Physics and Chemistry of Minerals

, Volume 11, Issue 3, pp 113–124 | Cite as

A new solid state diffusion model applied to inverse zoning and diffusion rims in minerals

  • Friedemann Freund
  • Bruce V. King
Article
  • 59 Downloads

Abstract

Any oxide and silicate mineral which is nominally anhydrous but crystallized in the presence of H2O incorporates traces of H2O in solid solution. In the case of MgO it can be shown that OH pairs convert into H2+O22−. If the H2 molecules are lost, the O22−remain in the lattice as excess oxygen stabilized by excess cation vacancies. When the O22−anions decay either thermally or by decompression unbound O states (positive holes) are generated which lead to surface charges and subsurface space charge layers. Calculated space charge profiles are presented. O concentrations as small as 10–20 ppm suffice to create electric surface fields of the order of 4·107 V·m−1. The diffusion mechanism which derives from these premises incorporates novel features: the cation diffusion is coupled to the counterdiffusion of unbound and vacancy-bound O states. The cation diffusion is predicted to be very fast because first, it is field-enhanced (electrochemically driven) and second, it is not rate-limited by the intrinsic cation vacancy concentration nor by the counter-diffusion of other cations. The model may apply to cases of inverse zoning and diffusion rim formation in minerals under certain P-T conditions.

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. Abraham MM, Chen Y, Unruh WP (1974) Formation and stability of V and V A1 centers in MgO. Phys Rev B 9:1842–1852Google Scholar
  2. Ackermann L, Cemic L, Langer K (1983) Hydrogarnet substitution in pyrope: a possible location for “water” in the mantle. Earth Planet Sci Lett 62:208–214Google Scholar
  3. Aines RD, Rossman GR (1984) The hydrous component in garnets. Am Mineral, in pressGoogle Scholar
  4. Allen JC, Modreski PJ, Haygood PJ, Boettcher AL (1972) The role of water in the mantle of the earth: the stability of amphiboles and micas. 24th Int Geol Congr Sect 2:231–240Google Scholar
  5. Beran A, Putnis A (1983) A model of the OH positions in olivine, derived from infrared-spectroscopic investigations. Phys Chem Minerals 9:57–60Google Scholar
  6. Best MG (1974) Mantle-derived amphibole within inclusions in alkali basalt lavas. J Geophys Res 79:2107–2113Google Scholar
  7. Bianco AS, Taylor LA (1977) Applications of dynamic crystallization studies: lunar olivine normative basalts. Proc 8th Lunar Sci Conf: 1593–1610Google Scholar
  8. Black JRH, Kingery WD (1979) Segregation of aliovalent solutes adjacent surfaces in MgO. J Am Ceram Soc 62:176–178Google Scholar
  9. Boettcher AL, O'Neill JR, Windom KR, Stewart DC, Wilshire HG (1979) Metasomatism of the upper mantle and the genesis of kimberlites and alkali basalts, in: The Mantle Sample: Inclusions in Kimberlites and other Volcanics, Boyd FR, Meyer HOA, (eds) Amer Geophys Union Publ, Washington, 173–182Google Scholar
  10. Bottinga Y, Kudo A, Weill D (1966) Some observations on oscillatory zoning and crystallization of magmatic plagioclase. Am Mineral 51:792–806Google Scholar
  11. Brauer G (1965) Handbook of Preparative Inorganic Chemistry 2:1325, Academic Press, New York NYGoogle Scholar
  12. Breckenbridge RG (1950) Low frequency dispersion in ionic crystals containing foreign ions. J Chem Phys 18:913–926Google Scholar
  13. Buening DK, Buseck PR (1973) Fe-Mg lattice diffusion in olivine. J Geophys Res 78:6852–6862Google Scholar
  14. Burnham CW (1975) Water and magmas, a mixing model. Geochim Cosmochim Acta 39:1077–1084Google Scholar
  15. Burns RG (1970) Mineralogical applications of Crystal Field Theory. Cambridge Univ Press: 54Google Scholar
  16. Chiang UM, Hendricksen AF, Kingery WD, Finello D (1981) Characterization of grain-boundary segregation in MgO. J Am Ceram Soc 64:385Google Scholar
  17. Colbourn EA, Mackrodt WC, Tasker PW (1983) The segregation of calcium ions at the surface of magnesium oxide: theory and calculation. J Mat Sci 18:1917–1924Google Scholar
  18. Crank J (1975) The Mathematics of Diffusion. Clarendon Press, OxfordGoogle Scholar
  19. Deer WA, Howie RA, Zussman J (1962) Rock Forming Minerals. Longmans Publ, New York pp 10–13Google Scholar
  20. Dawson JB, Powell DG (1969) Mica in the upper mantle. Contrib Mineral Petrol 22:233–237Google Scholar
  21. Eshelby JD, Newey CWA, Pratt PL, Lidiard AB (1958) Charged dislocations and the strength of ionic crystals. Phil Mag 3:75–89Google Scholar
  22. Freund F (1981a) Mechanism of the water and carbon dioxide solubility in oxides and silicates and the role of O. Contrib Mineral Petrol 76:474–482Google Scholar
  23. Freund F (1981b) Charge transfer and O formation in high and ultrahigh pressure phase transitions. Bull Minéral 104:177–185Google Scholar
  24. Freund F (1984) Volume instabilities in the mantle as a possible source for kimberlite formation. in: Kimberlites, 1: Kimberlites and Related Rocks: 405–414, Kornprobst J (ed) Elsevier Sci Publ, AmsterdamGoogle Scholar
  25. Freund F, Oberheuser G (1984) Fluid components dissolved in olivine: a single crystal infrared study. J Geophys Res: submittedGoogle Scholar
  26. Freund F, Wengeler H, Martens R (1982) A deuterium — hydrogen fractionation mechanism in magnesium oxide. Geochim Cosmochim Acta 46:1821–1829Google Scholar
  27. Freund F, Wengeler H (1982) The infrared spectrum of OH-compensated defect sites in C-doped MgO and CaO single crystals. J Phys Chem Solids 43:129–145Google Scholar
  28. Freer R (1981) Diffusion in silicate minerals and glasses: a data digest and guide to the literature. Contrib Mineral Petrol 76:440–454Google Scholar
  29. Frenkel J (1946) Kinetic Theory of Liquids. Oxford Univ Press, Oxford p 36Google Scholar
  30. Guggenheim EA (1957) Thermodynamics. North Holland Publ, Amsterdam pp 272–276Google Scholar
  31. Gurney JJ, Harte B (1980) Chemical variations in upper mantle nodules from Southern African kimberlites. Philos Trans Roy Soc London 297:273–293Google Scholar
  32. Hanneman RE, Anthony TR (1969) Effects of non-equilibrium segregation on near-surface diffusion. Acta Metall 17:1133–1140Google Scholar
  33. Henderson B, Wertz JE (1977) Defects in the Alkaline Earth Oxides. Taylor and Francis Publ, LondonGoogle Scholar
  34. Hopper RW, Uhlmann DR (1974) Solute redistribution during crystallization at constant velocity and constant temperature. J Cryst Growth 21:203–215Google Scholar
  35. Irvine TN (1980) Magmatic infiltration metasomatism, double diffusion fractonal crystallization, and adcumulus growth in the Muskoxalintrusion and other layered intrusions, in: Physics of Magmatic Processes, Hargrave RB (ed) Princeton University Press, Princeton, NJ pp 325–383Google Scholar
  36. Jost W (1960) Diffusion in Solids, Liquids and Gases. Academic Press, New York pp 135–207Google Scholar
  37. Justice MG, Graham EK, Tressler RE, Tsong IST (1982) The effect of water on high-temperature deformation of olivine. Geophys Res Lett 9:1005–1008Google Scholar
  38. Kathrein H, Nagy J, Freund F (1984) O-ions and their relation to traces of H2O and CO2 in magnesium oxide: and EPR study. J Phys Chem Solids, in pressGoogle Scholar
  39. King BV, Freund F (1984) Surface charges and subsurface spacecharge distribution in magnesium oxides containing dissolved traces of water. Phys Rev B 29:5814–5824Google Scholar
  40. Kingery WD (1974) Plausible concepts necessary and sufficient for interpretation of ceramic grain-boundary phenomena, I. Grain-boundary characteristics, structure, and electrostatic potential; II. Solute segregation, grain boundary diffusion, and general discussion. J Amer Ceram Soc 57:1–8 & 74–83Google Scholar
  41. Kliewer KL, Koehler JS (1965) Space charge in ionic crystals, I. General approach with application to NaCl. Phys Rev 140A:1226–1240Google Scholar
  42. Klusman RW (1972) Calcium fractionation in zoned plagioclase from the Tabacco Root batholith, southwestern Montana. Chem Geol 9:45–56Google Scholar
  43. Knobel R (1983) Evolution of H-C-N-O gases from the surface of magnesium oxide and silicates. PhD Thesis (in German), Univ CologneGoogle Scholar
  44. Kröger FA (1964) The Chemistry of Imperfect Crystals. North Holland Publ, AmsterdamGoogle Scholar
  45. Kushiro I, Syono Y, Akimoto S (1967) Stability of phlogopite at high pressures and possible presence of phlogopite in the earth's mantle. Earth Planet Sci Lett 3:197–203Google Scholar
  46. Lehovec K (1953) Space-charge layer and distribution of lattice defects at the surface of ionic crystals. J Chem Phys 21:1123–1128Google Scholar
  47. Lifshits IM, Geguzin YaE (1965) Surface phenomena in ionic crystals. Sov Phys Solid State 7:44–52Google Scholar
  48. Lifshift IM, Kossevich AM, Geguzin YaE (1967) Surface phenomena and diffusion mechanism of the movements of defects in ionic crystals. J Phys Chem Solids 28:783–798Google Scholar
  49. Lloyd EE, Bailey DK (1975) Light element metasomatism of the continental mantle: the evidence and consequences. Phys Chem Earth 9:389–416Google Scholar
  50. Lofgren GE (1974) Temperature-induced zoning in synthetic plagioclase feldspar, in: The Feldspars. Mackenzie WS, Zussman J (eds) Manchester Univ Press, Manchester pp 362–375Google Scholar
  51. Lofgren GE (1980) Experimental studies on the dynamic crystallization of silicate melts. In: Physics of Magmatic Processes, Hargraves RB (ed) Princeton Univ Press, Princeton pp 487–551Google Scholar
  52. Marfunin AS (1979) Spectroscopy, Luminescence and Radiation Centers in Minerals. Springer Verlag Berlin, Heidelberg, New York pp 278–281Google Scholar
  53. Martens R, Gentsch H, Freund F (1976) Hydrogen release during the thermal decomposition of magnesium hydroxide to magnesium oxide. J Catalysis 44:366–372Google Scholar
  54. Martin RF, Donnay G (1972) Hydroxyl in the mantle. Am Mineral 57:554–570Google Scholar
  55. McCune RC, Wynblatt P (1983) Calcium segregation to a magnesium oxide (100) surface. J Amer Ceram Soc 66:111–117Google Scholar
  56. Pope SA, Guest MF, Hillier IH, Colbourn EA, Mackrodt WC, Kendrik J (1983) Ab initio study of the symmetric reaction path of H2 with a surface V center in magnesium oxide. Phys Rev B 28:2191–2198Google Scholar
  57. Schmalzried H (1981) Solid State Reactions. Verlag Chemie, Weinheim, pp 59–130Google Scholar
  58. Shaw HR (1964) Theoretical solubility of H2O in silicate melts: quasicrystalline models. J Geol 72:601–617Google Scholar
  59. Shinno I (1981) A Mössbauer study of ferric iron in olivine. Phys Chem Minerals 7:91–95Google Scholar
  60. Sibley DF, Vogel TA, Walker BM, Byerly G (1976) The origin of oscillatory zoning in plagioclase: a diffusion and growth controlled model. Am J Sci 276:275–284Google Scholar
  61. Sonder E, Sibley WA (1972) Defect creation by radiation in polar crystals. In: Defects in Crystalline Solids, Crawford JH, Slifkin LM (eds) Plenum Press, New York, pp 201–290Google Scholar
  62. Spear FS, Selverstone J (1983) Water exsolution from quartz: implications for the generation of metamorphic fluids. Geology 11:82–85Google Scholar
  63. Speit B, Lehmann G (1982) Radiation defects in feldspars. Phys Chem Minerals 8:77–82Google Scholar
  64. Sze SM (1969) Physics of Semiconductor Devices. Wiley-Interscience Publ, New YorkGoogle Scholar
  65. Stopler E (1982) Water in silicate glasses: an infrared spectroscopic study. Contrib Mineral Petrol 81:1–17Google Scholar
  66. Stromer JC (1973) Calcium zoning in olivine and its relationship to silica activity and pressure. Geochim Cosmochim Acta 37:1815–1821Google Scholar
  67. Strickland-Constable RF (1968) Kinetics and Mechanism of Crystallization. Academic Press, New York, pp 130–145Google Scholar
  68. Tomlinson AC, Henderson B (1969) Some studies of defects in calcium oxide, I. Impurity effects. J Phys Chem Solids 33:1793–1799Google Scholar
  69. Tossell JA (1983) A qualitative molecular orbital study of the stability of polyanions in mineral structures. Phys Chem Minerals 9:115–123Google Scholar
  70. Vance JA (1962) Zoning in igneous plagioclase: normal and oscillatory zoning. Amer J Sci 260:746–760Google Scholar
  71. Vannerberg NG (1962) Peroxides, superoxides, and ozonides of the metals of group Ia, IIa and IIb. Progr Inorgan Chem 4:125–195Google Scholar
  72. Vieten K (1980) The minerals of the volcanic rock association of the Siebengebirge, I: Clinopyroxene, 2. Variation of chemical composition of Ca-rich clinopyroxenes (salites) in the course of crystallization. Neues Jahrb Mineral Abh 140:54–88Google Scholar
  73. Vieten K (1982) The minerals of the volcanic rock association of the Siebengebirge, II: Olivines, 1. Idiocrysts and xenocrysts. Neues Jahrb Mineral Abh 145:183–199Google Scholar
  74. Weiblen PW, Morey GB (1976) Textural and compositional characterization of sulfide ores from the basal contact zone of the South Kawishiwi intrusion, Duluth complex, northeastern Minnesota. Proc 37th Ann Mining Symp Minn Geol Surv Reprint Ser 32Google Scholar
  75. Wells AF (1962) Structural Inorganic Chemistry. Clarendon Press, Oxford, pp 408–409Google Scholar
  76. Wilkins RWT, Sabine W (1967) Water content of some nominally anhydrous silicates. Am Mineral 58:508–516Google Scholar
  77. Wu CK (1980) Nature of incorporated water in hydrated silicate glass. J Am Ceram Soc 63:453–457Google Scholar
  78. Wyllie PJ (1970) Ultramafic rocks and the upper mantle. Mineral Soc Am Spec Paper 3:3–32Google Scholar
  79. Wynblatt P, Ku RC (1977) Surface energy and solute strain energy effects in surface segregation. Surface Sci 65:511–531Google Scholar

Copyright information

© Springer-Verlag 1984

Authors and Affiliations

  • Friedemann Freund
    • 1
  • Bruce V. King
    • 1
  1. 1.Department of PhysicsArizona State UniversityTempeUSA

Personalised recommendations