Skip to main content
Log in

Effects of strong network modifiers on Fe3+/Fe2+ in silicate melts: an experimental study

  • Original Paper
  • Published:
Contributions to Mineralogy and Petrology Aims and scope Submit manuscript

Abstract

The effect of CaO, Na2O, and K2O on ferric/ferrous ratio in model multicomponent silicate melts was investigated in the temperature range 1450–1550 °C at 1-atm total pressure in air. It is demonstrated that the addition of these network modifier cations results in an increase of Fe3+/Fe2+ ratio. The influence of network modifier cations on the ferric/ferrous ratio increases in the order Ca < Na < K. Some old controversial conceptions concerning the effect of potassium on Fe3+/Fe2+ ratio in simple model liquids are critically evaluated. An empirical equation is proposed to predict the ferric/ferrous ratio in SiO2–TiO2–Al2O3–FeO–Fe2O3–MgO–CaO–Na2O–K2O–P2O5 melts at air conditions.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8

Similar content being viewed by others

References

  • Appora I, Eiler JM, Matthews A, Stolper EM (2003) Experimental determination of oxygen isotope fractionations between CO2 vapor and soda-melilite melt. Geochim Cosmochim Acta 67:459–471

    Article  Google Scholar 

  • Borisov A (2001) Loop technique: dynamic of metal/melt equilibration. Min Petrol 71:87–94

    Article  Google Scholar 

  • Borisov AA (2008) Experimental investigation of K and Na partitioning between miscible liquids. Petrology 16:552–564

    Article  Google Scholar 

  • Borisov AA (2009) Influence of SiO2 and Al2O3 on the activity coefficients of alkalis in melts: an experimental study. Petrology 17:579–590

    Article  Google Scholar 

  • Borisov A, McCammon C (2010) The effect of silica on ferric/ferrous ratio in silicate melts: an experimental investigation using Mössbauer spectroscopy. Am Miner 95:545–555

    Article  Google Scholar 

  • Borisov AA, Shapkin AI (1990) A new empirical equation relating Fe3+/Fe2+ in magmas to their composition, oxygen fugacity, and temperature. Geochem Int 27:111–116

    Google Scholar 

  • Borisov A, Lahaye Y, Palme H (2006) The effect of sodium on the solubilities of metals in silicate melts. Am Mineral 91:762–771

    Article  Google Scholar 

  • Borisov A, Pack A, Kropf A, Palme H (2008) Partitioning of Na between olivine and melt: an experimental study with application to the formation of meteoritic Na2O-rich chondrule glass and refractory forsterite grains. Geochim Cosmochim Acta 72:5558–5573

    Article  Google Scholar 

  • Borisov A, Behrens H, Holtz F (2013) The effect of titanium and phosphorus on ferric/ferrous ratio in silicate melts: an experimental study. Contrib Min Petrol 166:1577–1591

    Article  Google Scholar 

  • Borisov A, Behrens H, Holtz F (2015) Effects of melt composition on Fe3+/Fe2+ in silicate melts: a step to model ferric/ferrous ratio in multicomponent systems. Contrib Min Petrol 169: Article 24

  • Bychkov AM, Borisov AA, Khramov DA, Urusov VS (1993) Change in the immediate environment of Fe atoms during the melting of minerals (Review). Geochem Int 30:1–25

    Google Scholar 

  • Chuang H-C, Hwang W-S, Liu S-H (2009) Effects of basicity and FeO content on the softening and melting temperatures of the CaO–SiO2–MgO–Al2O3 slag system. Mat Trans 50:1448–1456

    Article  Google Scholar 

  • Cicconi MR, Giuli G, Ertel-Ingrisch W, Paris E, Dingwell DB (2015) The effect of the [Na/(Na + K)] ratio on Fe speciation in phonolitic glasses. Am Mineral 100:1610–1619

    Article  Google Scholar 

  • Cicconi MR, de Ligny D, Gall TM, Neuvill DR (2016) Ca neighbors from XANES spectroscopy: A tool to investigate structure, redox, and nucleation processes in silicate glasses, melts, and crystals. Am Mineral 101:1232–1235

    Article  Google Scholar 

  • Cottrell E, Kelley KA, Lanzirotti A, Fischer RA (2009) High-precision determination of iron oxidation state in silicate glasses using XANES. Chem Geol 268:167–179

    Article  Google Scholar 

  • Dickenson MP, Hess PC (1981) Redox equilibria and the structural role of iron in aluminosilicate melts. Contrib Mineral Petrol 78:352–357

    Article  Google Scholar 

  • Farges F, Lefrere Y, Rossano S, Berthereau A, Calas G, Brown GE Jr (2004) The effect of redox state on the local structural environment of iron in silicate glasses: a combined XAFS spectroscopy, molecular dynamics, and bond valence study. J Non-cryst Solids 344:176–188

    Article  Google Scholar 

  • Fudali RF (1965) Oxygen fugacities of basaltic and andesitic magmas. Geochim Cosmochim Acta 29:1063–1075

    Article  Google Scholar 

  • Hehlen B, Neuville DR (2015) Raman response of network modifier cations in alumino-silicate glasses. J Phys Chem B 119:4093–4098

    Article  Google Scholar 

  • Hirashima H, Yoshida T, Brückner R (1988) Redox equilibria and constitution of polyvalent ions in oxide melts and glasses. Glastech Ber 61: 283–291

    Google Scholar 

  • Holmquist SB (1966) Ionic formulation of redox equilibria in glass melts. J Am Ceram Soc 49:228–229

    Article  Google Scholar 

  • Ishihara S (2004) The redox state of granitoids relative to tectonic setting and earth history: the magnetite-ilmenite series 30 years later. Geological Society of America Special Papers 389: 23–33

    Google Scholar 

  • Jayasuriya KD, O’Neil HStC, Berry A, Campbell SJ (2004) A Mössbauer study of the oxidation state of Fe in silicate melts. Am Mineral 89:1597–1609

    Article  Google Scholar 

  • Kennedy GC (1948) Equilibrium between volatiles and iron oxides in igneous rocks. Am J Sci 246:529–549

    Article  Google Scholar 

  • Kilinc A, Carmichael ISE, Rivers ML, Sack RO (1983) The ferric-ferrous ratio of natural silicate liquids equilibrated in air. Contrib Mineral Petrol 83:136–140

    Article  Google Scholar 

  • Kjeldsen J, Smedskjaer MM, Mauro JC, Yue Y (2014) On the origin of the mixed alkali effect on indentation in silicate glasses. J Non-cryst Solids 406:22–26

    Article  Google Scholar 

  • Kress VC, Carmichael ISE (1989) The lime-iron-silicate melt system: redox and volume systematics. Geochim Cosmochim Acta 53:2883–2892

    Article  Google Scholar 

  • 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 Min Petrol 108:82–92

    Article  Google Scholar 

  • Lange RA, Carmichael ISE (1989) Ferric/ferrous equilibria in Na2O–FeO–Fe2O3–SiO2 melts: effects of analytical techniques on derived partial molar volumes. Geochim Cosmochim Acta 53:2195–2204

    Article  Google Scholar 

  • Le Losq C, Neuville DR (2013) Effect of the Na/K mixing on the structure and the rheology of tectosilicate silica-rich melts. Chem Geol 346:57–71

    Article  Google Scholar 

  • Moore G, Righter K, Carmichael ISE (1995) The effect of dissolved water on the oxidation state of iron in natural silicate liquids. Contrib Min Petrol 120:170–179

    Article  Google Scholar 

  • Mysen BO, Richet P (2005) Silicate glasses and melts, properties and structure. Elsevier, Amsterdam, p 544

    Google Scholar 

  • Mysen BO, Toplis MJ (2007) Structural behavior of Al3+ in peralkaline, metaluminous, and peraluminous silicate melts and glasses at ambient pressure. Am Mineral 92:933–946

    Article  Google Scholar 

  • O’Neill HStC (2005) A method for controlling alkali-metal oxide activities in one-atmosphere experiments and its application to measuring the relative activity coefficients of NaO 0.5 in silicate melts. Am Mineral 90:497–501

    Article  Google Scholar 

  • Ottonello G, Moretti R, Marini L, Zuccolini MV (2001) Oxidation state of iron in silicate glasses and melts: a thermochemical model. Chem Geol 174:157–179

    Article  Google Scholar 

  • Park Y, Min DJ (2016) Sulfide Capacity of CaO–SiO2–FeO–Al2O3–MgOsatd. Slag ISIJ Int 56:520–526

    Article  Google Scholar 

  • Paul A, Douglas RW (1965) Ferrous-ferric equilibrium in binary alkali silicate glasses. Phys Chem Glasses 6:207–211

    Google Scholar 

  • Putirka K (2016) Rates and styles of planetary cooling on Earth, Moon, Mars, and Vesta, using new models for oxygen fugacity, ferric-ferrous ratios, olivine-liquid Fe-Mg exchange, and mantle potential temperature. Am Mineral 101:819–840

    Article  Google Scholar 

  • Riebling EF (1966) Structure of Sodium Aluminosilicate Melts Containing at Least 50 mol % SiO2 at 1500 °C. J Chem Physics 44:2857–2865

    Article  Google Scholar 

  • Sack RO, Carmichael ISE, Rivers ML, Ghiorso MS (1980) Ferric-ferrous equilibria in natural silicate liquids at 1 bar. Contrib Mineral Petrol 75:369–376

    Article  Google Scholar 

  • Schreiber HD (1986) Redox processes in glass-forming melts. J Non-Cryst Solids 84:129–141

    Article  Google Scholar 

  • Schuessler JA, Botcharnikov RE, Behrens H, Misiti V, Freda C (2008) Oxidation state of iron in hydrous phono-tephritic melts. Am Mineral 93:1493–1504

    Article  Google Scholar 

  • Shand SJ (1927) Eruptive rocks; their genesis, composition, classification, and their relation to ore deposits, with a chapter on meteorites. 1st ed. 360 p. Thomas Murby and Co., London

  • Shibata K (1967) The oxygen partial pressure of the magma from Mihara Volcano, O-sima, Japan. Bull Chem Soc Jpn 40:830–834

    Article  Google Scholar 

  • Sisson TW, Grove TL (1993) Experimental investigation of the role of H2O in calc-alkaline differentiation and subduction zone magmatism. Contrib Min Petrol 113:143–166

    Article  Google Scholar 

  • Sukenaga S, Kanehashi K, Shibata H, Saito N, Nakashima K (2016) Structural role of alkali cations in calcium aluminosilicate glasses as examined using oxygen-17 solid-state nuclear magnetic resonance spectroscopy. Met Mat Trans 47B:2016–2177

    Google Scholar 

  • Tangeman JA, Lange R, Forman L (2001) Ferric-ferrous equilibria in K2O–FeO–Fe2O3–SiO2 melts. Geochim Cosmochim Acta 65:1809–1819

    Article  Google Scholar 

  • Thornber CR, Roeder PL, Foster JR (1980) The effect of composition on the ferric-ferrous ratio in basaltic liquids at atmospheric pressure. Geochim Cosmochim Acta 44:525–532

    Article  Google Scholar 

  • Toplis MJ, Dingwell DB (2004) Shear viscosities of CaO–Al2O3–SiO2 and MgO–Al2O3–SiO2 liquids: implications for the structural role of aluminium and the degree of polymerisation of synthetic and natural aluminosilicate melts. Geochim Cosmochim Acta 68:5169–5188

    Article  Google Scholar 

  • Tsuchiyama A, Nagahara H, Hushiro I (1981) Volatilization of sodium from silicate melt spheres and its application to the formation of chondrules. Geochim Cosmochim Acta 45:1357–1367

    Article  Google Scholar 

  • Vercamer V, Lelong G, Hijiya H, Kondo Y, Galoisy L, Calas G (2015) Diluted Fe3+ in silicate glasses: structural effects of Fe-redox state and matrix composition. An optical absorption and X-band/Q-band EPR study. J Non-Cryst Solids 428:138–145

    Article  Google Scholar 

  • Webb SL, Banaszak M, Köhler U, Rausch S, Raschke G (2007) The viscosity of Na2O–CaO–Al2O3–SiO2 melts. Eur J Mineral 19:681–692

    Article  Google Scholar 

  • Wilke M, Farges F, Partzsch GM, Schmidt C, Behrens H (2007) Speciation of Fe in silicate glasses and melts by in-situ XANES spectroscopy. Am Mineral 92:44–56

    Article  Google Scholar 

  • Wilson AD (1960) The micro-determination of ferrous iron in silicate minerals by a volumetric and a colorimetric method. Analyst 85:823–827

    Article  Google Scholar 

Download references

Acknowledgements

The stay of AB in Hannover was funded by the German Science Foundation (DFG project Ho 1337/30-1). We thank Eric Wolff and Renat Almeev for the electron microprobe assistance and Florian Pohl for the help in the determination of ferric/ferrous ratios in glasses. We are grateful to editor Chris Ballhaus and three anonymous reviewers for their comments and suggestions which allowed us to improve the paper. This study was partly supported by Russian Science Foundation (Grant 14-17-00491).

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Alexander Borisov.

Additional information

Communicated by Prof. Othmar Müntener.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Borisov, A., Behrens, H. & Holtz, F. Effects of strong network modifiers on Fe3+/Fe2+ in silicate melts: an experimental study. Contrib Mineral Petrol 172, 34 (2017). https://doi.org/10.1007/s00410-017-1337-1

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s00410-017-1337-1

Keywords

Navigation