Fluid-rock interaction during progressive migration of carbonatitic fluids, derived from small-scale trace element and Sr, Pb isotope distribution in hydrothermal fluorite

Associated with the Cretaceous Okorusu carbonatite complex (Namibia) is a hydrothermal fluorite mineralization hosted in Pan-African country rock marbles, which resulted from fluid–rock reaction between the marbles and orthomagmatic, carbonatitic fluids expelled from the carbonatite. Yellow fluorite I was deposited in veins up to 5 cm away from the wallrock contact, followed by purple and colorless fluorite II, smoky quartz and barite, a Mn-rich crust on early calcite, and pure calcite. This clear-cut sequence of mineral growth allows an investigation into fluid–rock interaction processes between the marble and the migrating carbonatitic fluid, and element fractionation patterns between the fluid and subsequent hydrothermal precipitates. Fluorite I shows a progressive change in color from dark yellow to colorless with purple laminations over time of deposition. Subsequent fluorite I precipitates show an increase in Ca, and a continuous decrease in F, Sr, REE, Y, Th, U and Pb contents. The ratios (Eu/Eu*)cn, Th/Pb and U/Pb increase whereas Y/Ho, Th/U and (La/Yb)cn decrease. The Sr-isotopic composition remains constant at 87Sr/86Sr = 0.70456–0.70459, but with varying, highly radiogenic Pb (206Pb/204Pb = 32–190, 238U/204Pb = 7–63). Fluorite II has 87Sr/86Sr = 0.70454–0.70459, 206Pb/204Pb = 18.349, and 207Pb/204Pb = 15.600, and a chemical composition similar to youngest fluorite I. The Mn-rich crust on early calcite accumulated REE, Ba, Pb, Zr, Cs, Th and U, developing into pure calcite with a prominent negative Ce anomaly and successively more radiogenic Sr. The calculated degrees of fluid–rock interaction, F = weight fraction of fluid/(fluid + marble), decrease from fluorite I and most fluorite II (f = 0.5) to calcite (f = 0.2–0.3) and hydrothermal quartz (f << 0.1). A crush-leach experiment for fluid inclusions in the hydrothermal quartz yielded a Rb-Sr isochron age of 103 ± 12 Ma. Crush-leach analysis for the carbonatitic fluid trapped in the wallrock yielded a trend from the fluid leachate to the host quartz (206Pb/204Pb = 18.224 and 18.602, 207Pb/204Pb = 15.616 and 15.636, respectively) extending from carbonatite towards crustal rocks. Calculated trace element distribution coefficients fluorite/fluid are below unity throughout, and increase from La to Yb. Elements largely excluded from fluorite (Ba, Pb, LREE relative to HREE) were incorporated later into the Mn-rich crust on calcite. The trace element patterns of the hydrothermal minerals are related to changing aCO2 and aF- in the fluid during continued fluid–marble reaction. A predominance of carbonate over fluoride complexing in the fluid as reactions proceeded controlled the Y/Ho, Th/U and REE patterns in the fluid and the crystallizing phases. Deviations from these trends indicate discontinuous processes of fluid–rock reaction.