Vertical distribution of As(III) and As(V) in a coastal sandy aquifer: factors controlling the concentration and speciation of arsenic in the Stuarts Point groundwater system, northern New South Wales, Australia

Arsenic species were measured in a bundled-piezometer installed in the Holocene barrier of the Stuarts Point coastal sands aquifer, northern New South Wales, Australia. Vertical distribution shows two peaks of elevated As concentration. At a depth of 10–11 m, concentrations of AsTot, As(V) and As(III) are in the range of 52–85, 38–67 and 14–18 μg/l respectively and the ratio of As(V)/As(III) is well above 1 at 3.7–2.7. The second peak, at a depth of 25 m, shows the highest concentrations of AsTot, As(V) and As(III) with values reaching 337, 125 and 212 μg/l, respectively. The As(V)/As(III) ratio is below 1 at 0.6–0.7. High AsTot and As(V) concentrations at shallower depths are associated with acidic conditions and very low concentrations of all ions. Desorption of As from Al-hydroxides and As-enriched Fe-oxyhydroxides are plausible mechanisms releasing As into the groundwater system. The elevated concentration of AsTot and As(III) at 25 m is potentially related to the leaching of the clay surfaces. Elevated HCO3- and alkaline pH conditions at this depth cause desorption of As which is later present as As(III) species in the reducing environment. The high concentrations of HCO3- further reduce the possible extent of As sorption on Fe and Mn oxyhydroxides. The identification of As in a groundwater system associated with the coastal barrier sand-dune environment raises serious questions of the suitability of human consumption of untreated groundwater, drawn from these aquifer types. Further investigation both in Australia and globally are needed to classified the extent of this hydrogeochemical occurrence near coastal communities that rely on groundwater.