The composition of fluid inclusions in ore and gangue minerals from the Silesian-Cracow Mississippi Valley-type Zn-Pb deposits Poland: Genetic and environmental implications

Abstract

The composition of fluids extracted from ore and gangue sulfide minerals that span most of the paragenesis of the Silesian-Cracow district was determined using a newly developed ion chromatographic (IC) technique. Ionic species determined were Na+, NH+4, Ca2+, Mg2+, K+, Rb+, Sr2+, Ba2+, Cl-, Br-, F-, I-, PO3-4, CO2-3, HS-, S2O2-3, SO2-4, NO-3, and acetate. Mineral samples included six from the Pomorzany mine and one from the Trzebionka mine which are hosted in the Triassic Muschelkalk Formation, and two samples of drill core from mineralized Upper Devonian strata. Nine paragenetically identifiable sulfide minerals occur throughout the Silesian-Cracow district. These include from earliest to latest: early iron sulfides, granular sphalerite, early galena, light-banded sphalerite, galena, dark-banded sphalerite, iron sulfides, late dark-banded sphalerite with late galena, and late iron sulfides. Seven of the minerals were sampled for fluid inclusion analysis in this study. Only the early iron sulfides and the last galena stage were not sampled. Although the number of analyses are limited to nine samples and two replicates and there is uncertainty about the characteristics of the fluid inclusions analyzed, the data show clear temporal trends in the composition of the fluids that deposited these minerals. Fluid inclusions in minerals deposited later in the paragenesis have significantly more K+, Br-, NH+4, and acetate but less Sr2+ than those deposited earlier in the paragenesis. The later minerals are also characterized by isotopically lighter sulfur and significantly more Tl and As in the solid minerals. The change in ore-fluid chemistry is interpreted to reflect a major change in the hydrologic regime of the district. Apparently, the migrational paths of ore fluids from the Upper Silesian basin changed during ore deposition and the fluids which deposited early minerals reacted with aquifers with very different geochemical characteristics than those that deposited late minerals. The early fluids may have reacted primarily with Devonian and Lower Carboniferous carbonate aquifers deeper in the basin, whereas the later fluids appear to have had extensive contact with organic-rich rocks, probably the shallower Middle and Upper Carboniferous flysch associated with coal measures. High concentrations of toxic Tl and As occur in the readily oxidized marcasite and pyrite minerals deposited by the later fluids. In general, the geochemistry of both the early and late fluids may be explained by an evaporite related origin or by water-rock modification of a saline basinal brine. When compared to the composition of fluid inclusions in Mississippi Valley-type (MVT) ore minerals from the Ozark region of the United States, fluid inclusions in minerals from Silesian-Cracow are fundamentally different, containing more Ca2+, Mg2+, NH+4, Br-, Sr2+ and acetate in all mineral stages with significantly more K+ in later stage minerals. The differences in ore fluid chemistry between the two regions are consistent with the lithologic differences of the respective basins thought to be the source of the mineralizing brines.