Diamond-hosted inclusions provide information on the composition of the upper mantle. Many researchers found molecular CO2 inclusions, along with mineral and melt ones, in diamonds. Available experimental data on simplified systems suggest that CO2 fluid cannot occur in equilibrium with rock-forming mantle minerals. However, it was suggested that the complex composition of minerals contributes to their stabilization. This paper presents thermodynamic calculations for reactions of diopside–jadeite and pyrope–grossular solid solutions with CO2. It is shown that the formation of the solid solutions expands the stability field of CO2 fluid with eclogite minerals to lower temperatures, corresponding to the geothermal parameters of the continental lithosphere. The obtained relationships are confirmed by the results of preliminary experiments with model mixtures at high pressures and temperatures.
This is a preview of subscription content, access via your institution.
Buy single article
Instant access to the full article PDF.
Tax calculation will be finalised during checkout.
Y. V. Bataleva, A. N. Kruk, I. D. Novoselov, O. V. Furman, and Y. N. Palyanov, “Decarbonation reactions involving ankerite and dolomite under upper mantle P, T–parameters: Experimental modeling,” Minerals 10 (8), 715 (2020a).
Yu. V. Bataleva, I. D. Novoselov, A. N. Kruk, O. V. Furman, V. N. Reutsky, and Yu. N. Palyanov, “Experimental modeling of decarbonation resulting in Mg,Fe-garnets and CO2–fluid at the mantle P, T–parameters,” Russ. Geol. Geophys. 61 (S5–6), 650–662 (2020).
R. G. Berman, “Thermobarometry using multi–equilibrium calculations: a new technique with petrological application,” Can. Mineral. 29 (4), 833–855 (1991).
I. L. Chinn, “Cathodoluminescence properties of CO2–bearing and CO2–free diamonds from the George Creek K1 Kimberlite dyke,” Int. Geol. Rev. 37(3), 254–258 (1995).
J. A. Dalton and D. C. Presnall, “Carbonatitic melts along the solidus of model lherzolite in the system CaO–MgO–Al2O3–SiO2–CO2 from 3 to 7 GPa,” Contrib. Mineral. Petrol. 131, 123–135 (1998).
T. Gasparik, “Experimentally determined compositions of diopside–jadeite pyroxene in equilibrium with albite and quartz at 1200–1350°C and 15–34 kbar,” Geochim. Cosmochim. Acta 3 (49), 865–870 (1985).
G. D. Guthrie, D. R. Veblen, O. Navon, and G. R. Rossman, “Submicrometer fluid inclusions in turbid–diamond coats,” Earth Planet. Sci. Lett. 105 (1–3), 1–12 (1991).
T. Holland and R. Powell “An internally consistent thermodynamic data set for phases of petrological interest,” J. Metamorph. Geol. 16 (3), 309–343 (1998).
T. Holland and R. Powell, “Activity–composition relations for phases in petrological calculations: an asymmetric multicomponent formulation,” Contrib. Mineral. Petrol. 145, 492–501 (2003).
C. S. Kennedy and G. C. Kennedy, “The equilibrium boundary between graphite and diamond,” J. Geophys. Res. 81 (14), 2467–2470 (1976).
R. Knoche, R. J. Sweeney, and R. W. Luth, “Carbonation and decarbonation of eclogites: the role of garnet,” Contrib Mineral. Petrol. 135(4), 332–339 (1999).
A. M. Koziol and R. C. Newton, “Experimental determination of the reaction: Magnesite + enstatite = forsterite + CO2 in the ranges 6–25 kbar and 700–1100°C,” Am. Mineral. 83 (3–4), 213–219 (1998).
K. D. Litasov, “Physochemical conditions for melting in the Earth’s mantle containing a C–O–H–fluid (from experimental data),” Russ. Geol. Geophys. 52 (5), 475–492 (2011).
K. D. Litasov and A. F. Shatskiy, “MgCO3 + SiO2 reaction at pressures up to 32 GPa studied using in–situ X–ray diffraction and synchrotron radiation,” Geochem. Int. 57 (9), 1024–1033 (2019).
R. W. Luth, “Experimental determination of the reaction dolomite + 2 coesite = diopside + 2 CO2 to 6 GPa,” Contrib. Mineral. Petrol. 122 (1–2), 152–158 (1995).
O. Navon, I. Hutcheon, G. Rossman, and G. Wasserburg, “Mantle-derived fluids in diamond micro–inclusions,” Nature 335 (6193), 784–789 (1988).
A. Navrotsky, “Models of crystalline solutions,” In Thermodynamic Modeling of Geologic Materials: Minerals, Fluids, and Melts, Ed. by I. S. E. Carmichael and H. Eugster, (De Gruyter, 1987).
I. V. Podborodnikov, A. Shatskiy, A. V. Arefiev, A. Bekhtenova, and K. D. Litasov, “New data on the system Na2CO3–CaCO3–MgCO3 at 6 GPa with implications to the composition and stability of carbonatite melts at the base of continental lithosphere,” Chem. Geol. 515, 50–60 (2019).
I. V. Podborodnikov, A. Shatskiy, A. V. Arefiev, and K. D. Litasov, “Phase relations in the system Na2CO3–CaCO3–MgCO3 at 3 GPa with implications for carbonatite genesis and evolution,” Lithos 330–331, 74–89 (2019a).
N. P. Pokhilenko, A. M. Agashev, K. D. Litasov, and L. N. Pokhilenko, “Carbonatite metasomatism of peridotite lithospheric mantle: implications for diamond formation and carbonatite–kimberlite magmatism,” Russ. Geol. Geophys. 56 (1–2), 280–295 (2015).
H. N. Pollack and D. S. Chapman, “On the regional variation of heat flow, geotherms, and lithospheric thickness,” Tectonophysics 38, 279–296 (1977).
A. L. Ragozin, V. S. Shatsky, G. M. Rylov, and S. V. Goryainov, “Coesite inclusions in rounded diamonds from placers of the northeastern siberian platform,” Dokl. Earth Sci. 384 (4), 385–389 (2002).
A. L. Ragozin, V. S. Shatskii, and D. A. Zedgenizov, “New data on the growth environment of diamonds of the Variety V from placers of the northeastern Siberian Platform,” Dokl. Earth Sci. 425 (4), 527–531 (2009).
A. L. Ragozin, D. A. Zedgenizov, K. E. Kuper, and V. S. Shatsky, “Radial mosaic internal structure of rounded diamond crystals from alluvial placers of Siberian platform,” Mineral. Petrol. 110(6), 861–875 (2016).
M. Schrauder and O. Navon, “Solid carbon dioxide in natural diamond,” Nature 365 (6441), 42–44 (1993).
I. S. Sharygin, K. D. Litasov, A. F. Shatskiy, A. V. Golovin, E. Ohtani, and N. P. Pokhilenko, “Melting phase relations of the Udachnaya–East Group–I kimberlite at 3.0–6.5 GPa: experimental evidence for alkali–carbonatite composition of primary kimberlite melt and implication to mantle plumes,” Gondwana Res. 28 (4), 1391–1414 (2015).
I. S. Sharygin, K. D. Litasov, A. Shatskiy, O. G. Safonov, A. V. Golovin, E. Ohtani, and N. P. Pokhilenko, “Experimental constraints on orthopyroxene dissolution in alkali carbonate melts in the lithospheric mantle: implications for kimberlite melt composition and ascent,” Chem. Geol. 455, 44–55 (2017).
A. Shatskiy, K. D. Litasov, I. S. Sharygin, I. A. Egonin, A. M. Mironov, Y. N. Palyanov, and E. Ohtani, “The system Na2CO3–CaCO3–MgCO3 at 6 GPa and 900–1250°C and its relation to the partial melting of carbonated mantle,” High Pressure Res. 36 (1), 23–41 (2016).
A. Shatskiy, I. V. Podborodnikov, A. V. Arefiev, K. D. Litasov, A. D. Chanyshev, I. S. Sharygin, N. S. Karmanov, and E. Ohtani, “Effect of alkalis on the reaction of clinopyroxene with Mg–carbonate at 6 GPa: Implications for partial melting of carbonated lherzolite,” Am. Mineral. 102 (9), 1934–1946 (2017a).
A. Shatskiy, K. D. Litasov, I. S. Sharygin, and E. Ohtani, “Composition of primary kimberlite melt in a garnet lherzolite mantle source: constraints from melting phase relations in anhydrous Udachnaya–East kimberlite with variable CO2 content at 6.5 GPa,” Gondwana Res. 45, 208–227 (2017).
E. M. Smith, M. G. Kopylova, M. L. Frezzotti, and V. P. Afanasiev, “Fluid inclusions in Ebelyakh diamonds: Evidence of CO2 liberation in eclogite and the effect of H2O on diamond habit,” Lithos 216, 106–117 (2015).
A. A. Tomilenko, A. L. Ragozin, V. S. Shatskii, and A. P. Shebanin, “Variation in the fluid phase composition in the process of natural diamond crystallization,” Dokl. Earth Sci, 378 (6), 802–805 (2001).
B. J. Wood, T. Holland, R. C. Newton, and O. J. Kleppa, “Thermochemistry of jadeite–diopside pyroxenes,” Geochim. Cosmochim. Acta. 9 (44), 1363–1371 (1980).
P. J. Wyllie and W. Huang, “Peridotite, kimberlite, and carbonatite explained in the system CaO–MgO–SiO2–CO2,” Geology 3, 621–624 (1975).
G. M. Yaxley and G. P. Brey, “Phase relations of carbonate-bearing eclogite assemblages from 2.5 to 5.5 GPa: implications for petrogenesis of carbonatites,” Contrib. Mineral. Petrol. 146 (5), 606–619 (2004).
The study on a scanning electron microscope was carried out at the Center for Collective Use for Multielemental and Isotope Studies of the Siberian Branch, Russian Academy of Sciences.
This study was done on the state assignment for the Sobolev Institute of Geology and Mineralogy, Siberian Branch, Russian Academy of Sciences, and was supported by the Russian Foundation for Basic Research, project no. 21-55-14001. KDL was supported by the state assignment for the Institute for High Pressure Physics, Russian Academy of Sciences.
Translated by E. Kurdyukov
About this article
Cite this article
Vinogradova, Y.G., Shatskiy, A.F. & Litasov, K.D. Thermodynamic Analysis of Reactions of CO2 Fluid with Garnet and Clinopyroxene at 3–6 GPa. Geochem. Int. 59, 851–857 (2021). https://doi.org/10.1134/S0016702921080103
- thermodynamic calculations
- CO2 fluid
- upper mantle