Magnesium isotope fractionation during natural travertine deposition from Baishuitai, SW China

Travertine samples deposited in Earth's surface environments can be used as an effective archive for paleo-climatic reconstruction. As a common element in carbonates, magnesium (Mg) and its isotopic composition in travertine could provide useful information for evaluating paleo-environment changes. In this study, we investigate the Mg isotope systematics in both endogenic travertines (mainly calcite) and spring/stream waters at Baishuitai, Yunnan, SW China. Our results show a systematic increase in δ²⁶Mg value from −1.37 to −1.26‰ for water samples downstream, but varied δ²⁶Mg values between −4.12 and −3.95‰ (average −4.02‰) for solid carbonates, thus a corresponding fractionation Δ²⁶Mg_{calcite-water} between −2.76 to −2.59‰ (mean value of −2.69‰). Therefore, the solid carbonates preferentially incorporate light Mg isotopes during travertine formation. More interestingly, the Mg distribution coefficient (K_Mg/Ca) between travertine and water exhibits two variation trends with the calcite deposition rate (R_p) along the canal, which can be explained by the change of calcite formation mechanism from direct nucleation to precipitation via amorphous calcium carbonate (ACC) intermediate. In the upper-stream, the direct nucleation of calcite results in the rapid incorporation of Mg ions into crystal lattice, while a relatively slow precipitation of calcite downstream would incorporate Mg via ACC formation pathway in a quasi-equilibrium pattern. This is consistent with the grain size distribution and crystal morphology observed under SEM. Our results show the important control of water Mg/Ca ratios on the calcite precipitation during travertine formation, and imply the potential and complexity of using Mg isotopes of travertine deposits to reconstruct paleo-environments.