Mobility and speciation of geogenic arsenic in bedrock groundwater from the Canadian Shield in western Quebec, Canada.

High arsenic concentrations occur in groundwater collected from a fractured crystalline bedrock aquifer in western Quebec (Canada). Sampling and analysis of water from 59 private wells reveal that more than half of the bedrock wells exceed the Canadian guideline value of 10μg/l for arsenic, whereas shallow wells in unconsolidated surficial deposits are not affected by the contamination. The weathering of arsenic-bearing sulfides present along the mineralized fault zone is considered to be the primary source of arsenic in groundwater. High-arsenic wells are generally characterized by mildly reducing conditions (Eh<250mV), weak alkaline conditions (pH>7.4), low Ca/Na ratios, elevated dissolved Fe and Mn concentrations and high proportions of As(III). Private bedrock wells are open boreholes that likely receive groundwater from multiple contributing fractures. Hence, it is proposed that dissolved arsenic is mainly derived from the contribution to the well discharge of reducing and alkaline geochemically evolved groundwater that contains arsenic as As(III). Geochemically evolved groundwater provides favorable conditions to release arsenic by reductive dissolution of iron and manganese oxyhydroxides and alkaline desorption from mineral surfaces. Thus, high-arsenic wells would contain a high proportion of geochemically evolved groundwater, while oxidizing low-pH recharge water causes dilution and sequestration of arsenic. In relation with the chemical evolution of groundwater along the flow path, most contaminated wells are located in confined areas whereas most of the wells located in unconfined recharge areas are not contaminated. The occurrence of boreholes with high dissolved arsenic as As(V) and oxidizing conditions is attributed to extensive sulfide oxidation and alkaline desorption. This work shows that the determination of arsenic speciation provides a valuable tool to investigate the behavior of arsenic in bedrock groundwater.