Phase equilibria involving humite minerals in impure dolomitic limestones

The natural occurrence of critical assemblages among the phases clinohumite, calcite, dolomite, tremolite, forsterite, diopside, chlorite, and spinel in metamorphosed impure limestones, together with experimental and thermodynamic data, permits the calculation of phase equilibria governing the stability of clinohumite in terms of the variables P, T, and composition of a CO₂-H₂O-HF fluid. Equilibrium constant expressions are given for 23 equilibria that describe the stable phase relations between the above phases. Pure OH-clinohumite is considered to be metastable at relatively low pressures. The occurrence of clinohumite in natural marbles is the result of nonideal fluorine substitution which increases the stability of clinohumite. The stability field for clinohumite +calcite, governed primarily by the equilibrium 4forsterite+dolomite+H₂O = clinohumite+calcite +CO₂, expands to more CO₂-rich fluid compositions with increasing fluorine contents and decreasing total pressure. The F/(F+OH) ratio of clinohumite coexisting with calcite, dolomite, and forsterite is a sensitive indicator of the composition of the mixedvolatile fluid phase. The thermodynamic model is in good agreement with observed phase relations and can be used to gain useful information concerning the P-T-X _fluid conditions responsible for the formation of clinohumite.