Fluorine concentrations of ore fluids in the Illinois-Kentucky district: Evidence from SEM-EDS analysis of fluid inclusion decrepitates

The Illinois-Kentucky district is an atypical occurrence of Mississippi Valley-type (MVT) mineralization that consists predominantly of fluorite rather than metal sulfide minerals. A long-standing assumption for the predominance of fluorite in the Illinois-Kentucky district is that the ore fluids there were anomalously rich in dissolved fluorine compared to typical sedimentary brines and other MVT ore fluids. This hypothesis is based on the unusual close temporal and spatial association of fluorine-rich ultramafic igneous rocks to MVT mineralization in the district, high K and Sr concentrations in the igneous rocks and in MVT ore-hosted fluid inclusions, a significant mantle 3He/4He component in ore-hosted fluid inclusions, and reaction path models that show titration of a HF-rich fluid into sedimentary brine is capable of producing a fluorite-dominated MVT ore mineral assemblage.The purpose of the present study was to test this hypothesis more directly by determining the fluorine concentration of the Illinois-Kentucky ore fluid through SEM-EDS analysis of evaporative solute mounds resulting from thermal decrepitation of fluid inclusions hosted in sphalerite. All 26 evaporative solute mounds from Illinois-Kentucky sphalerite samples analyzed contained detectable concentrations of fluorine of 1-4 weight percent. Based on calibration to standard solutions and previously published fluid inclusion major element concentrations, these solute mound fluorine concentrations correspond to fluid inclusion fluorine concentrations of about 680-4300 ppm, indicating that the Illinois-Kentucky ore fluids were quite rich in fluorine compared to typical sedimentary brines, which have fluorine concentrations mainly on the order of 1's to 10's of ppm. In contrast, solute mounds from sphalerite-hosted fluid inclusions from the Tri-State district did not contain fluorine in excess of the detection limit. The detection limit equates to an aqueous fluorine concentration between 87 and 169 ppm. The high apparent fluorine concentrations of the Illinois-Kentucky fluid inclusions suggest that the ore fluids were very acidic with a pH ranging between 0 and 1.4, much lower than the typical pH range of MVT ore fluids of 4-5.5. Such a low pH would have greatly increased the solubility of metal sulfide minerals, suppressing their precipitation and contributing further to the predominance of fluorite in the Illinois-Kentucky district.