Geochemical modeling of mercury in coastal groundwater

The systematic analysis of groundwater in the Greek island of Skiathos revealed a seasonal increase of total mercury concentrations after the extensive groundwater abstraction during the busy and heavily touristic summer months. This contamination was accompanied by a corresponding increase of the chloride content of groundwater, attributed to seawater intrusion into the freshwater-depleted aquifer within mercury-rich bedrock. The effects of elevated concentrations of chloride anions in the mobilization of mercury and its speciation were addressed by geochemical equilibrium modeling, considering cinnabar (HgS) as the mineral source of mercury. Adsorption onto hydrous ferric oxide (Fe₂O₃·H₂O) was a necessary ingredient of the geochemical model for bringing the calculated concentrations in agreement with field measurements, after optimization of the cinnabar/adsorbent mass ratio to a value of 4.9 × 10^-8. The speciation of mercury was found to depend on the acidity and redox status as well as on the chloride content of groundwater. Mercury concentrations in the groundwater of Skiathos rise above the World Health Organization limit of 1 μg L^-1 for a seawater intrusion higher than 3 %, with HgCl₂ being the dominant species followed by HgClOH, HgCl₃^- and HgCl₄^2-. The assumed concentration of dissolved organic matter in groundwater had a negligible impact on the mercury speciation and its mobilization by chloride.