(Micro)spectroscopic analyses of particle size dependence on arsenic distribution and speciation in mine wastes.

The chemical speciation and distribution of potentially toxic metal(loid)s in mine wastes is critical to assessing the risks posed by these wastes and predicting the potential bioavailability of the metal(loid)s present. Of additional potential importance is the role of particle size in the fate, transport, and toxicity of contaminated mining materials. Spectroscopic analyses of size-separated mine tailings and adjacent background samples from the Randsburg Historic Mining District, California were conducted to quantify the speciation and distribution of arsenic (As) as a function of particle size. Micro-X-ray fluorescence (μXRF) mapping of separate size fractions was used to identify multiple populations of particles with different As:Fe ratios, indicating a variety of distinct arsenic-bearing species. Bulk extended X-ray absorption fine structure (EXAFS) spectroscopy identified phases including arseniosiderite, Ca2Fe3(3+)(AsO4)3O3·3H2O, and As(V) sorbed to iron hydroxides (ferrihydrite, goethite), confirming a strong statistical correlation between arsenic and iron observed in both μXRF studies and bulk chemical analyses. Differences in As speciation between the mine tailings and background samples also suggest that weathering of crystalline As-bearing phases in tailings leads to sorption of dissolved arsenic to iron hydroxides in nontailings background material.