Synthesis, characterization and thermochemistry of synthetic Pb–As, Pb–Cu and Pb–Zn jarosites

The enthalpy of formation from the elements of well characterized Pb-As, Pb-Cu, and Pb-Zn synthetic jarosites, corresponding to chemical formulas (H3O)0.68±0.03Pb0.32±0.002Fe2.86±0.14(SO4)1.69±0.08(AsO4)0.31±0.02(OH)5.59±0.28(H2O)0.41±0.02, (H3O)0.67±0.03Pb0.33±0.02Fe2.71±0.14Cu0.25±0.01(SO4)2±0.00(OH)5.96±0.30(H2O)0.04±0.002 and (H3O)0.57±0.03Pb0.43±0.02Fe2.70±0.14Zn0.21±0.01(SO4)2±0.00(OH)5.95±0.30(H2O)0.05±0.002, was measured by high temperature oxide melt solution calorimetry and gave ΔH°f = -3691.2 ± 8.6 kJ/mol, ΔH°f = -3653.6 ± 8.2 kJ/mol, and ΔH°f = -3669.4 ± 8.4 kJ/mol, respectively. Using estimated entropies, the standard Gibbs free energy of formation from elements at 298 K ΔG°f of the three compounds were calculated to be -3164.8 ± 9.1 kJ/mol, -3131.4 ± 8.7 kJ/mol, and -3153.6 ± 8.9 kJ/mol, respectively. Based on these free energies, their logKsp values are -13.94 ± 1.89, -4.38 ± 1.81 and -3.75 ± 1.80, respectively. For this compounds, a log10{Pb2+} - pH diagram is presented. The diagram shows that the formation of Pb-As jarosite may decrease aqueous arsenic and lead concentrations to meet drinking water standards. The new thermodynamic data confirm that transformation of Pb-As jarosite to plumbojarosite is thermodynamically possible

Toxic metal(loid) speciation during weathering of iron sulfide mine tailings under semi-arid climate

Toxic metalliferous mine-tailings pose a significant health risk to ecosystems and neighboring communities from wind and water dispersion of particulates containing high concentrations of toxic metal(loid)s (e.g., Pb, As, Zn). Tailings are particularly vulnerable to erosion before vegetative cover can be reestablished, i.e., decades or longer in semi-arid environments without intervention. Metal(loid) speciation, linked directly to bioaccessibility and lability, is controlled by mineral weathering and is a key consideration when assessing human and environmental health risks associated with mine sites. At the semi-arid Iron King Mine and Humboldt Smelter Superfund site in central Arizona, the mineral assemblage of the top 2 m of tailings has been previously characterized. A distinct redox gradient was observed in the top 0.5 m of the tailings and the mineral assemblage indicates progressive transformation of ferrous iron sulfides to ferrihydrite and gypsum, which, in turn weather to form schwertmannite and then jarosite accompanied by a progressive decrease in pH (7.3 to 2.3). Within the geochemical context of this reaction front, we examined enriched toxic metal(loid)s As, Pb, and Zn with surficial concentrations 41.1, 10.7, 39.3 mM kg-1 (3080, 2200, and 2570 mg kg-1), respectively. The highest bulk concentrations of As and Zn occur at the redox boundary representing a 1.7 and 4.2 fold enrichment relative to surficial concentrations, respectively, indicating the translocation of toxic elements from the gossan zone to either the underlying redox boundary or the surface crust. Metal speciation was also examined as a function of depth using X-ray absorption spectroscopy (XAS). The deepest sample (180 cm) contains sulfides (e.g., pyrite, arsenopyrite, galena, and sphalerite). Samples from the redox transition zone (25-54 cm) contain a mixture of sulfides, carbonates (siderite, ankerite, cerrusite, and smithsonite) and metal(loid)s sorbed to neoformed secondary Fe phases, principally ferrihydrite. In surface samples (0-35 cm), metal(loid)s are found as sorbed species or incorporated into secondary Fe hydroxysulfate phases, such as schwertmannite and jarosites. Metal-bearing efflorescent salts (e.g., ZnSO4·nH2O) were detected in the surficial sample. Taken together, these data suggest the bioaccessibility and lability of metal(loid)s are altered by mineral weathering, which results in both the downward migration of metal(loid)s to the redox boundary, as well as the precipitation of metal salts at the surface.24 month embargo; published online: 7 February 2015This item from the UA Faculty Publications collection is made available by the University of Arizona with support from the University of Arizona Libraries. If you have questions, please contact us at [email protected]

Oxidative weathering decreases bioaccessibility of toxic metal(loid)s in PM emissions from sulfide mine tailings

Environmental contamination from legacy mine-waste deposits is a persistent problem due to the long history of hard-rock mining. Sulfide ore deposits can contain elevated levels of toxic metal(loid)s that, when mobilized by weathering upon O2 and H2O infusion, can result in groundwater contamination. Dry-climate and lack of vegetative cover result in near-surface pedogenic processes that produce fine-particulate secondary minerals that can be translocated as geo-dusts leading to ingestion or inhalation exposure in nearby communities. In this study, in vitro bioassays were combined with synchrotron-based x-ray spectroscopy and diffraction to determine the potential risk for toxic element release from dust (PM10) samples into biofluid simulants. PM10 were isolated from across the oxidative reaction front in the top meter of tailings subjected to 50 years of weathering under semi-arid climate, and introduced to synthetic gastric- and alveolar-fluids. Aqueous concentrations were measured as a function of reaction time to determine release kinetics. X-ray diffraction and absorption spectroscopy analyses were performed to assess associated changes in mineralogy and elemental speciation. In vitro bioaccessibility of arsenic and lead was highest in less-weathered tailings samples (80-110 cm) and lowest in samples from the sub-oxic transition zone (40-52 cm). Conversely, zinc release to biofluids was greatest in the highly-weathered near-surface tailings. Results indicate that bioaccessibility of As and Pb was controlled by (i) the solubility of Fe2+-bearing solids, (ii) the prevalence of soluble SO42-, and (iii) the presence of poorly-crystalline Fe(III) oxide sorbents, whereas Zn bioaccessibility was controlled by the pH-dependent solubility of the stable solid phase.NIEHS Superfund Research Program [2 P42 ES04940]Open access journalThis item from the UA Faculty Publications collection is made available by the University of Arizona with support from the University of Arizona Libraries. If you have questions, please contact us at [email protected]