Subgrain-scale decoupling of Re and 187Os and assessment of laser ablation ICP-MS spot dating in molybdenite

Abstract

Reproducibility of Re-Os molybdenite ages depends on sample size and homogeneity, suggesting that Re and Os are decoupled within individual molybdenite crystals and do not remain spatially linked over time. In order to investigate the Re-Os systematics of molybdenite at the subgrain (micron) scale, we report LA-ICP-MS Re-Os ages for an Archean molybdenite crystal from Aittojärvi, Finland, analyzed in situ in a white aplite matrix. A related Aittojärvi molybdenite (A996D), in the form of a very fine-grained mineral separate, is used as one of our in-house NTIMS standards, and thus its age of 2760 ± 9 Ma is well established. Measurements of ( 187Re + 187Os)/ 185Re on micron scale spots along 200 μm traverses across the crystal yield a wide range of ages demonstrating that, in this case, microsampling of molybdenite does not produce geologically meaningful ages. Experimentation with mineral separations and sample size over a 7-yr period predicted that this would be the outcome. We suggest that 187Os is more likely to be the mobile species, based on its charge and ionic radius, and that 187Os becomes decoupled from parent 187Re with time on the micron and larger scale. Incompatible charge and ionic radius for Os ions formed during reduction of molybdenite-forming fluids may explain the widely observed absence of common (initial) Os in molybdenite. Geologically accurate ages for molybdenite can only be obtained for fully homogenized crystals (or crystal aggregates) so that any post-crystallization 187Re- 187Os decoupling is overcome. A growing number of geologically accurate ID-NTIMS 187Re- 187Os ages for homogenized molybdenite suggest that postcrystallization mobility of radiogenic 187Os must be limited to within the molybdenite mineral phase. We suggest that radiogenic 187Os may be stored in micron scale dislocations, kink bands, and delamination cracks produced by deformation, and that the unusual structure and deformation response of molybdenite results in an increased chemical stability in this mineral. Migration of 187Os into adjacent silicate phases is highly unlikely, but other contacting sulfides may take in Os. In an example from a Proterozoic skarn deposit at Pitkäranta (western Russia), we demonstrate minor loss of radiogenic 187Os from molybdenite and a corresponding gain in adjacent chalcopyrite such that the molybdenite age is not perceptibly disturbed, whereas the resulting chalcopyrite ages are impossibly old. Therefore, it is unadvisable to perform Re-Os analytical work on any sulfide in contact or intimate association with molybdenite. In addition to large errors in the age, if the isochron method is employed, initial 187Os/ 188Os ratios could be erroneously high, leading to seriously errant genetic interpretations.