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The phase diagrams of Na 2 CO 3 and K 2 CO 3 have been determined with multianvil (MA) and diamond anvil cell (DAC) techniques. In MA experiments with heating, γ -Na 2 CO 3 is stable up to 12 GPa and above this pressure transforms to P 6 3 /mcm-phase. At 26 GPa, Na 2 CO 3 - P 6 3 /mcm transforms to the new phase with a diffraction pattern similar to that of the theoretically predicted Na 2 CO 3 - P 2 1 /m. On cold compression in DAC experiments, γ -Na 2 CO 3 is stable up to the maximum pressure reached of 25 GPa. K 2 CO 3 shows a more complex sequence of phase transitions. Unlike γ Na 2 CO 3 , γ -K 2 CO 3 has a narrow stability field. At 3 GPa, K 2 CO 3 presents in the form of the new phase, called K 2 CO 3 -III, which transforms into another new phase, K 2 CO 3 -IV, above 9 GPa. In the pressure range of 9–15 GPa, another new phase or the mixture of phases III and IV is observed. The diffraction pattern of K 2 CO 3 -IV has similarities with that of the theoretically predicted K 2 CO 3 - P 2 1 /m and most of the diffraction peaks can be indexed with this structure. Water has a dramatic effect on the phase transitions of K 2 CO 3 . Reconstruction of the diffraction pattern of γ -K 2 CO 3 is observed at pressures of 0.5–3.1 GPa if the DAC is loaded on the air.

Potassic dolomitic melts are believed to be responsible for the metasomatic alteration of the shallow continental lithosphere. However, the temperature stability and range of compositions of these melts are poorly understood. In this regard, we performed experiments on phase relationships in the system K2CO3–CaCO3–MgCO3 at 3 GPa and at 750–1100 °C. At 750 and 800 °C, the system has five intermediate compounds: Dolomite, Ca0.8Mg0.2CO3 Ca-dolomite, K2(Ca≥0.84Mg≤0.16)2(CO3)3, K2(Ca≥0.70Mg≤0.30)(CO3)2 bütschliite, and K2(Mg≥0.78Ca≤0.22)(CO3)2. At 850 °C, an additional intermediate compound, K2(Ca≥0.96Mg≤0.04)3CO3)4, appears. The K2Mg(CO3)2 compound disappears near 900 °C via incongruent melting, to produce magnesite and a liquid. K2Ca(CO3)2 bütschliite melts incongruently at 1000 °C to produce K2Ca2(CO3)3 and a liquid. K2Ca2(CO3)3 and K2Ca3(CO3)4 remain stable in the whole studied temperature range. The liquidus projection of the studied ternary system is divided into nine regions representing equilibrium between the liquid and one of the primary solid phases, including magnesite, dolomite, Ca-dolomite, calcite-dolomite solid solutions, K2Ca3(CO3)4, K2Ca2(CO3)3, K2Ca(CO3)2 bütschliite, K2Mg(CO3)2, and K2CO3 solid solutions containing up to 24 mol % CaCO3 and less than 2 mol % MgCO3. The system has six ternary peritectic reaction points and one minimum on the liquidus at 825 ± 25 °C and 53K2CO3∙47Ca0.4Mg0.6CO3. The minimum point resembles a eutectic controlled by a four-phase reaction, by which, on cooling, the liquid transforms into three solid phases: K2(Mg0.78Ca0.22)(CO3)2, K2(Ca0.70Mg0.30)(CO3)2 bütschliite, and a K1.70Ca0.23Mg0.07CO3 solid solution. Since, at 3 GPa, the system has a single eutectic, there is no thermal barrier for liquid fractionation from alkali-poor toward K-rich dolomitic compositions, more alkaline than bütschliite. Based on the present results we suggest that the K–Ca–Mg carbonate melt containing ~45 mol % K2CO3 with a ratio Ca/(Ca + Mg) = 0.3–0.4 is thermodynamically stable at thermal conditions of the continental lithosphere (~850 °C), and at a depth of 100 km.

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