High Hexavalent Chromium Concentration in Groundwater from a Deep Aquifer in the Baiyangdian Basin of the North China Plain

Hexavalent chromium (Cr(VI)) is known to occur naturally in shallow oxic groundwater, typically from aquifers associated with mafic and ultramafic formations, but information on the occurrence of Cr(VI) in deep groundwater from large sedimentary basins is limited. This study shows that groundwater from the Baiyangdian Lake Basin (BYB), home to the future second capital city of China, had high Cr concentration (>10 μg/L, up to 86 μg/L) in the deep aquifer (>150 m), while shallow groundwater had lower Cr concentration (<10 μg/L). Chromium occurred predominantly as Cr(VI) (>95%). Shallow groundwater was characterized by higher Mn and Fe concentrations relative to deep groundwater, likely indicating more reducing conditions. Sequential extraction experiments from aquifer sediments suggest that Cr(VI) may derive from silicate weathering and that Mn oxides in the aquifer play a major role in the formation of Cr(VI) in groundwater. Inverse correlations between Mn and Cr(VI) suggest that reductive dissolution of Mn oxides constrains Cr(VI) mobilization in the shallow groundwater, while oxic–suboxic conditions in the deep aquifer limit Mn solubility, which enhances oxidation of Cr(III) to Cr(VI) and promotes desorption of Cr(VI) under alkaline conditions. This study demonstrates the potential geogenic occurrence of high Cr(VI) concentration in deep groundwater from a nonmafic, large sedimentary basin containing Mn oxides in the aquifer sediments.