Environmental factors controlling the precipitation of Cu-bearing hydrotalcite-like compounds from mine waters. The case of the "Eve verda" spring (Aosta Valley, Italy) | INSTITUT DE PHYSIQUE DU GLOBE DE PARIS

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  Environmental factors controlling the precipitation of Cu-bearing hydrotalcite-like compounds from mine waters. The case of the "Eve verda" spring (Aosta Valley, Italy)

Publication Type:

Journal Article

Source:

European Journal of Mineralogy, Volume 20, Issue 1, p.73-94 (2008)

ISBN:

0935-1221

Accession Number:

WOS:000254250000005

Keywords:

UMR 7154 ; Géobiosphère actuelle et primitive

Abstract:

In the Cu-Fe-sulphide mining district of Servette-Chuc (Saint-Marcel, Aosta Valley, Italy), a streambed called Eve Verda and covered with a colloidal blue-green precipitate has been known since the 18th century. X-ray and chemical analyses reveal that the precipitate is a mixture of a nanocrystalline Cu-Al-sulphate hydrotalcite-like compound close to hydrowoodwardite (Cu1-xAlx[SO4](x/2)[OH](2)center dot mH(2)O) (49 +/- 10 vol.%), and amorphous Al and Si oxyhydroxides. The Al/(Al + Cu) ratio of hydrowoodwardite (i.e., x) ranges between 0. 10 and 0.30 with a mean value of 0. 17 +/- 0.04. The average formula may be expressed as follows: Cu0.81Zn0.02Al0.17(SO4)(0.08)(OH)(2)center dot 1.10 H2O. In order to construct phase diagrams, we estimated the thermodynamic properties of the hydrowoodwardite solid solution starting from calorimetric measurements available in the literature, i.e., those for Mg, Co, Ni and Zn hydrotalcites. At least for x < 0.35, hydrowoodwardite may be treated either as an ideal or as a non-ideal solid solution between the two end-members Cu(OH)(2) (spertiniite) and Al(SO4)(0.5)(OH)(2) (aluminite). For x = 1/3 (i.e., woodwardite sensu stricto following IMA nomenclature) and m = 0, the ideal solid solution model provided a Gibbs free energy of formation (Delta G(f)(0)) of -684.4 kJ/mol and an enthalpy of formation (Delta H-f(0)) of -795.0 kJ/mol, while the non-ideal solution model yielded Delta G(f)(0) = -658.6 kJ/mol and Delta H-f(0) = -767.5 kJ/mol. f f The estimated data agree well with the solubility measurements reported for hydrotalcites. Since hydrowoodwardite precipitates where mineralised, acidic waters from an ephemeral stream are mixing with alkaline, diluted waters of a perennial spring, we calculated pH-X-u pseudosections (i.e., isochemical phase diagrams), where X-w is the molar proportion of the two mixing waters. The thermodynamic modelling indicates that the formation of hydrowoodwardite is related to a geochemical barrier represented by the perennial spring waters. It also demonstrates that the composition of hydrowoodwardite (i.e., x) is mainly a function of pH, while the modal composition of the precipitate depends instead on X-w. This explains the variations observed in the precipitate composition at Eve Verda.