Occurrence, Geochemistry and Speciation of Elevated Arsenic Concentrations in a Fractured Bedrock Aquifer System

The presence of elevated arsenic concentrations (≥ 10 µg L^-1) in groundwaters has been widely reported in areas of South-East Asia with recent studies showing its detection in fractured bedrock aquifers is occurring mainly in regions of north-eastern USA. However, data within Europe remain limited; therefore, the objective of this work was to understand the geochemical mobilisation mechanism of arsenic in this geologic setting using a study site in Ireland as a case study. Physicochemical (pH, Eh, d-O₂), trace metals, major ion and arsenic speciation samples were collected and analysed using a variety of field and laboratory-based techniques and evaluated using statistical analysis. Groundwaters containing elevated dissolved arsenic concentrations (up to 73.95 µg L^-1) were characterised as oxic-alkali groundwaters with the co-occurrence of other oxyanions (including Mo, Se, Sb and U), low dissolved concentrations of Fe and Mn, and low Na/Ca ratios indicated that arsenic was mobilised through alkali desorption of Fe oxyhydroxides. Arsenic speciation using a solid-phase extraction methodology (n = 20) showed that the dominant species of arsenic was arsenate, with pH being a major controlling factor. The expected source of arsenic is sulphide minerals within fractures of the bedrock aquifer with transportation of arsenic and other oxyanion forming elements facilitated by secondary Fe mineral phases. However, the presence of methylarsenical compounds detected in groundwaters illustrates that microbially mediated mobilisation processes may also be (co)-occurring. This study gives insight into the geochemistry of arsenic mobilisation that can be used to further guide research needs in this area for the protection of groundwater resources.