The effect of alkalis and polymerization on the solubility of H2O and CO2 in alkali-rich silicate melts

  • Francesco Vetere
  • Francois Holtz
  • Harald Behrens
  • Roman E. Botcharnikov
  • Sara Fanara
Original Paper
First Online:
Received:
Accepted:

Abstract

The effect of alkalis on the solubility of H2O and CO2 in alkali-rich silicate melts was investigated at 500 MPa and 1,250 °C in the systems with H2O/(H2O + CO2) ratio varying from 0 to 1. Using a synthetic analog of phonotephritic magma from Alban Hills (AH1) as a base composition, the Na/(Na + K) ratio was varied from 0.28 (AH1) to 0.60 (AH2) and 0.85 (AH3) at roughly constant total alkali content. The obtained results were compared with the data for shoshonitic and latitic melts having similar total alkali content but different structural characteristics, e.g., NBO/T parameter (the ratio of non-bridging oxygens over tetrahedrally coordinated cations), as those of the AH compositions. Little variation was observed in H2O solubility (melt equilibrated with pure H2O fluid) for the whole compositional range in this study with values ranging between 9.7 and 10.2 wt. As previously shown, the maximum CO2 content in melts equilibrated with CO2-rich fluids increases strongly with the NBO/T from 0.29 wt % for latite (NBO/T = 0.17) to 0.45 wt % for shoshonite (NBO/T = 0.38) to 0.90 wt % for AH2 (NBO/T = 0.55). The highest CO2 contents determined for AH3 and AH1 are 1.18 ± 0.05 wt % and 0.86 ± 0.12 wt %, respectively, indicating that Na is promoting carbonate incorporation stronger than potassium. At near constant NBO/T, CO2 solubility increases from 0.86 ± 0.12 wt % in AH1 [Na/(Na + K)] = 0.28, to 1.18 ± 0.05 wt % in AH3 [Na/(Na + K)] = 0.85, suggesting that Na favors CO2 solubility on an equimolar basis. An empirical equation is proposed to predict the maximum CO2 solubility at 500 MPa and 1,100–1,300 °C in various silicate melts as a function of the NBO/T, (Na + K)/∑cations and Na/(Na + K) parameters: \({\text{wt}}\% \;{\text{CO}}_{2} = - 0.246 + 0.014\exp \left( {6.995 \cdot \frac{\text{NBO}}{T}} \right) + 3.150 \cdot \frac{{{\text{Na}} + {\text{K}}}}{{\varSigma {\text{cations}}}} + 0.222 \cdot \frac{\text{Na}}{{{\text{Na}} + {\text{K}}}}.\) This model is valid for melt compositions with NBO/T between 0.0 and 0.6, (Na + K)/∑cation between 0.08 and 0.36 and Na/(Na + K) ratio from 0.25 to 0.95 at oxygen fugacities around the quartz–fayalite–magnetite buffer and above.

Keywords

H2O CO2 Fe2+/Fetot NBO/T Solubility Silicate melt Alkali Infrared spectroscopy 
This is a preview of subscription content, log in to check access.

Notes

Acknowledgments

We thank the editor Prof. G. Moore for handling the paper and Dr. Masotta and two anonymous reviewers for constructive comments and suggestions that greatly improved the manuscript. A. Husen is acknowledge for the Fe redox state determination and J. Feige for EPMA and IR samples preparation. This research has been supported by Marie Curie Fellowship IEF_SolVoM #297880 to F.VETERE.

References

  1. Baker DR, Alletti M (2012) Fluid saturation and volatile partitioning between melts and hydrous fluids in crustal magmatic systems: the contribution of experimental measurements and solubility models. Earth Sci Rev 114:298–324CrossRefGoogle Scholar
  2. Behrens H (1995) Determination of water solubilities in high-viscosity silicate glasses. An experimental study on NaAlSi3O8 and KAlSi3O8 melts. Eur J Mineral 7:905–920Google Scholar
  3. Behrens H, Ohlhorst S, Holtz F, Champenois M (2004) CO2 solubility in dacitic melts equilibrated with H2O–CO2 fluids—Implications for modeling the solubility of CO2 in silicic melts. Geochim Cosmochim Acta 68:4687–4703CrossRefGoogle Scholar
  4. Behrens H, Misiti V, Freda C, Vetere F, Botcharnikov RE, Scarlato P (2009) Solubility of H2O and CO2 in ultrapotassic melts at 1200 and 1250 & #xB0;C and pressure from 50 to 500 MPa. Am Mineral 94:105–120CrossRefGoogle Scholar
  5. Berndt J, Liebske C, Holtz F, Freise M, Nowak M, Ziegenbein D, Hurkuck W, Koepke J (2002) A combined rapid-quench and H2-membrane setup for internally heated pressure vessels: description and application for water solubility in basaltic melts. Am Mineral 87:1717–1726Google Scholar
  6. Blank JG, Brooker RA (1994) Experimental studies of carbon dioxide in silicate melts: solubility, speciation and stable isotope behavior. In: Carroll MR, Holloway JR (Eds) Volatiles in Magmas 30: 157–186. Reviews in Mineralogy, Mineralogical Society of America Chantilly, VirginiaGoogle Scholar
  7. Blank JG, Stolper EM, Carroll MR (1993) Solubilities of carbon dioxide and water in rhyolitic melt at 850 & #xB0;C and 750 bars. Earth Planet Sci Lett 119:27–36CrossRefGoogle Scholar
  8. Botcharnikov RE, Freise M, Holtz F, Behrens H (2005a) Solubility of C–O–H mixtures in natural melts: new experimental data and application range of recent models. Ann Geophys 48:633–646Google Scholar
  9. Botcharnikov RE, Koepke J, Holtz F, McCammon C, Wilke M (2005b) The effect of water activity on the oxidation and structural state of Fe in a ferro-basaltic melt. Geochim Cosmochim Acta 69:5071–5085CrossRefGoogle Scholar
  10. Botcharnikov RE, Behrens H, Holtz F (2006) Solubility and speciation of C–O–H fluids in andesitic melt at T = 1100–1300 & #xB0;C and P = 200 and 500 MPa. Chem Geol 229:125–143CrossRefGoogle Scholar
  11. Brooker RA, Kohn SC, Holloway JR, McMillan PF (2001a) Structural controls on the solubility of CO2 in silicate melts Part I: bulk solubility data. Chem Geol 174:225–239CrossRefGoogle Scholar
  12. Brooker RA, Kohn SC, Holloway JR, McMillan PF (2001b) Structural controls on the solubility of CO2 in silicate melts Part II: IR characteristics of carbonate groups in silicate glasses. Chem Geol 174:241–254CrossRefGoogle Scholar
  13. Davi M, Behrens H, Vetere F, De Rosa R (2009) The viscosity of latitic melts from Lipari (Aeolian Islands, Italy): inference on mixing-mingling processes in magmas. Chem Geol 259:89–97CrossRefGoogle Scholar
  14. Di Matteo V, Carroll MR, Behrens H, Vetere F, Brooker RA (2004) Water solubility in trachytic melts. Chem Geol 213:187–196CrossRefGoogle Scholar
  15. Dixon JE (1997) Degassing of alkalic basalts. Am Mineral 82:368–378Google Scholar
  16. Dixon JE, Pan V (1995) Determination of the molar absorptivity of dissolved carbonate in basanitic glass. Am Mineral 80:1339–1342Google Scholar
  17. Dixon JE, Stolper EM (1995) An experimental study of water and carbon dioxide solubilities in Mid-Ocean Ridge Basaltic liquids. Part II: applications to degassing. J Petrol 36:1633–1646Google Scholar
  18. Dixon JE, Stolper EM, Holloway JR (1995) An experimental study of water and carbon dioxide solubilities in mid-ocean ridge basaltic liquids. Part I: calibration and solubility models. J Petrol 36:1607–1631Google Scholar
  19. Fine G, Stolper EM (1986) Dissolved carbon dioxide in basaltic glasses: concentrations and speciation. Earth Planet Sci Lett 76:263–278CrossRefGoogle Scholar
  20. Fogel R, Rutherford M (1990) The solubility of carbon dioxide in rhyolitic melts: a quantitative FTIR study. Am Mineral 75:1311–1326Google Scholar
  21. Freda C, Gaeta M, Misiti V, Mollo S, Dolfi D, Scarlato P (2008) Magma-carbonate interaction: an experimental study on ultrapotassic rocks from Alban Hills (Central Italy). Lithos 101:397–415CrossRefGoogle Scholar
  22. Ghiorso MS, Carmichael ISE, Rivers ML, Sack RO (1983) The Gibbs free energy of mixing of natural silicate liquids; an expanded regular solution approximation for the calculation of magmatic intensive variables. Contrib Mineral Petrol 84:107–145CrossRefGoogle Scholar
  23. Holloway JR, Blank JG (1994) Application of experimental results to C-O-H species in natural melts. In: Carroll MR, Holloway JR (Eds) Volatiles in Magmas 30: 187–230. Reviews in MineralogyGoogle Scholar
  24. Holtz F, Behrens H, Dingwell DB, Johannes W (1995) Water solubility in haplogranitic melts. Compositional, pressure and temperature dependence. Am Mineral 80:94–108Google Scholar
  25. Huizenga JM (2001) Thermodynamic modeling of C–O–H fluids. Lithos 55:101–114CrossRefGoogle Scholar
  26. Iacono-Marziano G, Gaillard F, Pichavant M (2007) Limestone assimilation and the origin of CO2 emissions at the Alban Hills (Central Italy): constraints from experimental petrology. J Volcanol Geoth Res 166:91–105CrossRefGoogle Scholar
  27. Iacono-Marziano G, Morizet Y, Le Trong E, Gaillard F (2012) New experimental data and semi-empirical parameterization of H2O–CO2 solubility in mafic melt. Geochim Cosmochim Acta 97:1–23CrossRefGoogle Scholar
  28. Iacovino K, Moore G, Roggensack K, Oppenheimer C, Kyle P (2013) H2O–CO2 solubility in mafic alkaline magma: applications to volatile sources and degassing behavior at Erebus volcano, Antartica. Contribution to Mineralogy and Petrology. doi  10.1007/s00410-013-0877-2
  29. Jakobsson S (1997) Solubility of water and carbon dioxide in an icelandite at 1400 & #xB0;C and 10 kilobars. Contrib Miner Petrol 127:129–135CrossRefGoogle Scholar
  30. Kent AJR (2008) Melt inclusion in basaltic and related rocks. Rev Mineral Petrol 69:273–331CrossRefGoogle Scholar
  31. King PL, Holloway JR (2002) CO2 solubility and speciation in intermediate (andesitic) melts: the role of H2O and composition. Geochimica et Cos-mochimica Acta 66:1627–1640CrossRefGoogle Scholar
  32. King PL, Vennemann TW, Holloway JR, Hervig RL, Lowenstern JB, Forneris JF (2002) Analytical techniques for volatiles: a case study using intermediate (andesitic) glasses. Am Mineral 87:1077–1089Google Scholar
  33. Kress VC, Carmichael ISE (1991) The compressibility of silicate liquids containing Fe2O3 and the effect of composition, temperature, oxygen fugacity and pressure on their redox states. Contrib Mineral Petrol 108:82–92CrossRefGoogle Scholar
  34. Le Losq C, Neuville DR (2013) Effect of the Na/K mixing on the structure and rheology of tectosilicate silica-rich melts. Chem Geol 346:57–71CrossRefGoogle Scholar
  35. Liu YT, Zhang Y, Behrens H (2005) Solubility of H2O in rhyolitic melts at low pressure and a new empirical model for mixed H2O–CO2 solubility in rhyolitic melts. J Volcanol Geoth Res 143:219–235CrossRefGoogle Scholar
  36. Marra F, Freda C, Scarlato P, Taddeucci J, Karner DB, Renne PR, Gaeta M, Palladino DM, Trigila R, Cavarretta G (2003) Post-caldera activity in the Alban Hills volcanic district (Italy): 40Ar/39Ar geochronology and insights into magma evolution. Bull Volc 65:227–247CrossRefGoogle Scholar
  37. Mattey DP (1991) Carbon dioxide solubility and carbon isotope fractionation in basaltic melt. Geochim Cosmochim Acta 55:3467–3473CrossRefGoogle Scholar
  38. Moore G (2008) Interpreting H2O and CO2 contents in melt Inclusions: constraints from solubility experiments and modeling. Rev Mineral Geochem 69:333–362CrossRefGoogle Scholar
  39. Moretti R (2005) Polymerization, basicity, oxidation state and their role in ionic modeling of silicate melts. Annals of Geophysic 48: N. 4/5, 583–608Google Scholar
  40. Morizet Y, Brooker RA, Kohn SC (2002) CO2 in haplo-phonolite Melt: solubility, speciation and carbonate complexation. Geochim Cosmochim Acta 66:1809–1820CrossRefGoogle Scholar
  41. Morizet Y, Paris M, Gaillard F, Scaillet B (2010) C–O–H fluid solubility in haplobasalt under reducing conditions: an experimental study. Chem Geol 279:1–16CrossRefGoogle Scholar
  42. Mysen BO (1988) Structure and properties of silicate melts. Elsevier, AmsterdamGoogle Scholar
  43. Mysen BO, Cody GD (2004) Solubility and solution mechanism of H2O in alkali silicate melts and glasses at high pressure and temperature. Geochim Cosmochim Acta 68:5113–5126CrossRefGoogle Scholar
  44. Mysen BO, Virgo D, Seifert FA (1985) Relationships between properties and structure of aluminosilicate melts. Am Mineral 70:88–105Google Scholar
  45. Newman S, Lowenstern JB (2002) VolatileCalc: a silicate melt-H2O–CO2 solution model written in Visual Basic for excel. Comput Geosci 28:597–604CrossRefGoogle Scholar
  46. Ni H, Keppler H (2013) Carbon in silicate melts. Rev Mineral Geochem 75:251–287CrossRefGoogle Scholar
  47. Pan V, Holloway JR, Hervig RL (1991) The pressure and temperature dependence of carbon dioxide solubility in tholeiitic basalt melts. Geochim Cosmochim Acta 55:1587–1595CrossRefGoogle Scholar
  48. Papale P (1999) Modelling of the solubility of H2O + CO2 fluid in silicate liquids. Am Mineral 84:477–792Google Scholar
  49. Papale P, Moretti R, Barbato D (2006) The compositional dependence of the saturation surface of H2O + CO2 fluids in silicate melts. Chem Geol 229:78–95CrossRefGoogle Scholar
  50. Pawley AR, Holloway JR, McMillan PF (1992) The effect of oxygen fugacity on the solubility of carbon-oxygen fluids in basaltic melt. Earth Planet Sci Lett 110:213–225CrossRefGoogle Scholar
  51. Pitzer KS, Sterner SM (1994) Equations of state valid continuously from zero to extreme pressures for H2O and CO2. J Chem Phys 101:3111–3116CrossRefGoogle Scholar
  52. Scaillet B, Evans BW (1999) The June 15, 1991 eruption of Mount Pinatubo. I. Phase equilibria and pre-eruption P-T–fO2–fH2O conditions of the dacite magma. J Petrol 40:381–411CrossRefGoogle Scholar
  53. Scaillet B, Pichavant M (2004) Role of fO2 on fluid saturation in oceanic basalt. Nature: 430Google Scholar
  54. Schuessler JA, Botcharnikov RE, Behrens H, Misiti V, Freda C (2008) Oxidation state of iron in hydrous phono-tephritic melts. Am Mineral 93:1493–1504CrossRefGoogle Scholar
  55. Shishkina T, Botcharnikov RE, Holtz F, Almeev RR, Portnyagin MV (2010) Solubility of H2O and CO2-bearing fluids in tholeiitic basalts at pressures up to 500 MPa. Chem Geol 277:115–125CrossRefGoogle Scholar
  56. Spera FJ, Bergman SC (1980) Carbon dioxide in igneous petrogenesis: I. Contrib Miner Petrol 74:55–66CrossRefGoogle Scholar
  57. Stolper EM (1982) Water in silicate glasses: an infrared spectroscopic study. Contrib Miner Petrol 81:1–17CrossRefGoogle Scholar
  58. Tamic N, Behrens H, Holtz F (2001) The solubility of H2O and CO2 in rhyolitic melts in equilibrium with a mixed CO2–H2O fluid phase. Chem Geol 174:333–347CrossRefGoogle Scholar
  59. Thibault Y, Holloway JR (1994) Solubility of CO2 in a Ca-rich leucitite: effects of pressure, temperature, and oxygen fugacity. Contrib Miner Petrol 116:216–224CrossRefGoogle Scholar
  60. Vetere F, Behrens H, Misiti V, Ventura G, De Rosa R, Holtz F, Deubener J (2007) Viscosity of shoshonitic melt (Vulcanello Aeolian Islands, Italy) and inference on the dynamics of magma ascent. Chem Geol 245:89–102CrossRefGoogle Scholar
  61. Vetere F, Botcharnikov RR, Behrens H, Holtz F, De Rosa R (2011) Solubility of H2O and CO2 in shoshonitic melts at 1250 & #xB0;C and pressure from 50 to 400 MPa. J Volcanol Geoth Res 202:251–261CrossRefGoogle Scholar
  62. Wilson AD (1960) The micro-determination of ferrous iron in silicate minerals by a volumetric and colorimetric method. Analyst 85:823–827CrossRefGoogle Scholar
  63. Ya Aranovitch L, Newton RC (1999) Experimental determination of CO2–H2O activity-composition relations at 600–1,000°C and 6–14 kbar by reversed decarbonation and dehydration reactions. Am Mineral 84:1319–1332Google Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2014

Authors and Affiliations

  • Francesco Vetere
    • 1
  • Francois Holtz
    • 1
  • Harald Behrens
    • 1
  • Roman E. Botcharnikov
    • 1
  • Sara Fanara
    • 1
  1. 1.Institute for MineralogyLeibniz University of HannoverHannoverGermany

Personalised recommendations