Water solubility in pyrope to 100 kbar

The solubility and incorporation mechanism of water in natural, almost pure pyrope from Dora Maira, Western Alps was investigated. The infrared spectrum of the natural, untreated sample (58 ppm water) shows several exceptionally sharp bands in the OH-stretching region, including a single band at 3601.9 cm(-1) and a band system with main components at 3640.5, 3650.8 and 3660.6 cm(-1). High-temperature and high-pressure infrared spectra suggest that the two absorption features arise from almost free OH groups in sites with different compressibility and thermal expansivity, with the site causing the 3601.9 cm(-1) band being much stiffer. Pyrope samples were annealed in a piston-cylinder or multianvil apparatus for several days in the presence of excess water, excess SiO2 and excess Al2SiO5 to determine the equilibrium solubility of water in pyrope to 100 kbar. Total solubility increases with pressure, however, this is exclusively due to the high-frequency band system, while the intensity of the low-frequency band decreases with pressure. At 1000 degrees C and the oxygen fugacity of the Ni-NiO buffer, the bulk solubility can be described the equation c(OH) = Af(H2O)(0.5) exp(-P Delta V/RT) with A = 0.679 ppm/bar(0.5) and Delta V = 5.71 cm(3)/mol. This equation implies the incorporation of water in the crystal as isolated OH groups. With increasing temperature, solubility appears to decrease with Delta H = - 14 kJ/mol. At Fe-FeO buffer conditions, solubility is 30 to 50% lower than with the Ni-NiO buffer, suggesting that the incorporation of OH is not coupled to the reduction of Fe3+. Possibly, the 3601.9 cm(-1) band is associated with the tetrahedral OH B defect and the high-frequency system with the dodecahedral OH Li defect. Based on the experimentally established solubility model, it is estimated that garnet in a hot subducted slab will transport 170 ppm of water into the mantle beyond the breakdown limit of amphibole. In a cold slab, 470 ppm of water can be incorporated into garnet at the breakdown limit of phengite. These numbers imply that a significant fraction of the total water in the hydrosphere has been recycled into the mantle since the Proterozoic.