Jarosite versus Soluble Iron-Sulfate Formation and Their Role in Acid Mine Drainage Formation at the Pan de Azúcar Mine Tailings (Zn-Pb-Ag), NW Argentina

Secondary jarosite and water-soluble iron-sulfate minerals control the composition of acid mine waters formed by the oxidation of sulfide in tailings impoundments at the (Zn-Pb-Ag) Pan de Azúcar mine located in the Pozuelos Lagoon Basin (semi-arid climate) in Northwest (NW) Argentina. In the primary zone of the tailings (9.5 wt % pyrite-marcasite) precipitation of anglesite (PbSO4), wupatkite ((Co,Mg,Ni)Al2(SO4)4) and gypsum retain Pb, Co and Ca, while mainly Fe2+, Zn2+, Al3+, Mg2+, As3+/5+ and Cd2+ migrate downwards, forming a sulfate and metal-rich plume. In the oxidation zone, jarosite (MFe3(TO4)2(OH)6) is the main secondary Fe3+ phase; its most suitable composition is M = K+, Na+, and Pb2+and TO4 = SO42−; AsO42−. During the dry season, iron-sulfate salts precipitate by capillary transport on the tailings and at the foot of DC2 (tailings impoundment DC2) tailings dam where an acid, Fe2+ rich plume outcrops. The most abundant compounds in the acid mine drainage (AMD) are SO42−, Fe2+, Fe3+, Zn2+, Al3+, Mg2+, Cu2+, As3+/5+, Cd2+. These show peak concentrations at the beginning of the wet season, when the soluble salts and jarosite dissolve. The formation of soluble sulfate salts during the dry season and dilution during the wet season conform an annual cycle of rapid metals and acidity transference from the tailings to the downstream environment.Fil: Murray, Jesica María. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Salta. Instituto de Bio y Geociencias del NOA. Universidad Nacional de Salta. Facultad de Ciencias Naturales. Museo de Ciencias Naturales. Instituto de Bio y Geociencias del NOA; ArgentinaFil: Kirschbaum, Alicia Matilde. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Salta. Instituto de Bio y Geociencias del NOA. Universidad Nacional de Salta. Facultad de Ciencias Naturales. Museo de Ciencias Naturales. Instituto de Bio y Geociencias del NOA; ArgentinaFil: Dold, Bernhard. Sustainable Mining Research & Consult EIRL; ChileFil: Mendes Guimaraes, Edi. Universidade do Brasilia; BrasilFil: Pannunzio Miner, Elisa Victoria. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentin

Sources et dynamique du chrome dans les sols ultramafiques de Niquelandia, Brésil

La disponibilité et la mobilité du chrome ont été étudiées sur quatre sols développés sur le complexe ultramafique de Niquelândia (état du Goiàs, Brésil), à l aide d expérimentations en laboratoire et in situ. La teneur totale en chrome de ces sols est particulièrement élevée, et sa compartimentation évolue avec la position dans la toposéquence et la profondeur du sol. La majorité du chrome est associée aux oxydes de fer bien cristallisés qui constituent la matrice solide des sols. Il est également présent au sein des chromites, et de phases mineurs silicatées. La quantité de chrome extractibles est importante et majoritairement sous sa forme toxique (CrVI). Cette fraction atteint 1000 mg kg-1 soit plus de 10% du chrome total ; ces teneurs sont dix fois supérieures à celles observées en Nouvelle-Calédonie. Des cinétiques d échange isotopique du chromate ont confirmé la labilité de cette fraction. Elles ont également mis en évidence une vitesse d échange rapide entre les phases porteuses et la solution, ainsi qu une capacité élevée de ces sols à maintenir une importante concentration de chromate en solution. L ensemble des résultats indique que le Cr(VI) labile est désorbé depuis la fraction fine composée d oxydes de fer qui contrôle ainsi sa disponibilité et sa mobilité. Les résultats suggèrent que le chromate labile est faiblement adsorbé aux phases porteuses. La disponibilité du chrome est très hétérogène à des échelles décimétrique et décamétrique. L étude des eaux du sol et de surface à l échelle du bassin versant a mis en évidence une mobilité importante du Cr(VI) et des concentrations en chromate supérieures aux teneurs considérées comme toxiques, suggérant un impact sur les organismes vivants du complexe et également les écosystèmes environnants. D autre part, l analyse des solutions du sol a confirmé la faible teneur en nutriments, le rapport défavorable Ca:Mg et la disponibilité de certains métaux (Cr, Ni) typiques de ces milieux. Ces trois caractéristiques sont souvent considérés comme responsable de la faible fertilité de ce type de sol et du particularisme de ces écosystèmes. Enfin, les résultats suggèrent que la disponibilité en Cr(VI) de ces sols résulte de leur capacité d échange anionique et non d oxydation du Cr(III).Chromium availability and mobility were studied on four soils developed on the complex ultramafic of Niquelândia (Goias state, Brazil), using laboratories and in situ experiments. Total chromium content is particularly high, and its partitioning evolves according to landscape position and depth. Chromium is mainly associated to well crystallized iron oxides, forming the soil matrix. However, extractable chromium is important, and mainly under the toxic form (CrVI). It reached 1,000 mg kg-1 (more than 10 % of total chromium), those contents are ten times higher than those observed in New Caledonia. Results indicate that Cr (VI) in solution is released from the fine fraction composed by iron-oxides, which consequently control the Cr(VI) availability and mobility. Isotopic exchange kinetics of chromate has confirmed the exchange between the bearing phases and solution. They also highlighted a rapid exchange between the Cr-bearing phases and the solution, and the important Cr(VI) buffer capacity of these soils. They also suggest that the chromate is slightly absorbed on iron-oxides. The chromate concentrations in soil solutions are important, higher than the usual hazardous contents. The chromate labibily is very heterogeneous with the locality at a centimetric and metric scale. The soil solution and surface water study on the catchment area has highlighted an important Cr(VI) mobility at soil and complex scale, suggesting an impact on organisms of the complex and surrounding ecosystems. Moreover, the soil solutions analysis show the low nutrients content, the imbalance Ca:Mg and the metals (Cr, Ni) availability, often considered responsible to the low fertility of those soils and the specificity of ultramafic ecosystems. Finally, results suggest that the Cr(VI) availability of those results from their anionic exchange capacity and not from their capacity to oxidize Cr (III).ORSAY-PARIS 11-BU Sciences (914712101) / SudocSudocFranceF

Cr(VI) genesis and dynamics in Ferralsols developed from ultramafic rocks: The case of Niquelandia, Brazil

Despite high chromium concentrations in soils developed on ultramafic rocks, Cr availability is generally low, as Cr-bearing minerals are considered stable in supergene conditions. However, KH2PO4 extractions have shown high hexavalent chromium availability in Ferralsols developed on the ultramafic massif of Niquelandia (Brazil). A study combining mineralogical, geochemical, mu SXRF and XANES approaches was performed to assess the solid speciation of Cr and to understand its genesis. Chromium is mostly present in the trivalent form and is included in chromites and Fe-oxides. Nevertheless, a large amount of Cr(VI) is associated with the clay-sized fraction in the mineral horizons. Mn-oxides, the only natural Cr(III) oxidants, are also present in these horizons. Microscale investigations revealed the close association of Cr(VI) with Mn-oxides and strongly suggest that Mn-oxides can oxidize Cr(III) into Cr(VI). The XANES analyses show the occurrence of Cr(VI), which is removed by KH2PO4 extraction, demonstrating that the Cr(VI) is completely sorbed onto the soil matrix, i.e., Fe-oxides. Finally, the high mobility of Cr(VI), associated with the finest Fe-oxide particles mobilized during runoff following rainy events, may have harmful environmental consequences. This approach of combining direct and indirect observations allows us to characterize the total extractable Cr(VI) pool of these soils and to give key information on its mobility and localization