^1,2Yankun Di,²Qing-Zhu Yin,³François L.H. Tissot,^1,4Yuri Amelin
Geochimica et Cosmochimica Acta (in Press) Open Access Link to Artile [https://doi.org/10.1016/j.gca.2024.06.012]
¹Research School of Earth Sciences, Australian National University, Acton, ACT 2601, Australia
²Department of Earth and Planetary Sciences, University of California Davis, Davis, CA 95616, USA
³The Isotoparium, Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, CA 91125, USA
⁴Korea Basic Science Institute, Building 202, 162 YeonGu DanJi-ro, Ochang, Cheongwon, Cheongju, Chungbuk 28119, Republic of Korea
Copyright Elsevier

We introduce a new isotope chronological model in which the natural mass-dependent isotopic fractionation effects of the radioactive (“parent”) and radiogenic (“daughter”) elements are systematically and rigorously considered. Using this model, we show that internally-normalized radiogenic isotopic ratios, commonly determined for daughter elements such as Sr, Nd, Cr, Ni, Hf, W, and Os, are dependent on the extent of natural isotopic fractionation of the daughter and parent elements at the time of system closure. This dependence indicates that (1) in two samples derived from the same isotopically homogeneous source at the same time and with identical radiogenic ingrowth over time, the present-day internally-normalized radiogenic isotope ratios would be different if they were initially fractionated to different degrees, and (2) if different internally-normalized radiogenic isotopic ratios are observed for two co-genetic objects, the difference between them would include contributions from both radiogenic ingrowth and natural isotopic fractionation. Consequently, the isochron dating equations employed in traditional chronological studies will yield inaccurate results when significant natural isotopic fractionation are present among the studied samples. Modified isochron equations that can be used to retrieve correct chronological information from isotopically-fractionated samples are presented. These theoretical considerations are applied to the 87Rb–87Sr, 147Sm–143Nd, and 146Sm–142Nd isotope systems of calcium–aluminium-rich inclusions (CAIs), a set of samples that have undergone significant natural Sr, Nd, and Sm isotope fractionation during their formation. The large natural Sr isotope fractionation (up to ca. 5.3 ‰ for 88Sr/86Sr) in fine-grained CAIs can generate analytically well-resolvable biases (>120 ppm) in the internally-normalized 87Sr/86Sr ratios and lead to significant scatters of their 87Rb–87Sr isochron (in conjunction with scatters induced by open-system disturbances). The 87Rb–87Sr systems of coarse-grained CAIs, on the contrary, are essentially not affected by natural Sr isotopic fractionation due to their much subdued fractionation degrees, resulting in a more robust isochron. Similarly, the large natural Nd (up to ca. 4.0 ‰ for 146Nd/144Nd) and Sm (up to ca. 7.1 ‰ for 152Sm/148Sm) isotopic fractionation in fine-grained CAIs can induce significant scatters of the 147Sm–143Nd isochron if the natural fractionation followed the kinetic or power law, and 146Sm–142Nd isochron if the natural fractionation followed the equilibrium, Rayleigh, or power law. This implies that when studying radioactive isotope systems in objects whose daughter and parent elements can undergo significant isotope fractionation in nature, accompanying stable isotope analyses are necessary for accurate chronological interpretations.

¹Le Zhang,¹Cheng-Yuan Wang,²Hai-Yang Xian,¹Jintuan Wang,¹Yan-Qiang Zhang,³Zhian Bao,¹Mang Lin,¹Yi-Gang Xu
Geochimica et Cosmochimica Acta (in Press) Link to Article [https://doi.org/10.1016/j.gca.2024.06.019]
¹State Key Laboratory of Isotope Geochemistry and CAS Centre for Excellence in Deep Earth Science Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640, China
²CAS Key Laboratory of Mineralogy and Metallogeny/Guangdong Provincial Key Laboratory of Mineral Physics and Materials, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640, China
³State Key Laboratory of Continental Dynamics, Department of Geology, Northwest University, Xi’an 710069, China
Copyright Elsevier

Impact glasses are abundant in the lunar regolith, and Mg isotopes have the potential to trace components from various lunar crustal reservoirs, which have recently been shown to exhibit large Mg isotopic fractionations. However, it remains unclear whether Mg isotopic fractionation occurs during the formation of impact glasses. In this study, we report in situ Mg isotopic and elemental compositional data for agglutinatic glasses returned by the Chang’e 5 mission and obtained using the laser ablation split stream technique. Vesicular textures, Fe–Ni alloys, tiny Fe droplets, and high Ni contents suggest the studied agglutinatic glasses had an impact origin. The agglutinatic glasses exhibit large Mg isotopic fractionation, with δ26Mg values ranging from −1.36 ‰ to −0.01 ‰. The lack of correlations between δ26Mg values, Ni contents, and ratios between volatile and relatively refractory elements (K/La, Rb/Sr, and Ce/Pb) indicate the addition of a meteoritic component and evaporation was not the major process responsible for the measured Mg isotopic variations. In fact, the MgO profiles and correlations between δ26Mg and MgO, Na2O, Sc, Sr, CaO/Al2O3, and δEu reflect Mg isotopic fractionation caused by Mg diffusion from a region with high Mg contents (i.e., more melted pyroxene) to one with lower contents (i.e., more melted plagioclase). Diffusion modeling shows that the duration of diffusion was less than a fraction of a second. Our results indicate that chemical diffusion can produce large Mg isotopic fractionation in impact glasses on a scale of at least tens of microns, and that isotopic fractionation driven by chemical diffusion needs to be considered when the Mg isotopic compositions of impact glasses are used to identify different lunar rock reservoirs.