Minerals (Sep 2019)

The K<sub>2</sub>CO<sub>3</sub>–CaCO<sub>3</sub>–MgCO<sub>3</sub> System at 6 GPa: Implications for Diamond Forming Carbonatitic Melts

  • Anton V. Arefiev,
  • Anton Shatskiy,
  • Ivan V. Podborodnikov,
  • Konstantin D. Litasov

DOI
https://doi.org/10.3390/min9090558
Journal volume & issue
Vol. 9, no. 9
p. 558

Abstract

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Carbonate micro inclusions with abnormally high K2O appear in diamonds worldwide. However, the precise determination of their chemical and phase compositions is complicated due to their sub-micron size. The K2CO3−CaCO3−MgCO3 is the simplest system that can be used as a basis for the reconstruction of the phase composition and P−T conditions of the origin of the K-rich carbonatitic inclusions in diamonds. In this regard, this paper is concerned with the subsolidus and melting phase relations in the K2CO3−CaCO3−MgCO3 system established in Kawai-type multianvil experiments at 6 GPa and 900−1300 °C. At 900 °C, the system has three intermediate compounds K2Ca3(CO3)4 (Ca# ≥ 97), K2Ca(CO3)2 (Ca# ≥ 58), and K2Mg(CO3)2 (Ca# ≤ 10), where Ca# = 100Ca/(Ca + Mg). Miscibility gap between K2Ca(CO3)2 and K2Mg(CO3)2 suggest that their crystal structures differ at 6 GPa. Mg-bearing K2Ca(CO3)2 (Ca# ≤ 28) disappear above 1000 °C to produce K2Ca3(CO3)4 + K8Ca3(CO3)7 + K2Mg(CO3)2. The system has two eutectics between 1000 and 1100 °C controlled by the following melting reactions: K2Ca3(CO3)4 + K8Ca3(CO3)7 + K2Mg(CO3)2 → [40K2CO3∙60(Ca0.70Mg0.30)CO3] (1st eutectic melt) and K8Ca3(CO3)7 + K2CO3 + K2Mg(CO3)2 → [62K2CO3∙38(Ca0.73Mg0.27)CO3] (2nd eutectic melt). The projection of the K2CO3−CaCO3−MgCO3 liquidus surface is divided into the eight primary crystallization fields for magnesite, aragonite, dolomite, Ca-dolomite, K2Ca3(CO3)4, K8Ca3(CO3)7, K2Mg(CO3)2, and K2CO3. The temperature increase is accompanied by the sequential disappearance of crystalline phases in the following sequence: K8Ca3(CO3)7 (1220 °C) → K2Mg(CO3)2 (1250 °C) → K2Ca3(CO3)4 (1350 °C) → K2CO3 (1425 °C) → dolomite (1450 °C) → CaCO3 (1660 °C) → magnesite (1780 °C). The high Ca# of about 40 of the K2(Mg, Ca)(CO3)2 compound found as inclusions in diamond suggest (1) its formation and entrapment by diamond under the P−T conditions of 6 GPa and 1100 °C; (2) its remelting during transport by hot kimberlite magma, and (3) repeated crystallization in inclusion that retained mantle pressure during kimberlite magma emplacement. The obtained results indicate that the K−Ca−Mg carbonate melts containing 20−40 mol% K2CO3 is stable under P−T conditions of 6 GPa and 1100−1200 °C corresponding to the base of the continental lithospheric mantle. It must be emphasized that the high alkali content in the carbonate melt is a necessary condition for its existence under geothermal conditions of the continental lithosphere, otherwise, it will simply freeze.

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