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.
Article PDF
Similar content being viewed by others
Avoid common mistakes on your manuscript.
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
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
Barker C, Torkelson BE (1975) Gas adsorption on crushed quartz and basalt. Geochim Cosmochim Acta 39:212–218
Boettcher AL (1984) The system SiO2-H2O-CO2: melting, solubility mechanisms of carbon, and liquid structure to high pressures. Am Mineral 69:823–833
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
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
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
Brey G (1976) CO2 solubility and solubility mechanisms in silicate melts at high pressures. Contrib Mineral Petrol 57:215–221
Brey G, Green DH (1975) The role of CO2 in the genesis of olivine melilitite. Contrib Mineral Petrol 49:93–103
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
Duyckaerts G (1959) The infrared analysis of solid substances — a review. Analyst 84:201–214
Eggler DH (1973) Role of CO2 in melting processes in the mantle. Carnegie Inst Washington Yearb 72:457–467
Eggler DH (1974) Effect of CO2 on the melting of peridotite. Carnegie Inst Washington Yearb 73:215–224
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
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
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
Fine G, Stolper E (1984) Infrared spectroscopy of carbon dioxidebearing silicate glasses. Geol Soc Am Abstr with Prog 16:508
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
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
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
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
Kushiro I (1978) Viscosity and structural changes of albite (NaAlSi3O8) melt at high pressures. Earth Planet Sci Lett 41:87–90
Lacy ED (1963) Aluminum in glasses and in melts. Phys Chem Glasses 4:234–238
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)
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
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
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
Mysen BO, Virgo D (1980a) Solubility mechanisms of carbon dioxide in silicate melts: a Raman spectroscopic study. Am Mineral 65:885–899
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
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
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
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
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
Okuno M, Marumo F (1982) The structures of albite and anorthite melts. Mineral J Japan 11:180–196
Papike JJ, Stephenson NC (1966) The crystal structure of mizzonite, a calcium- and carbonate-rich scapolite. Am Mineral 51:1014–1027
Pearce ML (1964) Solubility of carbon dioxide and variation of oxygen ion activity in soda-silica melts. J Am Ceramic Soc 47:342–347
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
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
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
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
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
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
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
Stolper E (1982a) Water in silicate glasses: An infrared spectroscopic study. Contrib Mineral Petrol 81:1–17
Stolper E (1982b) The speciation of water in silicate melts. Geochim Cosmochim Acta 46:2609–2620
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
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
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
Tuddenham WM, Lyon RJP (1960) Infrared techniques in the identification and measurement of minerals. Anal Chem 32:1630–1634
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
Wagner C (1975) The concept of basicity of slags. Met Trans 6B:405–409
Watson EB, Sneeringer MA, Ross A (1982) Diffusion of dissolved carbonate in magmas: Experimental results and applications. Earth Planet Sci Lett 61:346–358
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
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
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
Received:
Accepted:
Issue Date:
DOI: https://doi.org/10.1007/BF00377759