RESUMEN

Mine tailings exposed to water and oxygen generate acid mine drainage (AMD) when the neutralizing minerals are insufficient to buffer the acid produced by sulfide oxidation. Mineral reactivity, such as sulfide oxidation and carbonate dissolution, leads to several changes within mine tailings in terms of their physical, mineralogical, and geochemical properties, which may lead to the release of metal(oid)s (e.g., As, Cu, Zn, Fe, S) into the environment. Fresh and oxidized tailings were sampled at two vertical profiles in a tailings storage facility (TSF). The TSF contains tailings from gold ore processing at a mine that has been closed for more than 25 years. Oxidized tailings have formed by in-situ oxidation of fresh tailings over more than 20 years. The collected samples were analyzed for: i) chemical composition by inductively coupled plasma atomic emission spectroscopy (ICP-AES), X-ray fluorescence (XRF), and total S/C; and ii) mineralogical composition by X-ray diffraction (XRD), Mineral Liberation Analyzer (MLA), Mossbauer spectroscopy, and Fe L-edge X-ray absorption near-edge spectroscopy (XANES). Mineralogically, the fresh tailings included more than 22 wt% carbonates and more than 10 wt% sulfides. In contrast, the oxidized tailings were composed mainly of secondary minerals such as iron oxy-hydroxides and gypsum. Geochemically, the fresh tailings exhibited a circumneutral behavior during weathering cell experiments and contaminants such as As were negligibly released (<0.3 mg/L). The latter is explained by formation of secondary iron oxy-hydroxides, which are known for the capacity to uptake several contaminants from the leachate. Long term oxidation of fresh tailings will lead to highly oxidized tailings similar to those collected in situ. The oxidized tailings exhibited an acidic behavior despite sulfide depletion due to latent acidity. The geochemical behavior was strongly controlled by the reactivity of secondary minerals (e.g., dissolution of gypsum and iron oxy-hydroxides). Quantitatively, the oxidized tailings released 163 mg/kg Fe, around 12,000 mg/kg S, and around 6 mg/kg Zn.

RESUMEN

We report the effect of the synthesis route of starch-functionalized magnetite nanoparticles (NPs) on their adsorption properties of As(V) and As(III) from aqueous solutions. NP synthesis was achieved by two different routes implying the alkaline precipitation of either a mixed Fe2+/Fe3+ salt solution (MC samples) or a Fe2+ salt solution in oxidative conditions (MOP samples). Syntheses were carried out with starch to Fe mass ratio (R) ranging from 0 to 10. The crystallites of starch-free MC NPs (14 nm) are smaller than the corresponding MOP (67 nm), which leads to higher As(V) sorption capacity of 0.3 mmol gFe -1 to compare with respect to 0.1 mmol gFe -1 for MOP at pH = 6. MC and MOP starch-functionalized NPs exhibit higher sorption capacities than a pristine one and the difference in sorption capacities between MOP and MC samples decreases with increasing R values. Functionalization tends to reduce the size of the magnetite crystallites and to prevent their agglomeration. Size reduction is more pronounced for MOP samples (67 nm (R0) to 12 nm (R10)) than for MC samples (14 nm (R0) to 9 nm (R10)). Therefore, due to close crystallite size, both MC and MOP samples, when prepared at R = 10, display similar As(V) (respectively, As(III)) sorption capacities close to 1.3 mmol gFe -1 (respectively, 1.0 mmol gFe -1). Additionally, according to the effect of pH on arsenic trapping, the electrostatic interactions appear as a major factor controlling As(V) adsorption while surface complexation may control As(III) adsorption.

RESUMEN

Layered double hydroxides (LDH) and their magnetic composites have been intensively investigated as recyclable high-capacity phosphate sorbents but with little attention to their stability as function of pH and phosphate concentration. The stability of a Fe3O4@SiO2-Mg3Fe LDH P sorbent as function of pH (5-11) and orthophosphate (Pi) concentration (1-300 mg P/L) was investigated. The composite has high adsorption capacity (approx. 80 mg P/g) at pH 5 but with fast dissolution of the LDH component resulting in formation of ferrihydrite as evidenced by Mössbauer spectroscopy. At pH 7 more than 60% of the LDH dissolves within 60 min, while at alkaline pH, the LDH is more stable but with less than 40% adsorption capacity as compared to pH 5. The high Pi sorption at acid to neutral pH is attributed to Pi bonding to the residual ferrihydrite. Under alkaline conditions Pi is sorbed to LDH at low Pi concentration while magnesium phosphates form at higher Pi concentration evidenced by solid-state 31P MAS NMR, powder X-ray diffraction and chemical analyses. Sorption as function of pH and Pi concentration has been fitted by a Rational 2D function allowing for estimation of Pi sorption and precipitation. In conclusion, the instability of the LDH component limits its application in wastewater treatment from acid to alkaline pH. Future use of magnetic LDH composites requires substantial stabilisation of the LDH component.

RESUMEN

The present study investigates for the first time the reduction of nitrite by biogenic hydroxycarbonate green rusts, bio-GR(CO3), produced from the bioreduction of ferric oxyhydroxycarbonate (Fohc), a poorly crystalline solid phase, and of lepidocrocite, a well-crystallized Fe(III)-oxyhydroxide mineral. Results show a fast Fe(II) production from Fohc, which leads to the precipitation of bio-GR(CO3) particles that were roughly 2-fold smaller (2.3 ± 0.4 µm) than those obtained from the bioreduction of lepidocrocite (5.0 ± 0.4 µm). The study reveals that both bio-GR(CO3) are capable of reducing nitrite ions into gaseous nitrogen species such as NO, N2O, or N2 without ammonium production at neutral initial pH and that nitrite reduction proceeded to a larger extent with smaller particles than with larger ones. On the basis of the identification of intermediates and end-reaction products using X-ray diffraction and X-ray absorption fine structure (XAFS) spectroscopy at the Fe K-edge, our study shows the formation of hydroxy-nitrite green rust, GR(NO2), a new type of green rust 1, and suggests that the reduction of nitrite by biogenic GR(CO3) involves both external and internal reaction sites and that such a mechanism could explain the higher reactivity of green rust with respect to nitrite, compared to other mineral substrates possessing only external reactive sites.

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RESUMEN

In this study, the reactivity of hydroxysulphate green rust (GR(SO(4)(2-))) toward reductive transformation, oxidative degradation and mineralization of organic compounds was evaluated using Methyl Red (MR) as model pollutant. The GR(SO(4)(2-)) was synthesized by co-precipitation method and characterized by X-ray diffraction (XRD), Mössbauer spectroscopy and Fourier Transform Infrared (FTIR) analyses. Reductive decolourization of MR solution occurred in the presence of GR(SO(4)(2-)), while no total organic carbon (TOC) decay was observed during the equilibration time. Significant TOC removal (87%) was noted when H(2)O(2) was added to the GR(SO(4)(2-))/MR mixture after the preliminary reduction step. UV-Vis analysis, dissolved iron and H(2)O(2) concentration measurement, and batch sorption test showed that the heterogeneous Fenton-like reaction is the main mechanism by which the pollutant was mineralized. Increasing of H(2)O(2)/Fe(II) ratio did not affect significantly the mineralization rate of MR. However, slight decolourization of MR and absence of TOC abatement were noted when both MR and H(2)O(2) were simultaneously mixed with the GR(SO(4)(2-)). XRD analysis, Mössbauer spectroscopy and FTIR spectroscopy revealed that the oxidation end-products of GR(SO(4)(2-)) were mainly a poorly crystallized goethite when GR was oxidized after equilibrating with MR in solution. However, a badly crystallized iron oxide was formed when GR was immediately oxidized. In all cases, the interlayer anion (SO(4)(2-)) was ejected from GR structure to aqueous solution. These results suggest that the GR(SO(4)(2-))/H(2)O(2) system could be used to promote the reduction/oxidation reaction of organic pollutants.

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RESUMEN

Bioreduction of the well-crystallized ferric oxyhydroxide gamma-FeOOH lepidocrocite was investigated in batch cultures using Shewanella putrefaciens bacterium (strain CIP 8040) at initial pH 7.5 in bicarbonate buffer. The cultures were performed with formate as electron donor without phosphate, in the presence or absence of anthraquinone-2,6-disulfonate (AQDS) as electron shuttle. During lepidocrocite reduction, the iron(II,III) hydroxycarbonate green rust GR(CO32-) was characterized by X-ray diffraction, transmission electron microscopy, and transmission Mössbauer spectroscopy. The AQDS accelerated the kinetics of GR formation. GR was the major end product when bacterial reduction was not stopped by lack of electron donor, and between 55 and 86% of the iron from gamma-FeOOH precipitated in GR(CO32-). However, when the bacterial reduction was stopped by freezing/thawing or the electron donor was exhausted, the large quantity of remaining lepidocrocite induced a transformation of GR into magnetite. This confirms that GR is metastable with respect to magnetite in the presence of gamma-FeOOH.

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