Rhenium in Molybdenite: a Database Approach to Identifying Geochemical Controls on the Distribution of a Critical Element

Abstract

Molybdenite is the world's principal source of rhenium (Re), a critical element in multiple high-tech applications. However, the Re contents in molybdenite vary by orders of magnitude on scales ranging from single grains to whole deposits. In order to better understand the systematics of this variation and what geochemical factors control molybdenite Re concentration, and hence overall Re resources, we examine global patterns in molybdenite Re contents through a compilation of > 3000 measurements of Re in molybdenite from > 700 mainly ore-bearing moderate- to high-temperature hydrothermal systems of different types. Our results are similar to but expand on those of earlier studies. Rhenium concentration in molybdenite has a lognormal distribution and varies systematically with type of geologic system, intrusive lithology, and Mo grade. The lowest-Re molybdenite occurs in greisens (geometric mean 1 ppm +/- a multiplicative standard deviation of 9), quartz vein-hosted W-Sn deposits (2 +/- 5 ppm), unmineralized granites and granodiorites (12 +/- 8 ppm), intrusion-related deposits (24 +/- 8 ppm), and porphyry W-Sn deposits (16 +/- 11 ppm). Rhenium is most enriched in molybdenites from volcanic sublimates (23,800 +/- 5 ppm), with skarn Fe and Au (560 +/- 5 ppm and 540 +/- 3 ppm respectively) and porphyry Cu and Cu-Au deposits next (470 +/- 4 and 430 +/- 7 ppm respectively). Among porphyries, skarns, and quartz vein-hosted deposits, Re is most highly concentrated in molybdenites from Cu and Au systems and its concentration decreases systematically through Cu-Mo, Mo, Sn, and W deposits. In nearly all cases, molybdenites from systems associated with intermediate igneous rocks contain more Re than molybdenites from systems of the same type with more felsic rock associations. The disparity between Re contents of molybdenite in felsic and intermediate systems is largest for porphyries, quartz vein-hosted, and skarn deposits and is near zero for subeconomic or barren granite and granodiorite Mo systems; felsic intrusion-related deposits have slightly higher molybdenite Re than their equivalents associated with intermediate intrusions. In most systems, molybdenite Re content does not correlate with metal grade, but may have an inverse correlation with Au grade in intrusion-related deposits (based on a small number of data points) and does exhibit a strong inverse correlation with deposit Mo grade. Dilution of Re through larger amounts (higher deposit grades) of molybdenite explains about 40% of this correlation, but the relative enrichment of Re in molybdenite from low-Mo deposits must also reflect some selective enrichment of Re/Mo in porphyry Cu systems compared to porphyry Mo systems. We found no evidence for secular increase or other systematic temporal variation in molybdenite Re content. The data regarding the use of molybdenite Re content as a proxy for mantle influence are ambiguous. Nearly all observed empirical correlations can be traced back to differences in redox state and sulfide concentration, the two geochemical factors identified here and by previous experimental work as the controlling influences on Re mobility under hydrothermal conditions. Hydrothermal systems with reducing conditions (W- and Sn-rich) tend to have low molybdenite Re even though compiled whole-rock data indicate that their source rocks have as much or more Re as those of more oxidized systems (e.g., Cu-rich). Vapor-phase exsolution, crustal assimilation, and mixing with external fluids may all enrich molybdenite Re concentrations in individual deposits and deposit types, but their extent and importance in overall hydrothermal concentration of Re is uncertain. Thus, it appears that the available molybdenite Re resource in an ore deposit largely depends on how the deposit's redox and sulfidation conditions have varied over time and space during the timespan of hydrothermal activity. Oxidized, high-sulfide conditions tend to concentrate Re in molybdenite, whereas reducing conditions tend to leave Re dispersed at low concentrations in the bulk rock.