First in situ Re-Os dating of molybdenite by LA-ICP-MS/MS

Abstract

Conventional dating of molybdenite (187Re-187Os) provides one of few options for direct dating of sulfide mineralization. Unfortunately, in situ dating of molybdenite is considered unreliable due to intra-granular decoupling of 187Re-187Os. In this study, we developed a new analytical protocol for studies of micron- to grain scale 187Re-187Os systematics in molybdenite. Online chemical separation using ICP-MS/MS technology enables in situ dating by β-decay systems (e.g., Rb-Sr and K-Ca in micas) using laser ablation. Here, the methodology is extended to the 187Re-187Os system, another β-decay system that cannot be resolved by mass spectrometry. Several reaction gases were evaluated, and production of OsCH2 by reaction with CH4 was found to produce strong separation of Os from Re. However, in contrast to the e.g., 87Rb-87Sr system, 1–2% of the parent isotope Re also reacted to ReCH2, leaving a significant interference. A mathematical correction of this remaining interference is possible, and 187Re-187Os (mass-shifted) can be measured accurately even for fairly extreme ratios. For laser ablation, standards were developed by pressing particulate pellets of conventionally dated molybdenite (Moly Hill and Merlin), because there are no appropriate reference materials available. Six natural molybdenite samples from a range of geological settings, containing > 10 ppm Re, were analyzed by 70 μm laser ablation spots, and ages were calibrated by analysis of molybdenite pellets. Contrary to our expectation, weighted average ages obtained were in agreement (within 1%) with conventional age determinations, with fairly good precision (from ~ 1 to 5% 2σ depending on Re concentration), suggesting limited or essentially nonexistent decoupling within crystals. Two important implications of this result are that decoupling Re-Os is not universal, and that our new analytical protocol is useful both for dating and for studies of decoupling. The benefit of in situ dating compared to conventional dating is, apart from lower cost and time consumption, the possibility of targeting smaller molybdenite crystals (≥ 100 μm) in thin sections and epoxy mounts. The youngest sample in the study is 920 Ma, but we see potential of dating significantly younger Re-rich molybdenite.