Speciation of arsenic in Greek travertines: Co-precipitation of arsenate with calcite

The western part of the Chalkidiki peninsula in Northern Greece is a geothermally active area that contains high levels of naturally derived arsenic in its alkaline groundwaters (up to 3760 μg/L). Near wells, equilibration of these groundwaters with atmospheric carbon dioxide leads to the precipitation of travertines that contain very high levels of arsenic (up to 913 mg/kg). To determine the mechanism of arsenic uptake in these travertines, we analyzed two different types of travertine from this region using both bulk and micro-focused X-ray absorption spectroscopy (XAS and μ-XAS) and micro-focused X-ray fluorescence spectroscopy (μ-XRF). Bulk XAS showed that in all of the studied samples arsenic is present in the pentavalent oxidation state (arsenate). μ-XRF analyses indicated that arsenic is closely associated with the calcite matrix and that it generally does not correlate well with iron. The arsenic K-edge XAS spectra of all samples closely matched each other and closely resembled a reference spectrum for arsenate coprecipitated with calcite (rather than adsorbed or pure calcium arsenate). Iron on the other hand was found to be mainly present as a constituent of clay minerals, of presumably detrital origin, suggesting that iron-(hydr)oxides were not sufficiently abundant to act as major scavengers for arsenic in the Chalkidiki travertines. We estimated that calcite in these travertines could sequester at least 25% of aqueous arsenic in the form of As(V) and thus immobilize a substantial part of arsenic present in the geothermal groundwaters. These results may also be relevant for other areas where geothermal groundwaters carry arsenic to the surface and possibly as well for arsenic geochemistry in other environments with CO2-enriched water.