized by a mixture of hydrated iron and manganese oxides, has been ascribed as a pigmenting agent. FigureFe K-edge XANES spectra of selected proto-majolica samples and reference compounds (FeO, Fe3O4, Fe2O3, Fe+SiO2). D pigmented, L not pigmented.

Arsenic-bearing calcite in natural travertines: evidence from sequential extraction, μXAS, and μXRF.

Recent studies demonstrated that synthetic calcite may host considerable amounts of arsenic (As). In this paper, the concentration of As in natural calcite was determined using two novel, specifically designed, sequential extraction procedures. In addition, the oxidation state of As and its distribution between calcite and coexisting Fe-oxyhydroxides was unravelled by μXRF elemental mapping and As K-edge μXAS spectroscopy. Our results conclusively demonstrate that arsenic can be found in natural calcite up to 2 orders of magnitude over the normal crustal As abundances. Because of the large diffusion of calcite in the environment, this phase may exert an important control on As geochemistry, mobility, and bioavailability.

New insights on the biomineralisation process developing in human lungs around inhaled asbestos fibres

Once penetrated into the lungs of exposed people, asbestos induces an in vivo biomineralisation process that leads to the formation of a ferruginous coating embedding the fibres. The ensemble of the fibre and the coating is referred to as asbestos body and is believed to be responsible for the high toxicological outcome of asbestos. Lung tissue of two individuals subjected to prolonged occupational exposure to crocidolite asbestos was investigated using synchrotron radiation micro-probe tools. The distribution of K and of elements heavier than Fe (Zn, Cu, As, and Ba) in the asbestos bodies was observed for the first time. Elemental quantification, also reported for the first time, confirmed that the coating is highly enriched in Fe (~20% w/w), and x-ray absorption spectroscopy indicated that Fe is in the 3+ oxidation state and that it is present in the form of ferritin or hemosiderin. Comparison of the results obtained studying the asbestos bodies upon removing the biological tissue by chemical digestion and those embedded in histological sections, allowed unambiguously distinguishing the composition of the asbestos bodies, and understanding to what extent the digestion procedure altered their chemical composition. A speculative model is proposed to explain the observed distribution of Fe.

Interaction of aqueous Se(IV)/Se(VI) with FeSe/FeSe2: Implication to Se redox process

Since reductive precipitation is considered as the most effective way to immobilize (79)Se, interaction of aqueous Se(IV)/Se(VI) with Fe(II)-bearing minerals has received extensive attention. In contrast to the thermodynamic calculations, as well as the prevalence of iron selenide phases observed in soil, sediments and ore deposits, most laboratory experiments have found that Se(0) was the reaction product. In this study, the interaction of Se(IV)/Se(VI) with FeSe/FeSe2 were investigated. The results demonstrate that FeSe and FeSe2 can be oxidized to Se(0) by Se(IV) with relatively fast kinetics, while reaction between Se(VI) and FeSe/FeSe2 only occurs under limited conditions (i.e. in the presence of high ferrous content and higher pH) with much slower kinetics, and there is no evident reaction in most case. Therefore, reduction of Se(IV) by Fe(II)-bearing minerals, in particular by natural occurring minerals, is envisioned to produce Se(0) at the early stage of experiments, rather than FeSe or FeSe2. Due to the formation of bulk Se(0) and its low solubility, the Fe-Se-O-H2O system will maintain redox disequilibrium in laboratory time-scale. This study also reveals that iron selenides, like iron sulfides, have strong reactivity toward Fe(3+). The findings in this study give insight into possible controls on Se redox process.

Kinetics of FeSe 2 oxidation by ferric iron and its reactivity compared with FeS 2

The mobility and bioavailability of selenium is a major health and environmental issue and a main concern for geological disposal of high-level radioactive waste. Chemically and/or microbially mediated oxidation of insoluble Se-bearing particulate, such as iron selenides, to dissolved and mobile phases controls the transport and distribution of Se in the environment. The oxidation of ferroselite (FeSe2) by ferric iron was investigated in anoxic conditions. The redox reaction can be represented by: FeSe2 + 2Fe3+ = 2Se0 + 3Fe2+. Kinetic studies indicated that the reaction can be described by second-order rate law, with rate constants of 0.49±0.01, 0.85±0.02, 1.84±0.04, and 3.29±0.13 L mol−1 s−1 at pH 1.62, 1.87, 2.23, and 2.49, respectively. The positive correlation between reaction rate and pH implies that diffusion of Fe3+ oxidant to the mineral surface is the rate-determining step. The strong reactivity of FeSe2 towards Fe3+ suggests that ferric iron may play a significant role in FeSe2 oxidation process (e.g., by Se4+, O2, etc.) and Se0 should be the first reaction product. Also, it was shown that the reduction rate of Fe3+ or Se4+ by pyrite (FeS2) can be significantly increased in the presence of FeSe2, suggesting a stronger reactivity of FeSe2 compared with pyrite. The results obtained extend our knowledge about the subtle interaction between Se, pyrite and iron selenides in the environment, and give insight into the transfer of selenium from iron selenides to bio-available selenium (i.e., selenite and selenate) in the Se-rich environment.