| Summary: | High–arsenic (As) groundwater poses a serious threat to human health. The upper and middle reaches of the Yellow River are well–known areas for the enrichment of high–arsenic groundwater. However, little is known about the distribution characteristics and formation mechanism of high-As groundwater in the lower reach of the Yellow River. There were 203 groundwater samples collected in different groundwater systems of the lower Yellow River for the exploration of its hydrogeochemical characteristics. Results showed that more than 20% of the samples have arsenic concentrations exceeding 10 μg/L. The high-As groundwater was mainly distributed in Late Pleistocene–Holocene aquifers, and the As concentrations in the paleochannels systems (C2 and C4) were significantly higher than that of the paleointerfluve system (C3) and modern Yellow River affected system (C5). The high-As groundwater is characterized by high Fe<sup>2+</sup> and NH<sub>4</sub><sup>+</sup> and low Eh and NO<sub>3</sub><sup>−</sup>, indicating that reductive dissolution of the As–bearing iron oxides is probably the main cause of As release. The arsenic concentrations strikingly showed an increasing tendency as the HCO<sub>3</sub><sup>−</sup> proportion increases, suggesting that HCO<sub>3</sub><sup>−</sup> competitive adsorption may facilitate As mobilization, too. In addition, a Gibbs diagram showed that the evaporation of groundwater could be another significant hydrogeochemical processes, except for the water–rock interaction in the study area. Different sources of aquifer medium and sedimentary structure may be the main reasons for the significant zonation of the As spatial distribution in the lower Yellow River.
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