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Globally numerous regions have been identified with elevated arsenic within groundwater which can result in potential adverse health risks. In Ireland, a previous national-scale research assessment of groundwater identified isolated clusters of elevated arsenic and indicated that lithology was a major controlling factor on arsenic in groundwater. Complementary comparisons of national-scale and regional-scale groundwater assessments of arsenic are lacking in Europe when compared to other global regions. The aims of this study were to demonstrate the value of a regional-scale groundwater hydrochemistry dataset with an existing national-scale approach, describe anomalies that can become the focus of attention for public health and economic reasons, and to provide a wider context for arsenic in groundwater within Ireland and Europe. Regional-scale data using 470 locations comprising 1,493 analyses using several hydrochemical parameters (arsenic, pH, conductivity, iron, manganese, sodium, potassium, calcium, magnesium, and total hardness) in south west Ireland were integrated with geological, hydrogeological, and land use datasets. Statistical analysis was performed using a combination of methods including score tests of geological groups using an empirical cumulative distribution function plot in addition to spatial analysis. Results revealed that hydrochemical parameters exhibited different spatial clusters, which was generally associated with lithology. Arsenic was elevated in sandstone derived bedrock. Weak correlation of arsenic with other hydrochemical parameters were observed and redox-sensitive elements like manganese and iron showed a greater diversity in spatial occurrence. This study has shown that the variation of hydrochemical parameters are controlled by regional geology. Finally, the paper focuses on anomalies identified by concentrations of individual ions or statistical associations in the context of, for example, historical mineral exploration and mining in the area and also discusses whether groundwater chemistry sampling on this scale can assist in future mineral exploration, as well as guiding the future development of high quality public and private water supplies.

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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.

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 mainly in regions of north-eastern United States. Data within Europe remains limited; therefore, the objective of this work was to understand the geochemical mobilisation mechanism of arsenic in this geologic setting. Physiochemical (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 including multivariate analysis. Elevated dissolved arsenic concentrations (up to 73.95 µg L-1) were observed in oxic-alkali groundwaters with the co-occurrence of other oxyanions (e.g. Mo, Se, Sb and U), low dissolved concentrations of Fe and Mn and low Na/Ca ratios indicating 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 present in groundwater was arsenate, with pH being a major controlling factor. The expected source of arsenic is sulfide 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 the groundwaters illustrates that microbially mediated mobilisation processes were also (co)-occurring. This study demonstrates how field speciation of arsenic can be utilised to overcome analytical limitations of conventional laboratory speciation and to facilitate in the interpretation of the environmental mobility of arsenic within groundwaters.