Solubility of grossular, Ca3Al2Si3O12, in H2O–NaCl solutions at 800 C and 10 kbar, and the stability of garnet in the system CaSiO3–Al2O3–H2O–NaCl

The solubility and stability of synthetic grossular were determined at 800 C and 10 kbar in NaCl–H2O solutions over a large range of salinity. The measurements were made by evaluating the weight losses of grossular, corundum, and wollastonite crystals equilibrated with fluid for up to one week in Pt capsules and a piston-cylinder apparatus. Grossular dissolves congruently over the entire salinity range and displays a large solubility increase of 0.0053 to 0.132 molal Ca3Al2Si3O12 with increasing NaCl mole fraction (XNaCl) from 0 to 0.4. There is thus a solubility enhancement 25 times the pure H2O value over the investigated range, indicating strong solute interaction with NaCl. The Ca3Al2Si3O12 mole fraction versus NaCl mole fraction curve has a broad plateau between XNaCl = 0.2 and 0.4, indicating that the solute products are hydrous; the enhancement effect of NaCl interaction is eventually overtaken by the destabilizing effect of lowering H2O activity. In this respect, the solubility behavior of grossular in NaCl solutions is similar to that of corundum and wollastonite. There is a substantial field of stability of grossular at 800 C and 10 kbar in the system CaSiO3–Al2O3–H2O–NaCl. At high Al2O3/CaSiO3 bulk compositions the grossular + fluid field is limited by the appearance of corundum. Zoisite appears metastably with corundum in initially pure H2O, but disappears once grossular is nucleated. At XNaCl = 0.3, however, zoisite is stable with corundum and fluid; this is the only departure from the quaternary system encountered in this study. Corundum solubility is very high in solutions containing both NaCl and CaSiO3: Al2O3 molality increases from 0.0013 in initially pure H2O to near 0.15 at XNaCl = 0.4 in CaSiO3-saturated solutions, a >100-fold enhancement. In contrast, addition of Al2O3 to wollastonite-saturated NaCl solutions increases CaSiO3 molality by only 12%. This suggests that at high pH (quench pH is 11–12), the stability of solute Ca chloride and Na–Al ± Si complexes account for high Al2O3 solubility, and that Ca–Al ± Si complexes are minor. The high solubility and basic dissolution reaction of grossular suggest that Al may be a very mobile component in calcareous rocks in the deep crust and upper mantle when migrating saline solutions are present. 2007 Elsevier Ltd. All rights reserved.