Characterization and quantification of groundwater sulfate sources at a mining site in an arid climate: The Monument Valley site in Arizona, USA

• Qualitative sulfate source ID using dual isotopes (34S and 18O) at a mining site.
• Quantification of the sources (sulfide oxidation vs. sulfuric acid) by two methods.
• Sulfate from sulfuric acid application served as the major source for 40 years.
• Proposed accumulation of sulfate salts formed from sulfuric acid in arid climate.

The Monument Valley site, a former uranium mining site located in the state of Arizona in the Southwest USA, has high concentrations of sulfate in groundwater. Stable isotope analysis of S and O for sulfate, in combination with geochemical and hydrogeological data, was used to characterize the sources and fate of sulfate. The results indicate the existence of two discrete sources of sulfate (in excess of baseline levels): sulfuric acid released during ore processing and sulfate generated via sulfide-mineral oxidation. The contributions of the sources are related to spatial distributions of sulfate in the plume through analysis of groundwater travel times. Quantification of the sources using two isotope-analysis methods yielded similar results. The results indicate that sulfuric acid served as the primary source (mean = 427 mg/L, 74%), with sulfide-mineral oxidation providing a smaller contribution (mean = 147 mg/L, 26%). It appears that the major contribution to the sulfide-mineral oxidation component originates from oxidation of sulfide minerals in exposed bedrock residing in the primary recharge zone of the local aquifer, which provides an elevated sulfate background for groundwater. Conversely, the oxidation of sulfide minerals associated with the mine tailings appears to provide a relatively minor contribution (∼8% of the overall total). Interestingly, it appears that sulfuric acid served as a sustained source of sulfate for approximately 40 years. This may be related to the accumulation of sulfate salts (formed after neutralization and disposal of the sulfuric acid) in the source zone due to the arid climate of the site. Contrary to the typical assumption applied at many mining sites that sulfide-mineral oxidation is the primary source of sulfate, these sulfate salts are hypothesized to be the primary source for this site.