The role of efflorescent salts associated with sulfide-rich mine wastes in the short-term cycling of arsenic: Insights from XRD, XAS, and µ-XRF studies.

The evaporation of As-rich leachates generated by the weathering of sulfide-rich mine wastes accumulated in abandoned tailing dams of the La Concordia mine, triggers the widespread precipitation of saline crusts and efflorescences. Because these salts are highly soluble, they may release high concentrations of arsenic after rainfall events. Thus, the goal of this work is to assess the solid speciation of As in these efflorescences, which may help to understand the short-term cycling of As in the site. The results reveal that As is present only as As(V), while its capacity to be retained in the salts highly depends on their mineralogical composition. Hydrous sulfates, such as gypsum and epsomite show a very low capacity to scavenge As, while copiapite retains the highest concentrations of this element. The spectroscopic evidences suggest that in this mineral, As(V) is included within the lattice, substituting sulfate in the tetrahedral sites. Because copiapite is highly soluble, it may be considered as one of the most important transient reservoirs of As in the site that can release high concentrations of this hazardous pollutant during the occasional rainfall events produced during the wet season.

Synchrotron XAS study on the As transformations during the weathering of sulfide-rich mine wastes.

This paper describes the weathering processes that occurred across two tailing dumps in the Concordia mine (Puna of Argentina) with the purpose of evaluating the formation of secondary As-bearing minerals due to arsenopyrite alteration. After 30 years of exposure, the gradual oxidation of the wastes produced a number of secondary mineral phases containing As in different chemical arrangements. Synchrotron-based X-ray absorption spectroscopy was used to determine both, As and Fe solid speciation and to identify the formed As-bearing minerals. The results reveal that in the first stages of oxidation, As released from arsenopyrite is adsorbed/substituted in the jarosite structure partially inhibiting its dissolution. When pH values in the system slightly increase As-jarosite transforms into schwertmannite, where the released As could be re-adsorbed or co-precipitated. When the available adsorption sites become oversaturated with As, the precipitation of amorphous ferric arsenates may occur. The latter, likely constitute the more labile As fractions in the sediments and are therefore the main phases contributing As to the nearby environments. These amorphous and labile phases are more abundant in the uppermost layers of the profiles, where oxidation has taken place for a more prolonged time-lapse. The described transformations are enhanced by the acidic pH, the absence of minerals attenuating the acidity and the high sulfate and As concentrations in pore water.

Mineralogical control on arsenic release during sediment-water interaction in abandoned mine wastes from the Argentina Puna.

The sulfide-rich residues of La Concordia mine, Argentina Puna, are accumulated in tailing dams that remained exposed to the weathering agents for almost 30years. In such period of time, a complex sequence of redox and dissolution/precipitation reactions occurred, leading to the gradual oxidation of the wastes and the formation of weathering profiles. The sources of arsenic in the wastes were analyzed by XRD and SEM/EDS analysis while a standardized sequential extraction procedure was followed to define solid As associations. In addition, the release of As during sediment-water interaction was analyzed in a period of 10months. The results indicate that primary As-bearing minerals are arsenian pyrite and polymetallic sulfides. As-jarosite and scarce arsenates are the only secondary As-bearing minerals identified by XRD and SEM/EDS. However, the rapid release (i.e., <1h) of arsenic from suspensions of the studied sediments in water, seems to be associated to the dissolution of highly soluble (hydrous)sulfates, as it was determined in samples of the efflorescences that cover the entire site. Contributions from the more abundant As-jarosite are also expected in longer periods of sediment-water interaction, due to its low rate of dissolution in acid and oxic conditions. Finally, near 30% of As remains adsorbed onto Fe (hydr)oxides thus representing a hazardous reservoir with the potential of mobilizing As into porewaters and streamwaters if the acidic and oxidizing conditions that predominate in the region are altered.