The Paleoproterozoic carbonate-hosted Pering Zn–Pb deposit, South Africa. II: fluid inclusion, fluid chemistry and stable isotope constraints

The Pering deposit is the prime example of Zn–Pb mineralisation hosted by stromatolitic dolostones of the Neoarchean to Paleoproterozoic Transvaal Supergroup. The hydrothermal deposit centers on subvertical breccia pipes that crosscut stromatolitic dolostones of the Reivilo Formation, the lowermost portion of the Campbellrand Subgroup. Four distinct stages of hydrothermal mineralisation are recognised. Early pyritic rock matrix brecciation is followed by collomorphous sphalerite mineralisation with replacive character, which, in turn, is succeeded by coarse grained open-space-infill of sphalerite, galena, sparry dolomite, and quartz. Together, the latter two stages account for ore-grade Zn–Pb mineralisation. The fourth and final paragenetic stage is characterised by open-space-infill by coarse sparry calcite. The present study documents the results of a detailed geochemical study of the Pering deposit, including fluid inclusion microthermometry, fluid chemistry and stable isotope geochemistry of sulphides (δ³⁴S) and carbonate gangue (δ¹³C and δ¹⁸O). Microthermometric fluid inclusion studies carried out on a series of coarsely grained crystalline quartz and sphalerite samples of the latter, open-space-infill stage of the main mineralisation event reveal the presence of three major fluid types: (1) a halite–saturated aqueous fluid H₂O–NaCl–CaCl₂ (>33 wt% NaCl equivalent) brine, (2) low-salinity meteoric fluid (<7 wt% NaCl) and (3) a carbonic CH₄–CO₂–HS⁻ fluid that may be derived from organic material present within the host dolostone. Mixing of these fluids have given rise to variable mixtures (H₂O–CaCl₂–NaCl ±(CH₄–CO₂–HS⁻), 2 to 25 wt% NaCl+CaCl₂). Heterogeneous trapping of the aqueous and carbonic fluids occurred under conditions of immiscibility. Fluid temperature and pressure conditions during mineralisation are determined to be 200–210°C and 1.1–1.4 kbar, corresponding to a depth of mineralisation of 4.1–5.2 km. Chemical analyses of the brine inclusions show them to be dominated by Na and Cl with lesser amounts of Ca, K and SO₄. Fluid ratios of Cl/Br indicate that they originated as halite saturated seawater brines that mixed with lower salinity fluids. Analyses of individual brine inclusions document high concentrations of Zn and Pb (∼1,500 and ∼200 ppm respectively) and identify the brine as responsible for the introduction of base metals. Stable isotope data were acquired for host rock and hydrothermal carbonates (dolomite, calcite) and sulphides (pyrite, sphalerite, galena and chalcopyrite). The ore-forming sulphides show a trend to ³⁴S enrichment from pyrite nodules in the pyritic rock matrix breccia (δ³⁴S = −9.9 to +3.7‰) to paragenetically late chalcopyrite of the main mineralisation event (δ³⁴S = +30.0‰). The observed trend is attributed to Rayleigh fractionation during the complete reduction of sulphate in a restricted reservoir by thermochemical sulphate reduction, and incremental precipitation of the generated sulphide. The initial sulphate reservoir is expected to have had an isotopic signature around 0‰, and may well represent magmatic sulphur, oxidised and leached by the metal-bearing brine. The δ¹⁸O values of successive generations of dolomite, from host dolostone to paragenetically late saddle dolomite follow a consistent trend that yields convincing evidence for extensive water rock interaction at variable fluid–rock ratios. Values of δ¹³C remain virtually unchanged and similar to the host dolostone, thus suggesting insignificant influx of CO₂ during the early and main stages of mineralisation. On the other hand, δ¹³C and δ¹⁸O of post-ore calcite define two distinct clusters that may be attributed to changes in the relative abundance in CH₄ and CO₂ during waning stages of hydrothermal fluid flow.