Rhenium, Os, and Pt are redox sensitive elements that are concentrated in highly reducing environments such as those associated with black shales but mobile under more oxidizing conditions such as those associated with arc volcanism. They are chalcophile in many terrestrial ore-forming environments, and their isotopic systematics provide unique opportunities to date the formation of sulfide ore deposits and understand their petrogenesis. Fractional crystallization of magmatic sulfide ores generates primary variations in Re/Os and Pt/Os that allow mineral and whole rock isochron ages to be determined and discrimination of crustal and mantle sources based on initial Os isotopic compositions. Molybdenite is especially well suited for geochronology due to its high Re/Os and resistance to resetting. Rhenium concentrations in molybdenite tend to reflect the composition or provenance of the ore-forming fluids, with higher concentrations associated with more primitive sources or more oxidized fluids and lower concentrations with more evolved and/or reduced conditions, although local and regional factors also have a significant influence. Many studies have used pyrite for dating but its typically low Re concentration, variable initial Os isotopic composition (reflecting fluid mxing), and susceptibility to re-equilibration makes its use as a geochronometer problematic in many cases. Other sulfide minerals such as bornite and arsenopyrite have shown promise for Re–Os isotope geochronology but additional studies are needed to evaluate their broader applicability for dating of ore deposits. The isobaric beta decay of parent isotope 187Re to 187Os has restricted investigation of this system by microbeam techniques such as ion microprobe or laser ablation mass spectrometry, especially for geochronology. This requires either chemically processing the sample to separate the elements or novel techniques such as collision-cells that preferentially ionize the Re and Os during the analysis. Thermal ionization mass spectrometry (TIMS) and inductively-coupled plasma mass spectrometry (ICPMS) are the most widely applied techniques for Re-Pt-Os isotopic analyses. Specialized techniques for sample digestion to ensure redox equilibrium between Os in the sample and the isotopically enriched spikes used for isotope dilution measurements are typically required. This chapter briefly reviews development of the 187Re-187Os and 190Pt-186Os isotopic systems for earth science, physico-chemical controls on their behavior in ore-forming environments, and applications to metallogenic systems.
