Effect of chlorine on water incorporation in magmatic amphibole: experimental constraints with a micro-Raman spectroscopy approach

Amphibole represents an important repository of water (among other volatiles, e.g., chlorine and fluorine) in the lithosphere in all those environments characterized by the circulation of fluids and hydrous melts, such as subduction zones and subcontinental lithospheric mantle. Therefore, detailed knowledge of the mechanisms ruling water incorporation in amphibole is essential to assess the amount of water that can be fixed in the lithosphere by this mineral and, ultimately, gain a better insight into the deep water cycle. Water is incorporated into the structure of amphibole as hydroxyl (OH-), which is hosted in the anion site O(3), and the incorporation is mainly controlled by the oxo-substitution mechanism Ti-M(1)(1)4++O-O(3)(2)2-M(1)(Mg2+, Fe2+)(-1)+ (O(3))(OH-)(-2)(-). However, the fluids and melts circulating in the lithospheric mantle can be variably enriched in halogens (Cl- and F-) that can substitute OH- in the anion site O(3) of amphibole, thus potentially affecting its water budget. The aim of this study is to evaluate the effect of Cl on the oxo-substitution and the incorporation of water in amphibole. End-loaded piston cylinder experiments were conducted at pressure and temperature conditions compatible with the upper-mantle depth (1.4 GPa and 1015-1050 degrees C) in order to favor the crystallization of amphibole at equilibrium with the coexisting melt. Alkali basalt powder was used as starting material, and water doped with different contents of Cl was added to each experiment. Two ranges of oxygen fugacity (fO(2)) were investigated at Delta FMQ = -2.6 (log fO(2) [experiment] - log fO(2) [FMQ buffer]) and Delta FMQ = +1.7, where FMQ is fayalite-magnetite-quartz, in order to preliminarily identify the potential influence of the fO(2) on the water budget in amphibole. In this contribution, we propose a new method to quantify water in amphiboles using confocal micro-Raman spectroscopy. The H2O contents range from 2.20 +/- 0.10 wt % to 5.03 +/- 0.47 wt % in glasses and from 0.93 +/- 0.08 wt % to 1.50 +/- 0.12 wt % in amphiboles, resulting in a partition coefficient of water between amphibole and glass (Amph/LDH2O) ranging from 0.29 +/- 0.06 to 0.52 +/- 0.08. Our results show a positive correlation between the Cl content of amphibole (from 0.18 wt % to 0.88 wt %) and the Amph/LDH2O. This effect is ascribed to the incorporation of Cl at the anion site O(3) that influences the oxo-substitution mechanism by impeding the entrance of Ti4+ at the M(1) sites and thus preventing the amphibole dehydrogenation. The effect of Cl reported in this study, which is related to a change in the amphibole crystal structure, highlights that high Cl concentrations in magmatic systems favor the incorporation of water in amphibole rather than in the coexisting melt, although the exchange coefficient between (DH2O)-D-Amph/L and (DCl)-D-Amph/L supports a preferential incorporation of water over Cl in amphibole. Therefore, the presence of abundant Cl influences the hydration state of magmas evolving from upper-mantle conditions towards crustal roots with the crystallization of amphibole.