Contrasting behaviors of groundwater arsenic and fluoride in the lower reaches of the Yellow River basin, China: Geochemical and modeling evidences

Abstract

Genesis of the contrasting distributions of high arsenic (>10 μg/L) and fluoride (>1 mg/L) groundwater and their negative correlations remain poorly understood. We investigated spatial distributions of groundwater arsenic and fluoride concentrations in the lower reaches of the Yellow River basin, Henan Province, China, using bivariate statistical analyses and geochemical simulations. Results suggest that high arsenic and fluoride groundwater showed contrasting distributions with few overlapped area. Groundwater arsenic concentrations were significantly negatively correlated with oxidation-reduction potential (ORP) values and positively with NH4+ and Fe(II) concentrations, while the opposites were true for groundwater fluoride concentrations. These may suggest that high arsenic groundwater is related to stronger organic matter degradation and Fe(III) oxide reduction, while groundwater fluoride enrichment occurs with less extent of organic matter degradation. Geochemical calculations supported that groundwater fluoride enrichment was governed by extent of fluorite dissolution, which was constrained by varied saturation indices of fluorite in groundwater. However, groundwater arsenic mobility may be explained by different solubility of Fe(III) oxides. Higher Fe(III) oxide solubility corresponding to goethite and lepidocrocite was related to higher arsenic concentrations, while hematite was too low in solubility to produce high arsenic groundwater. The study presented both geochemical and modeling evidences for the contrasting behaviors of groundwater arsenic and fluoride concentrations in anoxic aquifers.