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Nuclear volume effects in kinetic isotope fractionation: A case study of mercury oxidation by chlorine species

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Abstract

It is well-known that the equilibrium isotope fractionation of mercury (Hg) includes classical mass-dependent fractionations (MDFs) and nuclear volume effect (NVE) induced mass-independent fractionations (MIFs). However, the effect of the NVE on these kinetic processes is not known. The total fractionations (MDFs + NVE-induced MIFs) of several representative Hg-incorporated substances were selected and calculated with ab initio calculations in this work for both equilibrium and kinetic processes. NVE-induced MIFs were calculated with scaled contact electron densities at the nucleus through systematic evaluations of their accuracy and errors using the Gaussian09 and DIRAC19 packages (named the electron density scaling method). Additionally, the NVE-induced kinetic isotope effect (KIE) of Hg isotopes are also calculated with this method for several representative Hg oxidation reactions by chlorine species. Total KIEs for 202Hg/198Hg ranging from − 2.27‰ to 0.96‰ are obtained. Three anomalous 202Hg-enriched KIEs (δ202Hg/198Hg = 0.83‰, 0.94‰, and 0.96‰,) caused by the NVE are observed, which are quite different from the classical view (i.e., light isotopes react faster than the heavy ones). The electron density scaling method we developed in this study can provide an easier way to calculate the NVE-induced KIEs for heavy isotopes and serve to better understand the fractionation mechanisms of mercury isotope systems.

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Acknowledgements

This paper is supported by Chinese NSF project (42130114), the strategic priority research program (B) of CAS (XDB41000000) and the pre-research Project on Civil Aerospace Technologies No. D020202 funded by Chinese National Space Administration (CNSA)

Funding

Chinese NSF project (42130114), the strategic priority research program (B) of CAS (XDB41000000) and the pre-research Project on Civil Aerospace Technologies (No. D020202) funded by Chinese National Space Administration (CNSA).

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Authors and Affiliations

  1. Research Center for Planetary Science, College of Earth and Planetary Sciences, Chengdu University of Technology, Chengdu, 610059, China

    Chenlu Yang & Yun Liu

  2. State Key Laboratory of Ore Deposit Geochemistry, Institute of Geochemistry, Chinese Academy of Sciences, Guiyang, 550081, China

    Yining Zhang & Yun Liu

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  1. Chenlu Yang
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Yining Zhang and Yun Liu selected topics; Yining Zhang conceived and designed methods; Chenlu Yang calculated data, analyzed and compiled the first draft; Yining Zhang and Yun Liu reviewed and revised the first draft.

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Correspondence to Yun Liu.

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Yang, C., Zhang, Y. & Liu, Y. Nuclear volume effects in kinetic isotope fractionation: A case study of mercury oxidation by chlorine species. Acta Geochim (2024). https://doi.org/10.1007/s11631-024-00691-5

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