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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 Os (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. However, dating of molybdenite is hindered by several analytical complications and is only performed in highly specialized labs.
The youngest sample in the study is 920 Ma, but we see potential of dating significantly younger Re-rich molybdenite.) is the most attractive target for Re-Os dating due to high partitioning of Re, negligible “common” Os, and resistance to metamorphic resetting (Stein et al. The main problem is that the mass difference between Os cannot be resolved by mass spectrometry, and chemical separation of these isotopes is comparatively difficult. In situ dating of molybdenite by Re-Os using laser ablation (LA) multicollector (MC), or quadrupole (Q) inductively coupled plasma mass spectrometry (ICP-MS) has been attempted on very old samples, but the correction for the overlap of Os is rather extreme, and matrix-matched standardization was unavailable (Košler et al. With the introduction of ICP tandem mass spectrometry (MS/MS), it has become possible to control a range of isobaric interferences previously out of reach of quadrupole ICP-MS (Bolea-Fernandez et al. Several β-decay couples (Ca) are able to separate during analysis with the help of a range of reaction gases, allowing in situ dating of Rb (and K)-rich minerals (Zack and Hogmalm 2016; Hogmalm et al. Effective separation is possible because the daughter isotope reacts with a reaction gas and is measured in the so-called mass-shift mode, while the parent isotope does not react and is measured on-mass.Additionally, decoupling of Re and Os within molybdenite crystals has been reported, especially in older and coarser grains, which means that extra care has been urged in sample preparation (Selby and Creaser 2004; Stein et al. The same principle can potentially also be applied to the Re-Os system, since methane (CHOs ratios in molybdenite.In the absence of accessible Re-Os standards, homogeneous in both Re and Os, new reference material need to be developed to enable in situ Re-Os dating.