Arsenic-rich shallow groundwater in sandy aquifer systems buffered by rising carbonate waters: A geochemical case study from Mannar Island, Sri Lanka.

Major ion, trace elements, and stable isotope analyses were performed on groundwater samples collected from Mannar Island in the northern Indian Ocean. Arsenic concentrations up to 34μg/L have been observed in groundwater samples from the island. In addition, 23% of extensively used shallow drinking water wells showed higher arsenic contents than the recommended value by the World Health Organization (10μg/L). Groundwater in the island showed pH values between 6.9 and 8.9 and was dominated by Na, K, Ca, Mg, HCO, Cl and SO. The δO and δH composition of most groundwater plotted very close to the local meteoric waterline, however, some wells showed enriched isotope compositions that are most likely due to evaporation. Sea water intrusion in this island was likely of minor importance as indicated by the major ion composition. An approximated mass balance calculation using chloride concentrations indicated that out of the 35 investigated wells only 6 near-shore wells were influenced by sea water intrusion up to about 15%. Even though this is a sandy aquifer, groundwaters were characterized with higher contents of dissolved inorganic carbon (DIC) (2.11-10.9mmol/L). The corresponding δC values varied from -19.4‰ to -6.5‰. Except for a few samples with values approaching -20‰, these isotope values are more typical for carbonate dissolution and equilibration of CO in the aquifer. This study shows that the underlying carbonate system may buffer the aqueous geochemistry of the groundwater on the island. The high arsenic content in groundwater may have been mobilized through reductive dissolution of Fe-Mn oxides and oxy-hydroxides that are coated on sandy aquifer materials. The lower content of DOC (0.2-1.5mmol/L) provides evidence for the restricted formation of pyrite in the aquifer.