Vertical redox zones of Fe-S-As coupled mineralogy in the sediments of Hetao Basin - Constraints for groundwater As contamination

The formation of iron-sulfur-arsenic (Fe-S-As) minerals during biogeochemical processes in As contaminated aquifers remains poorly understood despite their importance to understanding As release and transport in such systems. In this study, X-ray absorption and Mossbauer spectroscopies complemented by electron microscopy, and chemical extractions were used to examine vertical changes of As, Fe and S speciation for the example of sediments in the Hetao Basin. Reduction of Fe(III), As(V) and SO42- species were shown to co-occur in the aquifers. Iron oxides were observed to be predominantly goethite and hematite (36 - 12%) and appeared to decrease in abundance with depth. Furthermore, reduced As (including arsenite and As sulfides) and sulfur species (including S(-II), S(-I) and S-0) increased from 16% to 76% and from 13% to 44%, respectively. Iron oxides were the major As carrier in the sediments, and the lower groundwater As concentration consists with less desorbable and reducible As in the sediments. The formation of As-Fe sulfides (e.g., As containing pyrite and greigite) induced by redox heterogeneities likely contribute to localized lower groundwater As concentrations. These results help to further elucidate the complex relationship between biogeochemical processes and minerals formation in As contaminated aquifers.

Automated summary

This study examined the vertical changes of arsenic, iron, and sulfur speciation in sediments in the Hetao Basin using various analytical techniques. It was found that reduction of Fe(III), As(V) and SO42- species co-occurred in the aquifers, with iron oxides predominantly being goethite and hematite. Additionally, the study observed an increase in reduced arsenic and sulfur species with depth, indicating the formation of As-Fe sulfides may contribute to localized lower groundwater As concentrations.