Application of Chromium Stable Isotopes to the Evaluation of Cr(VI) Contamination in Groundwater and Rock Leachates from Central Euboea, the Assopos Basin and Thebes Valley (Greece)

Tuesday, 16 December 2014
Robert Frei1, Karin Margarita Frei2, Maria Economou-Eliopoulos3, Cathy Atsarou3 and Dimitrios Koilakos4, (1)University of Copenhagen, Copenhagen, Denmark, (2)National Museum of Denmark, Copenhagen, Denmark, (3)University of Athens, Department of Geology and Geoenvironment, Athens, Greece, (4)Agricultural University of Athens, Department of Natural Resources Management & Agricultural Engineering, Athens, Greece
In order to identify the source(s) of toxic Cr(VI) prevalent in drinking and irrigation waters of Central Euboea (CE), the Assopos Basin (AB) and the Thebes Valley (TV;Greece), we have analyzed stable Cr isotopes, together with major and trace elements in porous, karstic and ultramafic mélange-hosted aquifers and groundwaters, ultramafic rocks from the hinterlands and soil samples from cultivated sites of this region. In addition we complemented our data with experimentally produced water leachates of rocks and soils.

Mg/Ca ratios >1 in much of the water samples indicate the influence of ultramafic rocks which dominate the geology on the geochemical composition of the groundwaters. Elevated Cr(VI) concentrations in experimental soil leachates, compared to those in rock pulp leachates, can be potentially explained by the presence of larger amounts of Fe(II) and lower amounts of Mn(IV) in the country rocks. Factor analysis on the 17 water samples from TV indicates a strong relationship between Na, Cl-, and Cr(VI), and also points to an aversion of Cr(VI) to nitrates (fertilizer-sewage sourced) and its independency from Mg and SiO2.

Assuming that redox processes produce significant Cr isotope fractionation (groundwater δ53Cr values range between +0.62 and +1.99‰), the compilation of the analytical data suggests that the dominant cause of Cr isotope fractionation is post-mobilization reduction of Cr(VI). However, the lack of a clear negative relationship between Cr(VI) concentrations and δ53Cr values may reflect that other processes complicate this interpretation. The variation in δ53Cr values, together with the results from the experimentally produced ultramafic rock pulp leachates, imply initial oxidative mobilization of Cr(VI) from the ultramafic host rocks, followed by reductive processes, as the main reason for the toxicity of the groundwaters. Using a Rayleigh distillation model and different fractionation factors of Cr(VI) reduction valid for aqueous Fe(II) and a variety of Fe(II)-bearing minerals, we calculate that more than ~53%, but maximum ~94%, of the originally mobile Cr(VI) pool was reduced to immobile Cr(III) in the waters from CE and AB. This indicates that efficient processes in the aquifers may facilitate natural attenuation of the toxic Cr(VI) to less harmful Cr(III).