Stable isotope fractionation by thermal diffusion through partially molten wet and dry silicate rocks

Water plays a fundamental role in affecting geochemical transport and physical properties of magmas. Here we show the previously undocumented behavior of water within partially molten silicate resting in a temperature gradient, producing O, Li and H isotope redistribution by thermal diffusion leading to enrichment of light isotopes at the hot end of the gradient. After weeks to months, fully molten as well as mostly crystalline portions of water-bearing experiments develop remarkably large isotope and chemical redistributions: up to 28‰ for δ18O, 144‰ for δD, and 18‰ for δ7Li. In contrast, long-term dry experiments develop smaller (∼5‰ δ18O) isotopic fractionations only in the hotter end where it is molten or partially molten. Isotope fractionation of oxygen is linearly related to temperature, and the magnitude of isotopic separation per °C is ∼2× larger for wet experiments than dry ones. We explain this by water de-polymerizing the silicate structure leading to a smaller size of diffusing SiOx fragments. The magnitude of isotope separation between the hot and cold ends for Li, Mg, Fe, O, and H isotopes increases linearly with ΔMheavy–light/Mlight. These relationships provide predictive tests for natural rocks and highlight the role of water in isotope and compositional redistribution during temperature gradient mediated processes. We discuss the implications to natural environments in which the lightest stable isotopes (H, Li, O) with the greatest ΔMheavy–light/Mlight and fastest diffusion coefficients are capable of achieving mass-dependent redistribution in a transient temperature gradient. These experiments underscore the importance of solution–reprecipitation in wet subsolidus systems and demonstrate that isotopic redistribution can be established ∼6 orders of magnitude quicker than by diffusion through a traditional silicate melt at higher temperature. This has important implications for timescales of natural isotope and chemical redistribution by thermal diffusion.