X-ray Absorption Spectroscopy of Lead and Zinc Speciation in a Contaminated Groundwater Aquifer

The formation of insoluble metal sulfides in the environment may reduce the mobility and bioavailability of heavy metal contaminants and potentially eliminate the need for ex situ remediation of certain hazardous waste sites. To assist in assessing remediation strategies for the Bypass 601 Superfund site, groundwater aquifer samples were analyzed using synchrotron X-ray absorption spectroscopy (XAS) to determine whether lead and zinc sulfides were dominant mineral phases. Moist aquifer solids contained between 150 and 1800 mg of Pb/kg and between 100 and 250 mg of Zn/kg. Lead sulfide was not dominant in any of the samples analyzed, including one sample collected from a well in a flood plain that contained 70% of zinc bonded to sulfur, probably as ZnS. This portion of the aquifer had apparently been under reducing conditions. In all other samples, first-shell bonding of Pb and Zn was predominantly to oxygen. Data indicated that PbO, PbCO3, PbSO4, and ZnO were not dominant metal species. The XAS analyses showed that with one exception, metal sulfides were not prevalent.