Watershed-scale distributions of heavy metals in the hyporheic zones of a heavily polluted Maozhou River watershed, southern China

Abstract

Hyporheic zone (HZ) sediments in river systems are often contaminated with heavy metals as a legacy of natural processes and anthropogenic activities. The geochemical behaviors of heavy metals in the HZ sediments at the laboratory scale have been extensively studied. However, the watershed-scale distributions of heavy metals in the HZ sediments and the processes controlling their distributions have not been well studied. Here, we report a watershed-scale study of heavy metals (i.e., Cr, Ni, Cu, Zn, Cd, and Pb) distributions in the HZ of the Maozhou River watershed, a heavily polluted area within the Pearl River Delta, southern China. Statistical analysis revealed that the spatial distribution of studied heavy metal concentrations was highly correlated with that of the sediment-associated sulfide at the watershed-scale. Metal extraction analysis and double-spherical aberration-corrected scanning transmission electron microscope imaging (Cs-STEM) further confirmed the strong association of heavy metals with sulfur. These observations demonstrated that the formation of metals-sulfide precipitates was the key process controlling the watershed-scale distributions of heavy metals (especially for Cr, Ni and Zn) in the HZ sediments. Additionally, high permeability of the HZ sediments may prevent Ni, Zn, Cd and Pb accumulation in sediments. Specially, Cu distribution was mainly affected by organic-Cu complexation. In the estuary area, salinity input likely affected the distributions of Ni, Zn and Cd through cation exchange processes. The findings improved our understanding of the distributions of heavy metals and the processes controlling their distributions at the watershed-scale, and have implications for remediating and managing contaminated HZ sediments.