Contributions to Mineralogy and Petrology

, Volume 93, Issue 1, pp 46–55 | Cite as

The effect of fluorine on phase relationships in the system KAlSiO4-Mg2SiO4-SiO2 at 28 kbar and the solution mechanism of fluorine in silicate melts

  • Stephen F. Foley
  • Wayne R. Taylor
  • David H. Green
Article
Received:
Accepted:

Abstract

Phase relationships in the system kalsilite-forsterite-quartz with fluorine added by direct substitution for oxygen were examined at 28 kb. A large liquidus field for fluorphlogopite exists with approx. 4 wt% F added to the system and the thermal stability of phlogopite is increased by ∼300° C relative to the water saturated system. Fluorine expands the phase volume of enstatite relative to forsterite so that the peritectic point PHL+EN+FO+L, a model for melting of a phlogopite harzburgite, lies in the silica-undersaturated field. Experimental phlogopites have excess Si which correlates with F content and are Al-deficient. The high Si contents indicate solid solution with an end member intermediate between tri- and di-octahedral micas. Glasses with compositions analogous to partial melts from phlogopite harzburgite were examined by infrared spectroscopy in the mid- and far-IR regions. Results show that fluorine polymerises the melt by bonding with all the network modifying cations K, Mg and Al. At higher F contents, but still less than 1 wt%, tetrahedral KAlO2-groups are complexed by fluorine and removed from the aluminosilicate network simultaneously polymerising and increasing the Si/(Si+Al) ratio of the network. However, when HF rather than F is present, the overall effect will be to depolymerise melts due to the effect of OH released by dissolution of HF. The presence of abundant Si-F bonds is considered unlikely even in silica-rich magmas: the viscosity decrease characteristic of fluorine-bearing melts can be attributed to the formation of fluoride complexes.

Keywords

Fluorine Aluminosilicate Forsterite Phase Relationship Enstatite 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.
This is a preview of subscription content, log in to check access.

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. Allmann R (1971) Fluorine. In: Wedepohl KH (ed) Handbook of Geochemistry Section 9A, 6ppGoogle Scholar
  2. Aoki K, Ishikawa K, Kanisawa S (1981) Fluorine geochemistry of basaltic rocks from continental and oceanic regions and petrogenetic application. Contrib Mineral Petrol 76:53–59Google Scholar
  3. Bailey JC (1977) Fluorine in granitic rocks and melts: a review. Chem Geol 19:1–42Google Scholar
  4. Best MG, Henage LF, Adams JAS (1968) Mica peridotite, wyomingite, and associated potassic igneous rocks in northeastern Utah. Am Mineral 53:1041–1048Google Scholar
  5. Bottinga Y, Weill DF, Richet P (1981) Thermodynamic modeling of silicate melts. In: RC Newton, A Navrotsky, BJ Wood (eds) Thermodynamics of minerals and melts: Adv Phys Geochem 1:207–245Google Scholar
  6. Brey GP, Green DH (1975) The role of CO2 in the genesis of olivine melilitite. Contrib Mineral Petrol 49:93–103Google Scholar
  7. Buerger MJ (1948) The structural nature of the mineraliser action of fluorine and hydroxyl. Am Mineral 33:744–746Google Scholar
  8. Burnham CW (1975) Water and magmas: a mixing model. Geochim Cosmochim Acta 39:1077–1084Google Scholar
  9. Burnham CW (1979a) The importance of volatile constituents. In: HS Yoder (ed) The Evolution of the Igneous Rocks: Fiftieth Anniversary perspectives, pp 439–482. Princeton University Press, Princeton, New JerseyGoogle Scholar
  10. Burnham CW (1979b) Magmas and hydrothermal fluids. In: HL Barnes (ed) Geochemistry of hydrothermal ore deposits. pp 71–136 WileyGoogle Scholar
  11. Collins WJ, Beams SD, White AJR, Chappell BW (1982) Nature and origin of A-type granites with particular reference to south-eastern Australia. Contrib Mineral Petrol 80:189–200Google Scholar
  12. de Jong BHWS, Brown GE (1980) Polymerisation of silicate and aluminate tetrahedra in glasses, melts, and aqueous solutions — I. Electronic structure of H6Si2O7, H6SiAlO7−, and H6Al2O72−. Geochim Cosmochim Acta 44:491–511Google Scholar
  13. Dingwell DB, Mysen BO (1985) The effect of water and fluorine on the viscosity of albite melt at high pressure: a preliminary investigation. Earth Planet Sci Lett 74:266–274Google Scholar
  14. Dingwell DB, Scarfe CM, Cronin DJ (1985) The effect of fluorine on viscosities in the system Na2O-Al2O3-SiO2: implications for phonolites, trachytes and rhyolites. Am Mineral 70:80–87Google Scholar
  15. Dupree E, Pettifer RF (1984) Determination of the Si-O-Si bond angle distribution in vitreous silica by magic angle spinning NMR. Nature 308:523–525Google Scholar
  16. Eggler DH (1974) Effect of CO2 on the melting of peridotite. Car-negie Inst Washington Yearb 73:215–224Google Scholar
  17. Eggler DH, Rosenhauer M (1978) Carbon dioxide in silicate melts, II, Solubilities of CO2 and H2O in CaMgSi2O6 (diopside) liquids and vapors at pressures to 40 kb. Am J Science 278:64–94Google Scholar
  18. Ferraro JR, Manghnani MH (1972) Infrared absorption spectra of sodium silicate glasses at high pressures. J Appl Phys 43:4595–4599Google Scholar
  19. Furukawa T, Fox KE, White WB (1981) Raman spectroscopic investigation of the structure of silicate glasses. III. Raman intensities and structural units in sodium silicate glasses. J Chem Phys 75:3226–3237Google Scholar
  20. Gallo F, Giametti F, Venturelli G, Vernia L (1984) The kamafugitic rocks of San Venanzo and Cupaello, central Italy. N Jahrb Mineral Mh 5:198–210Google Scholar
  21. Glyuk DS, Anfilogov VN (1973) Phase equilibria in the system granite-H2O-HF at a pressure of 1000 kg/cm2. Geochem Int 10:321–325Google Scholar
  22. Green DH, Liebermann RC (1976) Phase equilibria and elastic properties of a pyrolite model for the oceanic upper mantle. Tectonophysics 32:61–92Google Scholar
  23. Green TH (1981) Synthetic high-pressure micas compositionally intermediate between the dioctahedral and trioctahedral mica series. Contrib Mineral Petrol 78:452–458Google Scholar
  24. Hazen RM, Finger LW, Velde D (1981) Crystal structure of a silica- and alkali-rich trioctahedral mica. Am Mineral 66:586–591Google Scholar
  25. Holloway JR, Ford CE (1975) Fluid absent melting of the fluorhydroxy amphibole pargasite to 35 kilobars. Earth Planet Sci Lett 25:44–48Google Scholar
  26. Ito H, Yanagase T, Suginohara Y, Miyazaki N (1967) Studies on the structure of molten fluoride-silicate systems by infrared absorption spectra. Chem Abs 67:68972g from Nippon Kinzoku Gakkaishi 31:290–295Google Scholar
  27. Jaques AL, Lewis JD, Smith CB, Gregory GP, Ferguson J, Chappell BW, McCulloch MT (1984) The diamond bearing ultrapotassic (lamproitic) rocks of the West Kimberley region, Western Australia. In: Kornprobst J (ed) Kimberlites I:Kimberlites and related rocks. p 225–254Google Scholar
  28. Kogarko LN (1967) Lamination area in melts of the system Si, Al, Na//O, F. Dokl Akad Nauk Earth Sci See 176:203–205Google Scholar
  29. Kogarko LN (1974) Role of volatiles. In: H Sorensen (ed) The alkaline rocks, pp 474–487 Wiley, New YorkGoogle Scholar
  30. Kogarko LN, Krigman LD (1973) Structural position of fluorinein silicate melts (according to melting curves). Geochem Int 10:34–40Google Scholar
  31. Kogarko LN, Ryabchikov ID (1978) Volatile components in magmatic processes. Geochem Int 15:9–32Google Scholar
  32. Kogarko LN, Krigman LD, Sharudilo NS (1968) Experimental investigations of the effect of alkalinity of silicate melts on the separation of fluorine into the gas phase. Geochem Int 5:782–790Google Scholar
  33. Kovach JJ, Hiser AL, Karr C (1975) Far-infrared spectroscopy of minerals. In: C Karr (ed) Infrared and Raman spectroscopy of lunar and terrestrial minerals. p 231–254 Academic Press, London, New YorkGoogle Scholar
  34. Kovalenko NI (1977) The reactions between granite and aqueous hydrofluoric acid in relation to the origin of fluorine-bearing granites. Geochem Int 14:108–118Google Scholar
  35. Kozakevitch P (1954) Viscosity of blast furnace slags. Rev Metall Mem Sci 51:569–587Google Scholar
  36. Kumar D, Ward RG, Williams DJ (1961) Effect of fluorides on silicates and phosphates. Disc Faraday Soc 32:147–154Google Scholar
  37. Kumar D, Ward RG, Williams DJ (1965) Infrared absorption of some solid silicates and phosphates with and without fluoride additions. Trans Faraday Soc 61:1850–1857Google Scholar
  38. Kushiro I (1972) Effect of water on the compositions of magmas formed at high pressures. J Petrol 13:311–334Google Scholar
  39. Kushiro I (1975) On the nature of silicate melt and its significance in magma genesis: regularities in the shift of the liquidus boundaries involving olivine, pyroxene and silica minerals. Am J Sci 275:411–431Google Scholar
  40. Laughlin RB, Joannopoulos JD (1977) Phonons in amorphous silica. Phys Rev B 16:2942–2952Google Scholar
  41. Luth WC (1967) Studies in the system KAlSiO4-Mg2SiO4-SiO2-H2O: I, Inferred phase relations and petrologic applications. J Petrol 8:372–416Google Scholar
  42. Manning DAC (1981) The effect of fluorine on liquidus phase relationships in the system Qz-Ab-Or with excess water at 1 kb. Contrib Mineral Petrol 76:206–215Google Scholar
  43. Manning DAC, Hamilton DL, Henderson CMB, Dempsey MJ (1980) The probable occurrence of interstitial Al in hydrous, F-bearing and F-free aluminosilicate melts. Contrib Mineral Petrol 75:257–262Google Scholar
  44. McCauley JW, Newnham RE, Gibbs GV (1973) Crystal structure analysis of synthetic fluorphlogopite. Am Mineral 58:249–254Google Scholar
  45. Mitchell A (1967) Reactions of calcium silicates in solution in liquid calcium fluoride. Trans Faraday Soc 63:1408–1417Google Scholar
  46. Munoz JL, Eugster HP (1969) Experimental control of fluorine reactions in hydrothermal systems. Am Mineral 54:943–959Google Scholar
  47. Mysen BO (1977) The solubility of H2O and CO2 under predicted magma genesis conditions and some petrological and geophysical implications. Rev Geophys Space Phys 15:351–361Google Scholar
  48. Mysen BO, Virgo D (1985) Interaction between fluorine and silica in quenched melts on the joins SiO2-AlF3 and SiO2-NaF determined by Raman spectroscopy. Phys Chem Minerals 12:77–85Google Scholar
  49. Mysen BO, Virgo D, Seifert FA (1982) The structure of silicate melts: implications for chemical and physical properties of natural magmas. Rev Geophys Space Phys 20:353–383Google Scholar
  50. Palache C, Berman H, Frondel C (1951) Dana's system of mineralogy II pp 103–104 Wiley, New YorkGoogle Scholar
  51. Ramberg H (1952) Chemical bonds and distribution of cations in silicates. J Geol 60:331–355Google Scholar
  52. Rao KJ, Elliott SR (1981) Characteristic vibrations of cations in glasses. J Non-Cryst Solids 46:371–378Google Scholar
  53. Schilling J-G, Bergeron MB, Evans R (1980) Halogens in the mantle beneath the North Atlantic. Phil Trans R Soc London A 297:147–178Google Scholar
  54. Seifert F, Schreyer W (1971) Synthesis and stability of micas in the system K2O-MgO-SiO2-H2O and their relations to phlogopite. Contrib Mineral Petrol 30:196–215Google Scholar
  55. Seifert F, Mysen BO, Virgo D (1981) Structural similarity of glasses and melts relevant to petrological processes. Geochim Cosmochim Acta 45:1879–1884Google Scholar
  56. Seifert F, Mysen BO, Virgo D (1982) Three-dimensional network melt structure in the systems SiO2-NaAlO2, SiO2-CaAl2O4 and SiO2-MgAl2O4. Am Mineral 67:696–717Google Scholar
  57. Sekine T, Wyllie PJ (1982) Phase relationships in the system KAlSiO4-Mg2SiO4-SiO2-H2O as a model for hybridisation between hydrous siliceous melts and peridotite. Contrib Mineral Petrol 79:368–374Google Scholar
  58. Shell HR, Ivey KH (1969) Fluorine micas. US Bur Mines Bull 647:291ppGoogle Scholar
  59. Stolper EM (1982) The speciation of water in silicate melts. Geochim Cosmochim Acta 46:2609–2620Google Scholar
  60. Tarte P (1965) The determination of cation co-ordination in glasses by infra-red spectroscopy. In: JA Prins (ed) Physics of noncrystalline solids. pp 549–565 Wiley, New YorkGoogle Scholar
  61. Tarte P (1967) Infra-red spectra of inorganic aluminates and characteristic vibrational frequencies of AlO4 tetrahedra and AlO6 octahedra. Spectrochim Acta 23A: 2127–2143Google Scholar
  62. Taylor M, Brown GE, Fenn PM (1980) Structure of silicate mineral glasses III, NaAlSi3O8 supercooled liquid at 805° C and the effects of thermal history. Geochim Cosmochim Acta 44:109–119Google Scholar
  63. Taylor WR (1985) The role of C-O-H fluids in upper mantle processes: a theoretical, experimental and spectroscopic study. Ph.D thesis, University of Tasmania, HobartGoogle Scholar
  64. Tsunawaki Y, Iwamoto N, Hattori T, Mitsuishi A (1981) Analysis of CaO-SiO2 and CaO-SiO2-CaF2 glasses by Raman spectroscopy. J Non-Cryst Solids 44:369–378Google Scholar
  65. Velde D (1979) Trioctahedral micas in melilite-bearing eruptive rocks. Carnegie Inst Washington Yearb 78:468–475Google Scholar
  66. White WB (1975) Structural interpretation of lunar and terrestrial minerals by Raman spectroscopy. In: C Karr (ed) Infrared and Raman spectroscopy of lunar and terrestrial minerals. p 325–358 Academic Press, London New YorkGoogle Scholar
  67. Windom KE, Boettcher AL (1981) Phase relations for the joins jadeite-enstatite and jadeite-forsterite at 28 kb and their bearing on basalt genesis. Am J Sci 281:335–351Google Scholar
  68. Wyllie PJ, Tuttle OF (1961) Experimental investigation of silicate systems containing two volatile components. Part II. The effects of NH3 and HF in addition to H2O on the melting temperatures of albite and granite. Am J Sci 259:128–143Google Scholar
  69. Yoder HS, Tilley CE (1962) Origin of basalt magmas: an experimental study of natural and synthetic rock systems. J Petrol 3:342–532Google Scholar

Copyright information

© Springer-Verlag 1986

Authors and Affiliations

  • Stephen F. Foley
    • 1
  • Wayne R. Taylor
    • 1
  • David H. Green
    • 1
  1. 1.Geology DepartmentUniversity of TasmaniaHobartAustralia

Personalised recommendations