The effect of fluorine on the stability of wadsleyite: Implications for the nature and depths of the transition zone in the Earth's mantle

The Earth's mantle contains significant amounts of volatile elements, such as hydrogen (H), carbon (C) and the halogens fluorine (F), chlorine (Cl) and bromine (Br) and iodine (I). There is a wealth of knowledge about the global cycling of H and C, but there is only scant data on the concentrations of halogens in different Earth reservoirs and on the behavior of halogens during recycling in subduction zones. Here we focus on the storage potential of F in deeper parts of the Earth's mantle. The transition zone is a region in the Earth's mantle (410-660 km) known for its high water storage capacity, as the high pressure polymorphs of olivine, wadsleyite and ringwoodite are known to be able to incorporate several per-cent of water. In order to assess potential fractionation between water and F in the transition zone of the Earth's mantle, we set out to investigate the storage capacity of the halogen F in wadsleyite and olivine at transition zone conditions. Experiments were performed in a simplified mantle composition at temperatures from 1400 °C to 1900 °C and pressures from 17 up to 21 GPa in a multi anvil apparatus. The results show that F can shift the olivine-wadsleyite transition towards higher pressure. We find that F has an opposing effect to water, the latter of which extends the transition zone towards lower pressure. Moreover, the F storage capacity of wadsleyite is significantly lower than previously anticipated. F concentrations in wadsleyite range from 1470±60 μg/g to 2110±600 μg/g independent of temperature or pressure. The F storage capacity in wadsleyite is even lower than the F storage capacity of forsterite under transition zone conditions, and the latter can incorporate 3930±140 μg/g F under these conditions. Based on our data we find that the transition zone cannot be a reservoir for F as it is assumed to be for water. Furthermore, we argue that during subduction of a volatile-bearing slab, fractionation of water from F will occur, where water enters preferentially the transition zone and F remains in the peridotite of the lowermost upper mantle.