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To investigate the substitution of Ti 4+  for Si 4+  on tetrahedral sites in clinopyroxene, a series of Ti- bearing clinopyroxene compositions was synthesized in the system CaO-MgO-SiO 2 -TiO 2  (CMST) at pressures from 1 atm to 2 GPa and temperatures from 800 to 1200 °C. Along the join CaMgSi 2 O 6 (diopside)-CaMgTiSiO 6 , clinopyroxene crystallizes, depending on coexisting phases, as binary solid solutions (diopside-CaMgTiSiO 6 ) or ternary solid solutions (diopside-CaMgTiSiO 6 - enstatite). The solubility of Ti increases with increasing temperature, whereas it decreases with increasing pressure. The binary clinopyroxene has an invariant composition (CaMgSi 2 O 6 ) 93 (CaMgTiSiO 6 ) 7  (mol%) corresponding to a Ti content of 2.6 wt% at 1000 °C and 1 atm. Magnesium substitutes in the M2 site in ternary clinopyroxene and its solubility mainly in­creases with increasing temperature. The substitution of Si 4+  by the larger Ti 4+  cation on tetrahedral sites causes a linear increase hi a, b, c, β, and V by 0.0020 Å, 0.0012 Å, 0.0016 Å, 0.01°, and 0.28 Å 3  per mol% CaMgTiSiO 6 , respectively.

The stability of clinopyroxene in the system CaO-MgO-SiO 2 -TiO 2 (CMST)