Prediction of ore fluid metal concentrations from solid solution concentrations in ore-stage calcite: Application to the Illinois-Kentucky and Central Tennessee Mississippi Valley-type districts

Abstract

Knowledge of the concentrations of Zn and Pb in Mississippi Valley-type (MVT) ore fluids is fundamental to understanding MVT deposit origin. Most previous attempts to quantify the concentrations of Zn and Pb in MVT ore fluids have focused on the analysis of fluid inclusions. However, these attempts have yielded ambiguous results due to possible contamination from secondary fluid inclusions, interferences from Zn and Pb in the host mineral matrix, and uncertainties about whether the measured Zn and Pb signals represent aqueous solute or accidental solid inclusions entrained within the fluid inclusions. The purpose of the present study, therefore, was to try to determine Zn and Pb concentrations in MVT ore fluids using an alternate method that avoids these ambiguities by calculating Zn and Pb concentrations in MVT ore fluids theoretically based on their solid solution concentrations in calcite. This method was applied to the Illinois-Kentucky and Central Tennessee districts, which both contain ore-stage calcite.Experimental partition coefficient (D) values from Rimstidt et al. (1998) and Tsusue and Holland (1966), and theoretical thermodynamic distribution coefficient (KD) values were employed in the present study. Ore fluid concentrations of Zn were likely most accurately predicted by Rimstidt et al. (1998) D values, based on their success in predicting known fluid inclusion concentrations of Mg and Mn, and likely also most accurately predicted ore fluid concentrations of Fe. All four of these elements have a divalent ionic radius smaller than that of Ca2+ and form carbonate minerals with the calcite structure. For both the Illinois-Kentucky and the Central Tennessee district, predicted ore fluid Zn and Fe concentrations were on the order of up to 10’s of ppm. Ore fluid concentrations of Pb could only be predicted using Rimstidt et al. (1998) D values. However, these concentrations are unlikely to be reliable, as predicted ore fluid concentrations of Sr and Ba, which like Pb also have a divalent ionic radius larger than that of Ca2+ and form carbonate minerals with the aragonite structure, did not consistently agree well with known concentrations of Sr and Ba in fluid inclusions.The ore fluid Zn concentrations predicted in the present study lie within the range of Zn concentrations typical of modern sedimentary brines and are high enough to allow deposition of the observed amounts of Zn in the Illinois-Kentucky and Central Tennessee districts within ranges of geologically reasonable times and ore fluid flow velocities. If the pH of the Illinois-Kentucky and Central pH ore fluids was as low as current evidence suggests to be possible, then these ore fluids could simultaneously have transported enough sulfide with their Zn to account for the observed amounts of sphalerite in the districts.