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Li+ speciation and the use of 7Li/6Li isotope ratios for ancient climate monitoring
Bogatko, S.; Claeys, P.; De Proft, F.; Geerlings, P. (2013). Li+ speciation and the use of 7Li/6Li isotope ratios for ancient climate monitoring. Chem. Geol. 357: 1-7.
In: Chemical Geology. Elsevier: New York; London; Amsterdam. ISSN 0009-2541; e-ISSN 1872-6836, more
Peer reviewed article  

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Author keywords
    Aqueous lithium; Isotope fractionation; Ancient climate; Densityfunctional theory; Carbonate formation

Authors  Top 
  • Bogatko, S.
  • Claeys, P., more
  • De Proft, F.
  • Geerlings, P., more

    We have carried out a theoretical study of aqueous Li+ speciation including effects of ligand coordination, temperature and solution pH. We have calculated the isotope exchange equilibrium constant, K-OH-H2O(7/6LI), associated with the Li acid/base equilibrium and can constrain it to positive values. The consequences of this species dependent isotope fractionation are then studied using a model for Li-Carbonate coordination. We define an effective isotope fractionation, (eff)Delta Li-7/6(CO3)-H2O(2-), to model temperature and pH induced changes in Li isotope fractionation associated with the formation of Li-Carbonate species. We predict that, under normal oceanic conditions, (eff)Delta Li-7/6(CO3)-H2O(2-) is not sensitive to pH indeed but may be significantly influenced (on the order of 12 parts per thousand) by temperature. Since the isotope ratios found in Li containing calcium carbonate shells show no indications of variation in isotopic composition, we conclude that the mechanism by which Li is incorporated to this material is not dependent on aqueous Li speciation.

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