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Abstract: A comparative study of ferrihydrite and ferric green rust coated sand prepared by three synthesis routes has been outlined in the present contribution. The two minerals displayed inverse properties in terms of quantity of deposited iron for all three methods investigated. For ferric green rust coating, a newly proposed synthesis route named as dry contact method was efficient for the maximum quantity of iron with almost full coverage area. Considering the similar parameters, the modified wet synthesis method designated as reactive method provides the optimum results for ferrihydrite coated sand. These coatings have been characterised by different surface analysis techniques. In particular, due to the excellent sensitivity of miniaturised Mössbauer Spectrometer (MIMOS) it was possible to detect the lowest iron content (0.1 Fe w/w%). A distinct approach based on tribology between crystallised ferric green rust and sand has been proposed to explain the relatively high quality of coating using dry contact method. [Copyright &y& Elsevier]

Abstract: Pyrite oxidation processes by aqueous Cr(VI) were investigated at 25 °C under an argon atmosphere. Synthetic pyrite suspensions (6 g L−1) were reacted for 20 h with a range of Cr(VI) solutions from 0 to 700 μM and at pH 2–12. The main objective of this work was to investigate the reaction mechanisms by emphasizing the role of sulfur species. Aqueous chemical processes were well illustrated in acidic media where significant amounts of sulfate and iron species were determined. Sulfate anions are the final stable sulfur species involved in the reaction pathway. Experiments showing complete Cr(VI) removal from solution displayed ratios [S(VI)]/[Fe]tot <2, probably due to a deficit in aqueous sulfur species. Experiments showing incomplete Cr(VI) removal displayed ratios [Cr(VI)]removed/[S(VI)] close to 1.5. This ratio was found to be consistent with the formation of thiosulfate (S2O2− 3). Thiosulfate ions disproportionated into elemental sulfur S(0) and tetrathionate ions (S4O2− 6) that were finally oxidized to sulfate anions under acidic conditions. The distribution of the oxidation state of sulfur atoms at the pyrite surface determined by XPS was additional evidence for the multistep sulfur oxidation process. The presence of elemental sulfur in the S(2p) spectra correlated well with the disproportion of thiosulfate under acidic conditions. [Copyright &y& Elsevier]

Abstract: Optical microscopy, confocal Raman micro-spectrometry, X-ray photoelectron micro-spectroscopy (XPS) and synchrotron based micro-X-ray fluorescence (XRF), micro-X-ray absorption near edge spectroscopy (XANES) and micro-extended X-ray absorption fine structure (EXAFS) were used to investigate the reduction of aqueous Cr(VI) by pyrite. Special emphasis was placed on the characterisation of the solid phase formed during the reaction process. Cr(III) and Fe(III) species were identified by XPS analyses in addition to non-oxidised pyrite. Optical microscopy images and the corresponding Raman spectra reveal a strong heterogeneity of the samples with three different types of zones. (i) Reflective areas with E g and A g Raman wavenumbers relative to non-oxidised pyrite are the most frequently observed. (ii) Orange areas that display a drift of the E g and A g pyrite vibration modes of −3 and −6cm−1, respectively. Such areas are only observed in the presence of Cr(VI) but are not specifically due to this oxidant. (iii) Bluish areas with vibration modes relative to a corundum-like structure that can be assigned to a solid solution Fe2−x Cr x O3, x varying between 0.2 and 1.5. The heterogeneity in the spatial distribution of chromium observed by optical microscopy and associated Raman microspectroscopy is confirmed by μ-XRF. In agreement with both solution and XPS analyses, these spectroscopies clearly confirm that chromium is in the trivalent state. XANES spectra in the iron K-edge pre-edge region obtained in rich chromium areas reveal the presence of ferric ion thus revealing a systematic association between Cr(III) and Fe(III). In agreement with Raman analyses, Cr K-edge EXAFS can be interpreted as corresponding to Cr atoms involved in a substituted-type hematite structure Fe2−x Cr x O3. [Copyright &y& Elsevier]

Pyrite, an iron sulfide, occurs in many soils and sediments, making it an important natural reductant of toxic metal pollutants. This study investigated the processes leading to aqueous Cr(VI) reduction by pyrite in a closed thermostated (25 ± 0.1 °C) system and under an argon atmosphere. Synthetic pyrite suspensions were reacted with a range of Cr(VI) solutions from 0 to 7 × 10-4 M and at pH 2-8. Metal species concentrations were continuously monitored during a period lasting approximately 20 h. Preliminary experiments carried out in acidic media without Cr(VI) have shown that some pyrite dissolution occurred. Then, metal species concentration changes with time during pyrite oxidation by Cr(VI) solutions exhibited two distinct trends depending on the complete or incomplete Cr(VI) removal. As long as chromate existed in solution, the Cr-(III) to Fe(III) ratio was found to be an effective parameter to investigate the pyrite reaction stoichiometry with Cr- (VI). Experimental values close to 2 suggest that sulfur compounds with oxidation states between 0 and 2 should be formed during pyrite oxidation by Cr(VI). If Cr(VI) was completely reduced from solution, then the pyrite oxidation by Fe(III) ions took place to generate ferrous ions. [ABSTRACT FROM AUTHOR]

The ability of mackinawite, an iron(II) monosulphide, to reduce Cr(VI) was studied at pH values of 5 and 7, Cr(VI) solution concentrations ranging from 10-4 to 6 × 10-3M and fixed ionic strength. Mackinawite suspensions (0.6gL-1 and 1.2gL-1) and Cr(VI) solutions were reacted for 4.5h in a nitrogen atmosphere. The oxidation of mackinawite was determined by analysing both solutions and solid phases after Cr(VI) reaction. The solid phases were characterised by using complementary electrokinetic measurements and X-ray Photoelectron Spectroscopy and by Transmission Electron Microscopy. Solutions were analysed using colorimetric methods for Fe(II) and Cr(VI) and capillary electrophoresis for sulphur speciation. Mackinawite was found to be a very effective reductant of Cr(VI) under the conditions of the experiments. The removal capacity was determined to be around 130mg Cr(VI)/g FeS at pH 7 and 240mg Cr(VI)/g FeS at pH 5. The presence of an iron(III) and chromium(III) (oxyhydr)oxide layer covering the mackinawite crystals was evidenced with a constant Cr to Fe ratio of 1.4 ± 0.2. The extent of the metal (oxyhydr)oxide layer increases with the initial Cr(VI) concentration, thus probably limiting the Cr(VI) reduction at high initial Cr(VI) concentrations. [Copyright &y& Elsevier]

Tetragonal FeS 1− x mackinawite, has been synthesized by reacting metallic iron with a sodium sulfide solution and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), transmission Mössbauer spectroscopy (TMS) and X-ray photoelectron spectroscopy (XPS). Based on XRD and TEM analyses, synthetic mackinawite exhibits crystallization and is identical to the natural mineral. Unit cell parameters derived from XRD data are a = b = 0.3670 nm and c = 0.5049 nm. The bulk Fe:S ratio derived from the quantitative dispersive energy analysis is practically 1. XPS analyses, however, showed that mackinawite surface is composed of both Fe(II) and Fe(III) species bound to monosulfide. Accordingly, monosulfide is the dominant S species observed at the surface with lesser amount of polysulfides and elemental sulfur. TMS analysis revealed the presence of both Fe(II) and Fe(III) in the mackinawite structure, thus supporting the XPS analysis. We propose that the iron monosulfide phase synthesized by reacting metallic iron and dissolved sulfide is composed of Fe(II) and S(-II) atoms with the presence of a weathered thin layer covering the bulk material that consists of both Fe(II) and Fe(III) bound to S(-II) atoms and in a less extent of polysulfide and elemental sulfur. [ABSTRACT FROM AUTHOR]

Abstract: Biotite is a constituent Fe-bearing mineral of Delta subsoils in India and Bangladesh and has been hypothesized as a primary source of arsenic (As). The adsorption behavior of As onto structural Fe(II, III)-bearing biotite fractions (<50μm) was investigated in the pH range of 4–8 under a CO2-free, anoxic condition (O2 <1ppmv) using X-ray Photoelectron Spectroscopy (XPS) and X-ray Absorption Spectroscopy (XAS). The batch experiments indicate that As adsorption is strongly pH dependent and that As(V) adsorbs more efficiently than As(III). X-ray Absorption Near-Edge Structure (XANES) spectra show no oxidation or reduction of As by biotite after reaction with As(III) or As(V) solutions for 3days. Extended X-ray Absorption Fine Structure (EXAFS) spectroscopic results suggest that As(III) forms bidentate mononuclear edge-sharing (2E) and bidentate binuclear corner-sharing (2C) surface complexes at pH 7.7 as indicated by average As–Fe bond distances at 3.00±0.02Å and 3.37±0.03Å respectively. The surface speciation retrieved by XPS does not provide any evidence of reduction of As(V) on biotite after 30days further confirming the thermodynamic prediction and the XANES results. This study has therefore significant environmental implications for As contaminated areas, where biotite retards the release of As into reducing groundwater. The changes in soil redox conditions and weathering of biotite may likely contribute to the occurrence of high As in groundwater. [ABSTRACT FROM AUTHOR]

Abstract: Adhesion of the bacteria Campylobacter jejuni and Mycobacterium avium onto polyethylene terephtalate (PET), a polymer widely used within the bottled water industry was measured in two different groundwater solutions. From this, it was found that whilst the percentage cell adhesion for a given strain did not change between groundwater types, substantial variation was obtained between the two bacterial species tested: M. avium (10–30% adhered cells) and C. jejuni (1–2%) and no major variations were measured as a function of groundwater composition for a given strain. To explain this, the interfacial electro-hydrodynamic properties of the bacteria were investigated by microelectrophoresis, with the resultant data analysed on the basis of electrokinetic theory for soft biocolloidal particles. The results obtained showed that M. avium carries a significant volume charge density and that its peripheral layer exhibits limited hydrodynamic flow permeation compared to that of C. jejuni. It was also demonstrated that steric hindrance to flow penetration and the degree of hydrophobicity within/of the outer bacterial interface are larger for M. avium cells. In line with this, the larger amount of M. avium cells deposited onto PET substrates as compared to that of C. jejuni can be explained by hydrophobic attraction and chemical binding between hydrophobic PET and outer soft surface layer of the bacteria. Hydrophobicity of PET was addressed by combining contact angle analyses and force spectroscopy using CH3-terminated AFM tip. [Copyright &y& Elsevier]

Abstract: Exploitation of polymetallic deposits from calcareous mining sites exposes galena and others sulfides to weathering factors. Galena weathering leads to the formation of lead phases (e.g., PbSO4, PbCO3) with a higher bioaccessibility than galena, thus increasing the mobility and toxicity of lead. Despite the environmental impacts of these lead phases, the mechanisms of galena oxidation and the transformation of lead secondary phases, under neutral-alkaline carbonated conditions, have rarely been studied. In this work, an experimental approach, combining electrochemical and spectroscopic techniques, was developed to examine the interfacial processes involved in the galena weathering under simulated calcareous conditions. The results showed an initial oxidation stage with the formation of an anglesite-like phase leading to the partial mineral passivation. Under neutral-alkaline carbonated conditions, the stability of this phase was limited as it transformed into a cerussite-like one. Based on the surface characterization and the formation of secondary species, the weathering mechanisms of galena in calcareous soil and its environmental implications were suggested. [Copyright &y& Elsevier]

The influence of surface-bound Fe(II) on uranium oxidation state and speciation was studied as a function of time (6 min-72 h) and pH (6.1-8.5) in a U(VI)-Fe(II)-montmorillonite (Ca-montmorillonite, MONT) system under CO2-free, anoxic (O2 <1 ppmv) conditions. The results show a rapid removal of U(VI) from the aqueous solution within 1 h under all pH conditions. U LIII-edge X-ray absorption near-edge structure spectroscopy shows that 96% of the total sorbed U(VI) is reduced at pH 8.5. However, the extent of reduction significantly decreases at lower pH values as specifically sorbed Fe(II) concentration decreases. The reduction kinetics followed by X-ray photoelectron spectroscopy during 24 h at pH 7.5 demonstrates the presence of partially reduced surface species containing U(VI) and U(IV). Thermodynamically predicted mixed valence solids like U3O8/β-U3O7/U4O9 do not precipitate as verified by transmission electron microscopy and extended X-ray absorption fine-structure spectroscopy. This is also supported by the bicarbonate extraction results. The measured redox potentials of Fe(II)/Fe(III)-MONT suspensions are controlled by the Fe(II)/hydrous ferric oxide [HFO(s)] couple at pH 6.2 and by the Fe(II)/lepidocrocite [γ-FeOOH(s)] couple at pH 7.5. The key finding of our study is the formation of a sorbed molecular form of U(IV) in abiotic reduction of U(VI) by sorbed Fe(II) at the surface of montmorillonite. [ABSTRACT FROM AUTHOR]

Abstract: Microbiological reduction of a biogenic sulfated green rust , was examined using a sulfate reducing bacterium (Desulfovibrio alaskensis). Experiments investigated whether could serve as a sulfate source for D. alaskensis anaerobic respiration by analyzing mineral transformation. Batch experiments were conducted using lactate as the electron donor and biogenic as the electron acceptor, at circumneutral pH in unbuffered medium. transformation was monitored with time by X-ray diffraction (XRD), Transmission Mössbauer Spectroscopy (TMS), Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS), Transmission Electron Microscopy (TEM) and X-ray Photoelectron Spectroscopy (XPS). The reduction of sulfate anions and the formation of iron sulfur mineral were clearly identified by XPS analyses. TMS showed the formation of additional mineral as green rust (GR) and vivianite. XRD analyses discriminated the type of the newly formed GR as GR1. The formed GR1 was as indicated by DRIFTS analysis. Thus, the results presented in this study indicate that D. alaskensis cells were able to use as an electron acceptor. , vivianite and an iron sulfur compound were formed as a result of reduction by D. alaskensis. Hence, in environments where geochemical conditions promote biogenic formation, this mineral could stimulate the anaerobic respiration of sulfate reducing bacteria. [Copyright &y& Elsevier]