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Potassium-bearing clinopyroxene: a review of experimental, crystal chemical and thermodynamic data with petrological applications

Published online by Cambridge University Press:  05 July 2018

O. G. Safonov ,
L. Bindi  and
V. L. Vinograd
O. G. Safonov
Affiliation:
Institute of Experimental Mineralogy, Russian Academy of Science, Academician Ossipian str. 4, 142432, Russia Department of Geology, University of Johannesburg, Auckland Park, Johannesburg 2006, South Africa
L. Bindi*
Affiliation:
Museo di Storia Naturale, sezione di Mineralogia, Universitá degli Studi di Firenze, Via La Pira, 4, I-50121, Florence, Italy CNR – Istituto di Geoscienze e Georisorse, sezione di Firenze, Via La Pira, 4, I-50121, Florence, Italy
V. L. Vinograd
Affiliation:
Institute of Energy and Climate Research, Forschungszentrum Jülich GmbH 1, 52425 Jülich, Germany
*
*E-mail: luca.bindi@unifi.it
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Abstract

Available experimental data on chemical composition and crystal structure of K-bearing clinopyroxenes are compiled together with the results of atomistic simulations and thermodynamic calculations of mineral equilibria. It is shown that the limited solubility of K2O in clinopyroxene from crustal rocks cannot be ascribed to the strong non-ideality of mixing between diopside (CaMgSi2O6) and K-jadeite (KAlSi2O6) components. The more likely reason is the instability of the potassic endmember with respect to other K-bearing phases. As the volume effects of typical K-jadeite-forming reactions are negative, the incorporation of K in the clinopyroxene structure becomes less difficult at higher pressure. Atomistic simulations predict that the thermodynamic mixing properties of diopside-K-jadeite solid-solutions at high temperature approach those of a regular mixture with a relatively small positive excess enthalpy. The standard enthalpy of formation (ΔfH° = —2932.7 kJ/mol), the standard volume (V° = 6.479 J mol–1 bar–1) and the isothermal bulk modulus (K0 = 145 GPa) of K-jadeite were calculated from first principles, and the standard entropy (S° = 141.24 J mol–1 K–1) and thermal-expansion coefficient (α = 3.3 x 1CP–5 K–1) of the K-jadeite endmember were estimated using quasi-harmonic lattice-dynamic calculations based on a force-field model. The estimated thermodynamic data are used to compute compositions of K-bearing clinopyroxenes in diverse mineral assemblages within a wide P-T interval. The review substantiates the conclusion that clinopyroxene can serve as an effective container for K at upper-mantle conditions.

Keywords

clinopyroxenemantle rocksigneous geochemistryigneous mineralogypotassium
Type
Research Article
Information
Mineralogical Magazine , Volume 75 , Issue 4 , August 2011 , pp. 2467 - 2484
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2011

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References

Akaogi, M., Ito, E. and Navrotsky, A. (1989) Olivine-modified spinel transition in the system Mg2SiO4-Fe2SiO4: calorimetric measurements, thermochemi-cal calculation, and geophysical application. Journal of Geophysical Research, 94, 15671–15685.CrossRefGoogle Scholar
Arima, M. and Onuma, K. (1977) The solubility of alumina in enstatite and the phase equilibria in the join MgSiO3-MgAl2SiO6 at 10-25 kbar. Contributions to Mineralogy and Petrology, 61, 251–265.CrossRefGoogle Scholar
Benna, P., Chiari, G. and Bruno, E. (1987) Structural modifications in clinopyroxene solid solution: the Ca-Mg and Ca-Sr substitutions in the diopside structure. Mineralogy and Petrology, 36, 71—84.CrossRefGoogle Scholar
Bindi, L., Safonov, O.G., Litvin, Yu.A., Perchuk, L.L. and Menchetti, S. (2002) Ultrahigh potassium content in the clinopyroxene structure: an X-ray single-crystal study. European Journal of Mineralogy, 14, 929–934.CrossRefGoogle Scholar
Bindi, L., Safonov, O.G., Yapaskurt, V.O., Perchuk, L.L. and Menchetti, S. (2003) Ultrapotassic clino-pyroxene from the Kumdy-Kol microdiamond mine, Kokchetav Complex, Kazakhstan: occurrence, composition and crystal-chemical characterization. American Mineralogist, 88, 464—468.CrossRefGoogle Scholar
Bindi, L., Downs, R.T., Harlow, G.E., Safonov, O.G., Litvin, Yu.A., Perchuk, L.L. and Menchetti, S. (2006) Compressibility of synthetic potassium-rich clinopyroxene: In-situ high-pressure single-crystal X-ray study. American Mineralogist, 91, 802—808.CrossRefGoogle Scholar
Bishop, F.C., Smith, J.V. and Dawson, J.B. (1978) Na, K, P and Ti in garnet, pyroxene and olivine from peridotite and eclogite xenoliths from African kimberlites. Lithos 11, 155 — 173.CrossRefGoogle Scholar
Carpenter, M.A. (1980) Mechanisms of exsolution in sodic pyroxenes. Contributions to Mineralogy and Petrology, 71, 289–300.CrossRefGoogle Scholar
Chudinovskikh, L.T., Zharikov, V.A., Ishbulatov, R.A. and Matveev, Y.A. (2001) On the mechanism of incorporation of ultra-high amounts of potassium into clinopyroxene at high pressure. Doklady Earth Sciences, 380, 1–4.Google Scholar
Daniels, L.R.M. and Gurney, JJ. (1989) The chemistry of garnets, chromites and diamond inclusions from the Dokolwayo kimberlites, Kingdom of Swaziland. Pp. 1012—1021 in: Kimberlites and related rocks. Volume 2. Their Mantle/Crust Setting, Diamonds and Diamond Exploration (Ross, J., editor). Geological Society of Australia Special Publication, 14. Blackwell, Carlton, Australia.Google Scholar
Edgar, A.D. and Mitchell, R.H. (1997) Ultra high pressure-temperature melting experiments on an SiO2-rich lamproite from Smoky Butte, Montana: derivation of siliceous lamproite magmas from enriched sources deep in the continental mantle. Journal of Petrology, 38, 457–477.CrossRefGoogle Scholar
Edgar, A.D. and Vukadinovic, D. (1993) Potassium-rich clinopyroxene in the mantle: an experimental investigation of K-rich lamproite up to 60 kbar. Geochimica et Cosmochimica Ada, 57, 5063—5072.CrossRefGoogle Scholar
Erlank, A.J. and Kushiro, I. (1970) Potassium contents of synthetic pyroxenes at high temperatures and pressures. Carnegie Institution Washington Yearbook, 68, 267–271.Google Scholar
Foley, S.F. (1992) Petrological characterization of the source components of potassic magmas: geochem-ical and experimental constraints. Lithos, 28, 187–204.CrossRefGoogle Scholar
Foley, S.F., Yaxley, G.M., Rosenthal, A., Buhre, S., Kiseeva, E.S., Rapp, R.P. and Jacob, D.E. (2009) The composition of near-solidus melts of peridotite in the presence of CO2 and H2O between 40 and 60 kbar. Lithos, 112S, 274–283.CrossRefGoogle Scholar
Ghorbani, M.R. and Middlemost, E.A.K. (2000) Geochemistry of pyroxene inclusions from the Warrumbungle Volcano, New South Wales, Australia. American Mineralogist, 85, 1349—1367.CrossRefGoogle Scholar
Harlow, G.E. (1996) Structure refinement of natural K-rich diopside: the effect of K on the average structure. American Mineralogist, 81, 632—638.CrossRefGoogle Scholar
Harlow, G.E. (1997) K in clinopyroxene at high pressure and temperature: an experimental study. American Mineralogist, 82, 259–269.CrossRefGoogle Scholar
Harlow, G.E. (1999) Interpretation of Kcpx and CaEs in Clinopyroxene from Diamond Inclusions and Mantle Samples. Pp. 321—331 in: Proceedings of Seventh International Kimberlite Convention, volume I (Gurney, J.J., Gurney, J.L., Pascoe, M.D. and Richardson, S.H., editors). Redroof Design, Cape Town, South Africa.Google Scholar
Harlow, G.E. (2002) Diopside + F-rich phlogopite at high P and T: Systematics, crystal chemistry and stability of KMgF3, clinohumite and chondrodite. Geological Materials Research, 4, 1—28.Google Scholar
Harlow, G.E. and Davies, R. (2004) Status report on stability of K-rich phases at mantle conditions. Lithos, 77, 647–653.CrossRefGoogle Scholar
Harlow, G.E. and Veblen, D.R. (1991) Potassium in clinopyroxene inclusions from diamonds. Science, 251, 652–655.CrossRefGoogle ScholarPubMed
Hart, S. R. and Zindler, A. (1986) In search of a bulk-earth composition. Chemical Geology, 57, 247—267.CrossRefGoogle Scholar
Holland, T.J.B. and Powell, R. (1998) An internally-consistent thermodynamic data set for phases of petrological interest. Journal of Metamorphic Geology, 16, 309–343.CrossRefGoogle Scholar
Ikeda, K. and Yagi, K. (1972) Synthesis of kosmochlor and phase equilibria in the join CaMgSi2O6-NaCrSi2O6 . Contributions to Mineralogy and Petrology, 36, 63–72.CrossRefGoogle Scholar
Jagoutz, E., Palme, H., Baddenhausen, H., Blum, K., Cendales, M., Dreibus, G., Spettel, B., Lorenz, V. and Wanke H. (1979) The abundances of major, minor and trace elements in the Earth's mantle as derived from primitive ultramafic nodules. Pp. 2031—2050 in: Proceedings of the 10th Lunar and Planetary Science Conference, (Merrill, R.B. editor). Geochimica et Cosmochimica Acta Supplement 11. Pergamon Press, New York.Google Scholar
Jaques, A.L., O'Neill, H.St.C., Smith, C.B., Moon, I. and Chappell, B.W. (1990) Diamondiferous peridotite xenoliths from the Argyle (AK1) lamproite pipe, Western Australia. Contributions to Mineralogy and Petrology, 104, 255–276.CrossRefGoogle Scholar
Kaminsky, F.V., Zakharchenko, O.D., Griffin, W.L., Channer, DeR. D. M. and Khachatryan-Blinova, G.K. (2000) Diamond from the Guaniamo area, Venezuela. The Canadian Mineralogist, 38, 1347–1370.CrossRefGoogle Scholar
Konzett, J. and Fei, Y. (2000) Transport and storage of potassium in the Earth's upper mantle and transition zone: experimental study to 23 GPa in simplified and natural bulk compositions. Journal of Petrology, 41, 583–603.CrossRefGoogle Scholar
Konzett, J. andUlmer, P. (1999) The stability of hydrous potassic phases in lherzolitic mantle — an experimental study to 9.5 GPa in simplified and natural bulk compositions. Journal of Petrology, 40, 629–652.CrossRefGoogle Scholar
Konzett, J., Frost, D.J., Proyer, A. and Ulmer, P. (2008) The Ca-Eskola component in eclogitic clino-pyroxene as a function of pressure, temperature and bulk composition: an experimental study to 15 GPa with possible implications for the formation of oriented SiO2-inclusions in omphacite. Contributions to Mineralogy and Petrology, 155, 215–228.CrossRefGoogle Scholar
Liu, L. (1987) High-pressure transition of potassium aluminosilicates with an emphasis on leucite. Contributions to Mineralogy and Petrology, 95, 1–3.CrossRefGoogle Scholar
Luth, R.W. (1992) Potassium in clinopyroxene at high pressure: experimental constraints. EOS Transactions of the American Geophysical Union, 73, 608.Google Scholar
Luth, R.W. (1995) Potassium in clinopyroxene at high pressure. EOS Transactions of the American Geophysical Union, 76, F711.Google Scholar
Luth, R.W. (1997) Experimental study of the system phlogopite-diopside from 3.5 to 17 GPa. American Mineralogist, 82, 1198–1209.CrossRefGoogle Scholar
Matveev, Yu.A., Chudinovskikh, L.T. and Litvin, Yu.A. (2000) Formation of potassium-rich clinopyroxenes and carbonate-silicate melting relations in the K2(Ca,Mg)(CO3) 2-clinopyroxene-garnet system at 3.8—7.0 GPa: Modeling the genesis of diamond-bearing rocks of Kazakhstan metamorphic complex. Journal of Conference Abstracts VIII Symposium EMPG, Bergamo, 5 (1).Google Scholar
McDonough, W. F. and Sun, S.-S. (1995) The composition of the Earth. Chemical Geology, 120, 223–253.CrossRefGoogle Scholar
McDonough, W.F., Sun, S.-S., Ringwood, A.E., Jagoutz, E. and Hofmann, A.W. (1992) Potassium, rubidium, and cesium in the Earth and Moon and the evolution of the mantle of the Earth. Geochimica et Cosmochimica Acta, 56, 1001–1012.CrossRefGoogle Scholar
Mellini, M. and Cundari, A. (1989) On the reported presence of potassium in clinopyroxene from potassium-rich lavas: a transmission electron microscope study. Mineralogical Magazine, 53, 311—314.CrossRefGoogle Scholar
Mitchell, R.H. (1995) Melting experiments on a sanidine-phlogopite lamproite at 4—7 GPa and their bearing on the source of lamproitic magmas. Journal of Petrology, 36, 1455–1474.CrossRefGoogle Scholar
Modreski, P.J. and Boettcher, A.L. (1973) Phase relationships of phlogopite in the system K2O-MgO-CaO-Al2O3-SiO2-H2O to 35 kbars: a better model for mica in the interior of the Earth. American Journal of Sciences, 273, 385–414.Google Scholar
Newton, R.C., Charlu, T.V. and Kleppa, O.J. (1977) Thermochemistry of high pressure garnets and clinopyroxenes in the system CaO-MgO-Al2O3-SiO2 . Geochimica et Cosmochimica Acta, 41, 369–377.CrossRefGoogle Scholar
Okamoto, K. and Maruyama, S. (1998) Multi-anvil re-equilibration experiments of a Dabie Shan ultra-high pressure eclogite within the diamond-stability fields. Island Arc, 7, 52–69.CrossRefGoogle Scholar
Okamura, F.P., Ghose, S. and Ohashi, H. (1974) Structure and crystal chemistry of calcium Tschermack's pyroxene, CaAlAlSiO6 . American Mineralogist, 59, 549–557.Google Scholar
Papike, J.J. (1980) Pyroxene mineralogy of the Moon and meteorites. Pp 495—525 in: Pyroxenes (Prewitt, C.T., editor). Reviews in Mineralogy and Geochemistry, 7, Mineralogical Society of America, Washington D.C. Google Scholar
Perchuk, L.L., Safonov, O.G., Yapaskurt, V.O. and Barton, J.M., Jr. (2002) Crystal-melt equilibria involving potassium-bearing clinopyroxene as in-dicators of mantle-derived ultrahigh-potassic liquids: an analytical review. Lithos, 60, 89—111.CrossRefGoogle Scholar
Plá Cid, J., Nardi, L.V.S., Stabel, L.Z., Conceicao, R.V. and Balzaretti, N.M. (2003) High-pressure minerals in mafic microgranular enclaves: evidences for co-mingling between lamprophyric and syenitic magmas at mantle conditions. Contributions to Mineralogy and Petrology, 145, 444—459.CrossRefGoogle Scholar
Pokhilenko, N.P., Sobolev, N.V., Reutsky, V.N., Hall, A.E. and Taylor, L.A. (2004) Crystalline inclusions and C-isotope ratios in diamonds from the Snap Lake/King Lake kimberlite dyke system: evidence of ultradeep and enriched lithospheric mantle. Lithos, 77, 57–6.CrossRefGoogle Scholar
Prinz, M., Manson, D.V., Hlava, P.F. and Keil, K. (1975) Inclusions in diamonds: garnet lherzolite and eclogite assemblages. Physics and Chemistry of the Earth, 9, 797–815.CrossRefGoogle Scholar
Ricard, R.S., Harris, J.W., Gurney, J.J. and Cardoso, P. (1989) Mineral inclusions in diamonds from the Koffiefontein Mine. Geological Society of Australia Special Publications, 14, 1054–1062.Google Scholar
Safonov, O.G., Matveev, Y.A., Litvin, Y.A. and Perchuk, L.L. (2002) Experimental study of some joins of the system CaMgSi2O6-(Ca,Mg)3Al2Si3O12-KAlSi2O6-K2(Ca,Mg)(CO3)2 at 5-7 GPa in relation to the genesis of garnet-clinopyroxene-carbonate rocks of the Kokchetav Complex (northern Kazakhstan). Petrology, 10, 519–539.Google Scholar
Safonov, O.G., Litvin, Yu.A., Perchuk, L.L., Bindi, L. and Menchetti, L. (2003) Phase relations of potassium-bearing clinopyroxene in the system CaMgSi2O6-KAlSi2O6 at 7 GPa. Contributions to Mineralogy and Petrology, 146, 120—133.CrossRefGoogle Scholar
Safonov, O.G., Litvin, Y.A. and Perchuk, L.L. (2004) Synthesis of omphaeites and isomorphic features of clinopyroxenes in the system CaMgSi2O6-NaAlSi2O6-KAlSi2O6 . Petrology, 12, 84–97.Google Scholar
Safonov, O.G., Perchuk, L.L., Litvin, Yu.A. and Bindi, L. (2005a) Phase relations in the CaMgSi2O6-KAlSi3O8 join at 6 and 3.5 GPa as a model for formation of some potassium-bearing deep-seated mineral assemblages. Contributions to Mineralogy and Petrology, 149, 316–337.CrossRefGoogle Scholar
Safonov, O.G., Perchuk, L.L. and Litvin, Yu.A. (20056) Equilibrium K-bearing clinopyroxene-melt as a model for barometry of mantle-derived mineral assemblages. Russian Geology and Geophysics, 46, 1318–1334.Google Scholar
Safonov, O.G., Perchuk, L.L. and Litvin, Yu.A. (2006) Effect of carbonates on crystallization and composition of potassium-bearing clinopyroxene at high pressures. Doklady Earth Sciences, 408, 580—585.CrossRefGoogle Scholar
Schmidt, M.W. (1996) Experimental constraints on recycling potassium from subducted oceanic crust. Science, 272, 1927–1930.CrossRefGoogle ScholarPubMed
Schmidt, M.W. and Poli, S. (1998) Experimentally based water budgets for dehydrating slabs and consequences for arc magma generation. Earth and Planetary Science Letters, 163, 361—379.CrossRefGoogle Scholar
Shannon, R.D. (1976) Revised effective ionic radü and systematic studies of interatomic distances in halides and chalcogenides. Ada Crystallographica, A32, 751–767.Google Scholar
Shimizu, N. (1971) Potassium content of synthetic clinopyroxenes at high pressures and temperatures. Earth and Planetary Science Letters, 11, 374—380.CrossRefGoogle Scholar
Sobolev, N. V. (1977) Deep-seated inclusions in kimberlites and the problem of the composition of the upper mantle. AGU, Washington, 279 pp. [Translated from the Russian edition, 1974].CrossRefGoogle Scholar
Sobolev, N.V. and Shatsky, V.S. (1990) Diamond inclusions in garnets from metamorphic rocks: a new environment for diamond formation. Nature, 343, 742–746.CrossRefGoogle Scholar
Sobolev, N.V., Yefimova, E.S., Channer, D. M. DeR., Anderson, P.F.N. and Barron, K.M. (1998) Unusual upper mantle beneath Guaniamo, Guyana Shield, Venezuela: evidence from diamond inclusions. Geology, 26, 971–974.2.3.CO;2>CrossRefGoogle Scholar
Spandler, C., Yaxley, G., Green, D. H. and Rosenthal, A. (2008) Phase relations and melting of anhydrous K-bearing eclogite from 1200 to 1600°C and 3 to 5 GPa. Journal of Petrology, 49, 771.CrossRefGoogle Scholar
Stachel, T., Brey, G.P. and Harris, J.W. (2000) Kankan diamonds (Guinea) I: from the lithosphere down to the transition zone. Contributions to Mineralogy and Petrology, 140, 1–15.CrossRefGoogle Scholar
Swanson, D.K. and Prewitt, C.T. (1983) The crystal structure of K2SiVISi3 vO9 . American Mineralogist, 68, 581–585.Google Scholar
Thomsen, T.B. and Schmidt, M.W. (2008) Melting of carbonated pelites at 2.5—5.0 GPa, silicate—carbonatite liquid immiscibility, and potassium—carbon metasomatism of the mantle. Earth and Planetary Science Letters, 267, 17—31.CrossRefGoogle Scholar
Tronnes, R.G. (2002) Stability range and decomposition of potassic richterite and phlogopite end members at 5 — 15 GPa. Mineralogy and Petrology, 74, 129–148.Google Scholar
Tsuruta, K. and Takahashi, E. (1998) Melting study of an alkali basalt JB-1 up to 12.5 GPa: behavior of potassium in the deep mantle. Physics of the Earth and Planetary Interiors, 107, 119–130.CrossRefGoogle Scholar
Vinograd, V.L. (2002) Thermodynamics of mixing and ordering in the diopsidejjadeite system: I. A CVM model. Mineralogical Magazine, 66, 513—536.Google Scholar
Vinograd, V.L., Safonov, O.G., Wilson, D.J., Bindi, L., Gale, I.D., Perchuk, L.L. and Winkler, B. (2010) Thermodynamics of diopside-K-jadeite, CaMgSi2O6-KAlSi2O6, solid solution from quantum mechanical and static lattice energy calculations. Petrology, 18, 447–459.CrossRefGoogle Scholar
Wang, W. and Takahashi, E. (1999) Subsolidus and melting experiments of a K-rich basaltic composition to 27 GPa: Implication for behavior of potassium in the mantle. American Mineralogist, 84, 357—361.CrossRefGoogle Scholar
Wood, B.J. and Henderson, C.M.B. (1978) Compositions and unit-cell parameters of synthetic non-stoichiometric tschermakitic clinopyroxenes. American Mineralogist, 63, 66—72.Google Scholar
Wood, B.J. and Nichols, J. (1978) The thermodynamic properties of reciprocal solid solutions. Contributions to Mineralogy and Petrology, 66, 389–400.CrossRefGoogle Scholar
Wood, B.J., Holland, T.J.B., Newton, R.C. and Kleppa, O.J. (1980) Thermochemistry of jadeite-diopside pyroxenes. Geochimica et Cosmochimica Ada, 44, 1363–1371.CrossRefGoogle Scholar
Yong, W., Dachs, E., Withers, A.C. and Essene, E.J. (2006) Heat capacity and phase equilibria of hollandite polymorph of KAlSi3O8. Physics and . Chemistry of Minerals, 33, 167—177.Google Scholar