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Carbonation and melting reactions in the system CaO–MgO–SiO2–CO2 at mantle pressures with geophysical and petrological applications

Abstract

Bowen's petrogenetic grid was based initially on a series of decarbonation reactions in the system CaO-MgO-SiO2-CO2 with starting assemblages including calcite, dolomite, magnesite and quartz, and products including enstatite, forsterite, diopside and wollastonite. We review the positions of 14 decarbonation reactions, experimentally determined or estimated, extending the grid to mantle pressures to evaluate the effect of CO2 on model mantle peridotite composed of forsterite(Fo)+orthopyroxene(Opx)+clinopyroxene(Cpx). Each reaction terminates at an invariant point involving a liquid, CO2, carbonates, and silicates. The fusion curves for the mantle mineral assemblages in the presence of excess CO2 also terminate at these invariant points. The points are connected by a series of reactions involving liquidus relationships among the carbonates and mantle silicates, at temperatures lower (1,100–1,300° C) than the silicate-CO2 melting reactions (1,400–1,600° C). Review of experimental data in the bounding ternary systems together with preliminary data for the system CaO-MgO-SiO2-CO2 permits construction of a partly schematic framework for decarbonation and melting reactions at upper mantle pressures. The key to several problems in the peridotite-CO2 subsystem is the intersection of a subsolidus carbonation reaction with a melting reaction at an invariant point near 24 kb and 1,200°C. There is an intricate series of reactions between 25 kb and 35 kb involving changes in silicate and carbonate phase fields on the CO2-saturated liquidus surfaces. Conclusions include the following: (1) Peridotite Fo+Opx+Cpx can be carbonated with increasing pressure, or decreasing temperature, to yield Fo+Opx+Cpx+Cd (Cd=calcic dolomite), Fo+Opx+Cd, Fo+Opx+Cm (Cm=calcic magnesite), and finally Qz+Cm. (2) Free CO2 cannot exist in subsolidus mantle peridotite with normal temperature distributions; it is stored as carbonate, Cd. (3) The CO2 bubbles in peridotite nodules do not represent free CO2 in mantle peridotite along normal geotherms. (4) CO2 is as effective as H2O in causing incipient melting, our preferred explanation for the low-velocity zone. (5) Fusion of peridotite with CO2 at depths shallower than 80 km produces basic magmas, becoming more SiO2-undersaturated with depth. (6) The solubility of CO2 in mantle magmas is less than about 5 wt% at depths to 80 km, increasing abruptly to about 40 wt% at 80 km and deeper. (7) Deeper than 80 km, the first liquids produced are carbonatitic, changing towards kimberlitic and eventually, at considerably higher temperatures, to basic magmas. (8) Kimberlite and carbonatite magmas rising from the asthenosphere must evolve CO2 at depths 100-80 km, which contributes to their explosive emplacement. (9) Fractional crystallization of CO2-bearing SiO2-undersaturated basic magmas at most pressures can yield residual kimberlite and carbonatite magmas.

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Wyllie, P.J., Huang, W.L. Carbonation and melting reactions in the system CaO–MgO–SiO2–CO2 at mantle pressures with geophysical and petrological applications. Contr. Mineral. and Petrol. 54, 79–107 (1976). https://doi.org/10.1007/BF00372117

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Keywords

  • Magnesite
  • Forsterite
  • Wollastonite
  • Asthenosphere
  • Enstatite