Occurrence and enrichment mechanisms of groundwater hexavalent chromium in typical loess area of China

Abstract

Understanding the geochemical mechanisms governing hexavalent chromium (Cr(VI)) in groundwater is essential for mitigating health risks. However, the processes driving Cr(VI) accumulation and migration in loess regions remain insufficiently understood. This study investigated the occurrence, release, and migration mechanisms of Cr(VI) across different groundwater environmental units (GEUs) in the south-central Loess Plateau, China. This study used combined approach of isotopic analysis, multivariate statistical methods, hydrochemical graphical methods, and GIS technology to reveal the origins and processes influencing Cr(VI) hydrogeochemistry within these GEUs. The results revealed significant spatial variability in Cr(VI) concentrations among the GEUs, ranging from below the detection limit to 300 μg/L, with nearly 40% of samples exceeding the WHO limit. Pronounced enrichment of Cr(VI) was observed in the fissure-pore water of the loess tableland and pore water of the alluvial plain. Cr(VI) enrichment and release in the GEUs were facilitated by oxidative conditions (high Eh, SO₄²⁻/HCO₃⁻, Mn-oxide presence) and cation exchange processes under slightly alkaline conditions (pH > 7.80). Key hydrogeological processes and geomorphological factors, including lateral runoff recharge, slow groundwater flow in the loess tableland, vertical recharge, extensive water-rock interactions, and hydraulic gradients were identified as critical divers of Cr(VI) migration and enrichment across different GEUs. Under reductive conditions, Cr(VI) was reduced to Cr(III), particularly in the pore water of the alluvial plain, but competitive adsorption with nitrate allows the enrichment of Cr(VI) in groundwater, particularly in the fissure-pore aquifer. A conceptual model was developed to elucidate Cr(VI) sources and migration mechanisms in groundwater, offering a framework for risk mitigation and management of groundwater in loess regions.