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Coupling of Li–Fe: Li Isotope Fractionation during Sorption onto Fe-Oxides

Zhang, Xu Yvon; Wilson, David J; Hamers, Maartje F; Pogge von Strandmann, Philip AE; Plümper, Oliver; King, Helen E; (2024) Coupling of Li–Fe: Li Isotope Fractionation during Sorption onto Fe-Oxides. ACS Earth and Space Chemistry 10.1021/acsearthspacechem.4c00205. (In press). Green open access

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Abstract

Chemical weathering processes play a key role in regulating the global climate over geological time scales. Lithium (Li) isotope compositions have proven to be a robust proxy for tracing weathering processes that produce secondary minerals, such as clays and oxides, with a focus often placed on Li adsorption to, or incorporation into, clay minerals. In addition, the interaction between Li and Fe-oxides has long been assumed and discussed based on field observations, but experimental constraints on this process are lacking. Here, we investigated the geochemical behavior of Li during its sorption onto individual Fe-oxides, including goethite, hematite, wüstite, and magnetite. With a point of zero charge at ∼7.7, poorly crystallized goethite nanoparticles take up ∼20% of dissolved Li over a pH range from ∼4 to ∼10, rising to ∼90% at pH ∼12. In contrast, the sorption of dissolved Li is insignificant for well-crystallized Fe-oxides (hematite, wüstite, magnetite, and goethite). This Li uptake by poorly crystallized goethite is likely attributed to dissolution and reprecipitation reactions at poorly crystalline goethite surfaces. The goethite particles preferentially take up light 6Li isotopes, resulting in an isotope fractionation of Δ7Lioxide-fluid ∼ −16.7 to −20.1‰. Overall, our study provides valuable data to better understand the processes occurring in highly weathered soil and sediment profiles that are rich in Fe-oxides, such as laterites. This research also emphasizes the significance of chemistry at mineral surfaces during mineral–water interactions and illuminates the mechanisms of large-scale Li extraction for future applications.

Type: Article
Title: Coupling of Li–Fe: Li Isotope Fractionation during Sorption onto Fe-Oxides
Open access status: An open access version is available from UCL Discovery
DOI: 10.1021/acsearthspacechem.4c00205
Publisher version: http://dx.doi.org/10.1021/acsearthspacechem.4c0020...
Language: English
Additional information: This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
Keywords: lithium, weathering, water−rock interaction, iron oxides, crystallinity
UCL classification: UCL
UCL > Provost and Vice Provost Offices > UCL BEAMS
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Earth Sciences
URI: https://discovery.ucl.ac.uk/id/eprint/10200859
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