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The speciation of carbon dioxide in sodium aluminosilicate glasses

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Abstract

Infrared spectroscopy has been used to study the speciation of CO2 in glasses near the NaAlO2-SiO2 join quenched from melts held at high temperatures and pressures. Absorption bands resulting from the antisymmetric stretches of both molecular CO2 (2,352 cm−1) and CO 2−3 (1,610 cm−1 and 1,375 cm−1) are observed in these glasses. The latter are attributed to distorted Na-carbonate ionic-complexes. Molar absorptivities of 945 liters/mole-cm for the molecular CO2 band, 200 liters/mole-cm for the 1,610 cm−1 band, and 235 liters/mole-cm for the 1,375 cm−1 band have been determined. These molar absorptivities allow the quantitative determination of species concentrations in the glasses with a precision on the order of several percent of the amount present. The accuracy of the method is estimated to be ±15–20% at present.

The ratio of molecular CO2 to CO 2−3 in sodium aluminosilicate glasses varies little for each silicate composition over the range of total dissolved CO2 content (0–2%), pressure (15–33 kbar) and temperature (1,400–1,560° C) that we have studied. This ratio is, however, a strong function of silicate composition, increasing both with decreasing Na2O content along the NaAlO2-SiO2 join and with decreasing Na2O content in peraluminous compositions off the join.

Infrared spectroscopic measurements of species concentrations in glasses provide insights into the molecular level processes accompanying CO2 solution in melts and can be used to test and constrain thermodynamic models of CO2-bearing melts. CO2 speciation in silicate melts can be modelled by equilibria between molecular CO2, CO 2−3 , and oxygen species in the melts. Consideration of the thermodynamics of such equilibria can account for the observed linear relationship between molecular CO2 and carbonate concentrations in glasses, the proposed linear relationship between total dissolved CO2 content and the activity of CO2 in melts, and observed variations in CO2 solubility in melts.

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References

  • Aines RD, Silver LA, Rossman GR, Stolper E, Holloway JR (1983) Direct observation of water speciation in rhyolite at temperatures up to 850° C. Geol Soc Am Abstr with Prog 15:512

    Google Scholar 

  • Albarede F, Provost A (1977) Petrological and geochemical massbalance equations: an algorithm for least-squares fitting and general error analysis. Comp Geosci 3:309–326

    Google Scholar 

  • Barker C, Torkelson BE (1975) Gas adsorption on crushed quartz and basalt. Geochim Cosmochim Acta 39:212–218

    Google Scholar 

  • Boettcher AL (1984) The system SiO2-H2O-CO2: melting, solubility mechanisms of carbon, and liquid structure to high pressures. Am Mineral 69:823–833

    Google Scholar 

  • Boettcher AL, Windom KE, Bohlen SR, Luth RW (1981) Low friction, anhydrous, low to high-temperature furnace sample assembly for piston-cylinder apparatus. Rev Sci Instrum 52:1903–1904

    Google Scholar 

  • Boettcher AL, Burnham C, Wayne, Windom KE, Bohlen SR (1982) Liquids, glasses, and the melting of silicates to high pressures. J Geol 90:127–138

    Google Scholar 

  • Boettcher AL, Guo Q, Bohlen S, Hanson B (1984) Melting in feldspar-bearing systems to high pressures and the structures of aluminosilicate liquids. Geol 12:202–204

    Google Scholar 

  • Brey G (1976) CO2 solubility and solubility mechanisms in silicate melts at high pressures. Contrib Mineral Petrol 57:215–221

    Google Scholar 

  • Brey G, Green DH (1975) The role of CO2 in the genesis of olivine melilitite. Contrib Mineral Petrol 49:93–103

    Google Scholar 

  • Brey G, Green DH (1976) Solubility of CO2 in olivine melilitite at high pressures and the role of CO2 in the earth's upper mantle. Contrib Mineral Petrol 55:217–230

    Google Scholar 

  • Duyckaerts G (1959) The infrared analysis of solid substances — a review. Analyst 84:201–214

    Google Scholar 

  • Eggler DH (1973) Role of CO2 in melting processes in the mantle. Carnegie Inst Washington Yearb 72:457–467

    Google Scholar 

  • Eggler DH (1974) Effect of CO2 on the melting of peridotite. Carnegie Inst Washington Yearb 73:215–224

    Google Scholar 

  • Eggler DH (1978) The effect of CO2 upon partial melting of peridotite in the system Na2O-CaO-Al2O3-MgO-SiO2-CO2 to 35 kb, with an analysis of melting in a periodite-H2O-CO2 system. Am J Sci 278:305–343

    Google Scholar 

  • 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 Sci 278:64–94

    Google Scholar 

  • Eggler DH, Mysen BO, Hoering TC, Holloway JR (1979) The solubility of carbon monoxide in silicate melts at high pressures and its effect on silicate phase relations. Earth Planet Sci Lett 43:321–330

    Google Scholar 

  • Fine G, Stolper E (1984) Infrared spectroscopy of carbon dioxidebearing silicate glasses. Geol Soc Am Abstr with Prog 16:508

    Google Scholar 

  • Fine G, Stolper E (1985) Carbon dioxide in basaltic glasses: concentrations and speciation. Earth Planet Sci Lett (submitted)

  • Fine G, Stolper E, Mendenhall MH, Livi RP, Tombrello TA (1985) Measurement of the carbon content of silicate glasses using the 12C(d,p0)13C nuclear reaction. In: Armstrong JT (ed) Microbeam Analysis — 1985. San Francisco Press, pp 241–245

  • Filleux C, Tombrello TA, Burnett DS (1977) Direct measurement of surface carbon concentrations. Proc Lunar Sci Conf 8th, pp 3755–3772

  • Flory PJ (1944) Thermodynamics of heterogeneous polymers and their solutions. J Chem Phys 12:425–438

    Google Scholar 

  • Flory PJ (1953) Principles of polymer chemistry. Cornell University Press

  • Guggenheim EA (1952) Mixtures. Oxford University Press

  • Holland TB (1980) The reaction albite=Jadeite+quartz determined experimentally in the range 600–1,200° C. Am Mineral 65:129–134

    Google Scholar 

  • Holloway JR, Mysen BO, Eggler DH (1976) The solubility of CO2 in liquids on the join CaO-MgO-SiO2-CO2. Carnegie Inst Washington Yearb 75:626–630

    Google Scholar 

  • 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 275:411–431

    Google Scholar 

  • Kushiro I (1978) Viscosity and structural changes of albite (NaAlSi3O8) melt at high pressures. Earth Planet Sci Lett 41:87–90

    Google Scholar 

  • Lacy ED (1963) Aluminum in glasses and in melts. Phys Chem Glasses 4:234–238

    Google Scholar 

  • Livi RP, Mendenhall MH, Tombrello TA, Fine G, Stolper E (1984) High sensitivity carbon content analyses of geological materials using 1.4 MeV deterons. Proc Int Symposium on Nuclear Accelerator Physics (Laboratori Nazional di Legarno, Italy) (in press)

    Google Scholar 

  • Mathez EA, Blacic JD, Berry J, Maggiore C, Hollander M (1984) Carbon abundances in mantle minerals determined by nuclear reaction analysis. Geophys Res Lett 11:947–950

    Google Scholar 

  • McKeown DA, Waychunas GA, Brown GE (1984) Na and Al environments in some minerals and a series of glasses within the Na2O-Al2O3-SiO2 system. Geol Soc Am Abstr with Prog 16:589

    Google Scholar 

  • Mysen BO (1976) The role of volatiles in silicate melts: solubility of carbon dioxide and water in feldspar, pyroxene and feldspathoid melts to 30 kb and 1,625° C. Am J Sci 276:969–996

    Google Scholar 

  • Mysen BO, Virgo D (1980a) Solubility mechanisms of carbon dioxide in silicate melts: a Raman spectroscopic study. Am Mineral 65:885–899

    Google Scholar 

  • Mysen BO, Virgo D (1980b) The solubility behavior of CO2 in melts on the join NaAlSi3O8-CaAl2Si2O8-CO2 at high pressures and temperatures: a Raman spectroscopic study. Am Mineral 65:1166–1175

    Google Scholar 

  • Mysen BO, Arculus RJ, Eggler DH (1975) Solubility of CO2 in natural nephelinite, tholeite and andesite melts to 30 kb pressure. Contrib Mineral Petrol 53:227–239

    Google Scholar 

  • Mysen BO, Eggler DH, Seitz MG, Holloway JR (1976) Carbon dioxide in silicate melts and crystals: Part I. Solubility measurements. Am J Sci 276:455–479

    Google Scholar 

  • Nakamoto K (1978) Infrared and Raman spectra of inorganic and coordination compounds (3rd edn). John Wiley and Sons

  • Navrotsky A, Peraudeau G, McMillan P, Coutures JP (1982) A thermochemical study of glasses and crystals along the joins silica-calcium aluminate and silica-sodium aluminate. Geochim Cosmochim Acta 46:2039–2047

    Google Scholar 

  • Oberheuser G, Kathrein H, Demortier G, Gonska H, Freund F (1983) Carbon in olivine single crystals analyzed by the 12C(d,p)13C method and by photoelectron spectroscopy. Geochim Cosmochim Acta 47:1117–1129

    Google Scholar 

  • Okuno M, Marumo F (1982) The structures of albite and anorthite melts. Mineral J Japan 11:180–196

    Google Scholar 

  • Papike JJ, Stephenson NC (1966) The crystal structure of mizzonite, a calcium- and carbonate-rich scapolite. Am Mineral 51:1014–1027

    Google Scholar 

  • Pearce ML (1964) Solubility of carbon dioxide and variation of oxygen ion activity in soda-silica melts. J Am Ceramic Soc 47:342–347

    Google Scholar 

  • Rai CS, Sharma SK, Muenow DW, Matson DW, Byers CD (1983) Temperature dependence of CO2 solubility in high pressure quenched glasses of diopside composition. Geochim Cosmochim 47:953–958

    Google Scholar 

  • Russell JD (1974) Instrumentation and techniques. In: VC Farmer (ed) The infrared spectra of minerals. Mineral Soc London Mon 4:11–25

  • Seifert FA, Mysen BO, Virgo D (1981) Structural similarity of glasses and melts relevant to petrological processes. Geochim Cosmochim Acta 45:1879–1884

    Google Scholar 

  • Sharma SK (1979) Structure and solubility of carbon dioxide in silicate glasses of diopside and sodium melilite compositions at high pressures from Raman spectroscopic data. Carnegie Inst Washington Yearb 78:532–537

    Google Scholar 

  • Sharma SK, Virgo D, Mysen BO (1978) Structure of melts along the join SiO2-NaAlSiO4 by Raman spectroscopy. Carnegie Inst Washington Yearb 77:652–658

    Google Scholar 

  • Sharma SK, Hoering TC, Yoder HS (1979a) Quenched melts of akermanite composition with and without CO2 — Characterization by Raman spectroscopy and gas chromatography. Carnegie Inst Washington Yearb 78:537–542

    Google Scholar 

  • Sharma SK, Virgo D, Mysen BO (1979b) Raman study of the coordination of aluminum in Jadeite melts as a function of pressure. Am Mineral 64:779–787

    Google Scholar 

  • Spera FJ, Bergman SC (1980) Carbon dioxide in igneous petrogenesis: I. Aspects of the dissolution of CO2 in silicate liquids. Contrib Mineral Petrol 74:55–66

    Google Scholar 

  • Stolper E (1982a) Water in silicate glasses: An infrared spectroscopic study. Contrib Mineral Petrol 81:1–17

    Google Scholar 

  • Stolper E (1982b) The speciation of water in silicate melts. Geochim Cosmochim Acta 46:2609–2620

    Google Scholar 

  • Stolper E, Silver LA, Aines RD (1983) The effects of quenching rate and temperature on the speciation of water in silicate glasses. EOS, Trans Am Geophys Union 64:339

    Google Scholar 

  • Taylor M, Brown GE Jr, Fenn PM (1980) Structure of mineral glasses — III. NaAlSi3O8 supercooled liquid at 805° C and the effects of thermal history. Geochim Cosmochim Acta 44:109–117

    Google Scholar 

  • Tomlinson JW (1953) Some aspects of the constitution of liquid oxides. In: Physical chemistry of melts. London Inst Min Metall pp 22–33

  • Toop GW, Samis CS (1962) Activities of ions in silicate melts. Trans Met Soc AIME 224:878–887

    Google Scholar 

  • Tuddenham WM, Lyon RJP (1960) Infrared techniques in the identification and measurement of minerals. Anal Chem 32:1630–1634

    Google Scholar 

  • Verweij H, Van den Boom H, Breemer RE (1977) Raman scattering of carbonate ions dissolved in potassium silicate glasses. J Am Ceram Soc 60:529–534

    Google Scholar 

  • Wagner C (1975) The concept of basicity of slags. Met Trans 6B:405–409

    Google Scholar 

  • Watson EB, Sneeringer MA, Ross A (1982) Diffusion of dissolved carbonate in magmas: Experimental results and applications. Earth Planet Sci Lett 61:346–358

    Google Scholar 

  • White WB (1974) The carbonate minerals. In: WC Farmer (ed) The infrared spectra of minerals. Mineral Soc London Mon 4:227–284

  • Wong J, Angell CA (1976) Glass structure by spectroscopy. Marcel Dekker, Inc

  • Wyllie PJ (1979) Magmas and volatile components. Am Mineral 64:469–500

    Google Scholar 

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  1. Division of Geological and Planetary Sciences, California Institute of Technology, 91125, Pasadena, California

    Gerald Fine & Edward Stolper

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  1. Gerald Fine
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Fine, G., Stolper, E. The speciation of carbon dioxide in sodium aluminosilicate glasses. Contr. Mineral. and Petrol. 91, 105–121 (1985). https://doi.org/10.1007/BF00377759

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