Natural hexavalent chromium in groundwaters interacting with ophiolitic rocks

Thirty of the 58 groundwaters sampled in September-October 2000 in the study area (La Spezia Province, Italy) have Mg-HCO₃ to Ca-HCO₃ composition, undetectable Cr(III) contents, and virtually equal concentrations of total dissolved Cr and Cr(VI). Therefore, dissolved Cr is present in toto as Cr(VI), with concentrations of 5-73 ppb. These values are above the maximum permissible level for drinking waters (5 ppb). Local ophiolites, especially serpentinites and ultramafites, are Cr-rich and represent a Cr source for groundwaters. However, since Cr is present as Cr(III) in rock-forming minerals, its release to the aqueous solution requires oxidation of Cr(III) to Cr(VI). This can be performed by different electron acceptors, including Mn oxides, H₂O₂, gaseous O₂, and perhaps Fe(III) oxyhydroxides. Based on this evidence and due to the absence of anthropogenic Cr sources, the comparatively high Cr(VI) concentrations measured in the waters of the study area are attributed to natural pollution.