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Fe3+ reduction during biotite melting in graphitic metapelites: another origin of CO2 in granulites

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Abstract

The Fe3+/Fetot of all Fe-bearing minerals has been analysed by Mössbauer spectroscopy in a suite of biotite-rich to biotite-free graphitic metapelite xenoliths, proxies of an amphibolite-granulite transition through progressive biotite melting. Biotite contains 9 to 16% Fe3+/Fetot, whereas garnet, cordierite and ilmenite are virtually Fe3+ -free (0–1% Fe3+/Fetot) in all samples, regardless of biotite presence. Under relatively reducing conditions (graphite-bearing assemblages), biotite is the only carrier of Fe3+ during high-temperature metamorphism; therefore, its disappearance by melting represents an important event of iron reduction during granulite formation, because haplogranitic melts usually incorporate small amounts of ferric iron. Iron reduction is accompanied by the oxidation of carbon and the production of CO2, according to the redox reaction:

$$ 2{\text{Fe}}_2 {\text{O}}_3^{({\text{Bt}})} + {\text{C}}^{({\text{Gr}})} \Rightarrow 4{\text{FeO}}^{({\text{Crd}},{\text{Grt}},{\text{Ilm}},{\text{Opx}})} + {\text{CO}}_2^{({\text{fluid}},{\text{melt}},{\text{Crd}})} . $$

Depending on the nature of the peritectic Fe-Mg mineral produced (garnet, cordierite, orthopyroxene), the CO2 can either be present as a free fluid component, or be completely stored within melt and cordierite. The oxidation of graphite by iron reduction can account for the in situ generation of CO2, implying a consequential rather than causal role of CO2 in some granulites and migmatites. This genetic model is relevant to graphitic rocks more generally and may explain why CO2 is present in some granulites although it is not required for their formation.

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References

  • Baker LL, Rutherford MJ (1996) The effect of dissolved water on the oxidation state of silicic melts. Geochim Cosmochim Acta 60:2179–2187

    Google Scholar 

  • Brown M (2002) Retrograde processes in migmatites and granulites revisited. J Metamorph Geol 20:25–40

    Google Scholar 

  • Brown M (2003) Metamorphism. Geotimes Highlights: Discoveries in the Earth Sciences. 22:48–7

  • Cesare B, Maineri C (1999) Fluid-present anatexis of metapelites at El Joyazo (SE Spain): constraints from Raman spectroscopy of graphite. Contrib Mineral Petrol 135:41–52

    Article  Google Scholar 

  • Cesare B, Salvioli Mariani E, Venturelli G (1997) Crustal anatexis and melt extraction in the restitic xenoliths at El Hoyazo (SE Spain). Mineral Mag 61:15–27

    Google Scholar 

  • Cesare B, Cruciani G, Russo U (2003a) Hydrogen deficiency in Ti-rich biotite from anatectic metapelites (El Joyazo - SE Spain): crystal-chemical aspects and implications for high-temperature petrogenesis. Am Mineral 88:583–595.

    Google Scholar 

  • Cesare B, Marchesi C, Hermann J, Gomez-Pugnaire MT (2003b) Primary melt inclusions in andalusite from anatectic graphitic metapelites: Implications for the position of the Al2SiO5 triple point. Geology 31:573–576

    Article  Google Scholar 

  • Cesare B, Maineri C, Baron Toaldo A, Pedron D (2004) Crustal melting, granite formation and immiscibility with carbonic fluids: a fluid inclusion study of the restitic enclaves from the Neogene Volcanic Province of SE Spain. 32nd Int Geol Congr, Abs Vol 1, abs 86–6, 422–423

  • Chacko T, Ravindra Kumar GR, Newton RC (1987) Metamorphic conditions in the Kerala (South India) Khondalite Belt: a granulite-facies supracrustal terrain. J Geol 96:343–358

    Google Scholar 

  • Clemens JD (1990) The granulite - granite connexion. In: Vielzeuf D, Vidal P (eds) Granulites and Crustal Differentiation, Kluwer Academic Publishers, Dordrecht, pp 25–36

    Google Scholar 

  • Clemens JD (1993) Experimental evidence against CO2-promoted deep crustal melting. Nature 363:336–338

    Article  Google Scholar 

  • Clemens JD, Vielzeuf D (1987) Constraints on melting and magma production in the crust. Earth Planet Sci Lett 86:287–306

    Article  Google Scholar 

  • Dharma Rao CV (2000) Metapelitic migmatites from Pangidi, complex, Eastern Ghats Belt, India. Gondw Res 3:105–117

    Google Scholar 

  • Droop GTR (1987) A general equation for estimating Fe3+ concentrations in ferromagnesian silicates and oxides from microprobe analyses, using stoichiometric criteria. Mineral Mag 51:431–435

    CAS  Google Scholar 

  • Dyar MD, Burns RG (1986) Mössbauer spectral study of ferruginous one-layer trioctahedral micas. Am Mineral 71:955–965

    Google Scholar 

  • Dyar MD, Lowe EW, Guidotti CV, Delaney JS, (2002) Fe3+ and Fe2+ partitioning among silicates in metapelites: A synchrotron micro-XANES study. Am Mineral 87:514–52

    Google Scholar 

  • Edwards RL, Essene EJ (1989) Pressure, temperature and C-O-H fluid fugacities across the amphibolite - granulite facies transition, NW Adirondack Mountains, NY. J Petrol 29:39–73

    Google Scholar 

  • Engel AE, Engel CG (1958) Progressive metamorphism and granitization of the major paragneiss, Northwest Adirondack Mountains, New York. Part I. Total Rock. Bull Geol Soc of Am 69:1369–1414

    Google Scholar 

  • Farquhar J, Chacko T (1991) Isotopic evidence for involvement of CO2-bearing magmas in granulite formation. Nature 354:60–63

    Article  Google Scholar 

  • Ferraris C, Grobety B, Früh-Green GL, Wessicken R (2004) Intergrowth of graphite within phlogopite from Finero ultramafic complex (Italian, Western Alps): implications for mantle crystallization of primary-texture mica. Eur J Mineral 16:899–908

    Article  Google Scholar 

  • Fitzsimons ICW, Harley SL (1991) Geological relationships in high-grade gneiss of the Brattstrand Bluffs coastline, East Antarctica. Austr J Earth Sci 38:497–519

    Google Scholar 

  • Fitzsimons ICW, Mattey DP (1994) Carbon isotope constraints on volatile mixing and melt transport in granulite-facies migmatites. Earth Planet Sci Lett 134:319–328

    Article  Google Scholar 

  • Frost BR, Frost CD (1987) CO2, melts and granulite metamorphism. Nature 327:503–506

    Article  Google Scholar 

  • Geiger CA, Rager H, Czank M (2000) Cordierite III: the site occupation and concentration of Fe3+. Contrib Mineral Petrol 140:344–352

    Article  Google Scholar 

  • Guidotti CV (1970), The mineralogy and petrology of the transition from the lower to upper sillimanite zone in the Oquossoc area, Maine. J Petrol 11:277–336

    Google Scholar 

  • Hand M, Scrimgeour I, Powell R, Stüwe K, Wilson CJL (1994) Metapelitic granulites from Jetty Peninsula, east Antarctica: Formation during a single event or by polymetamorphism?. J Metamorph Geol 12:557–573

    Google Scholar 

  • Hansen EC, Janardhan AS, Newton RC, Pram WKBN, Ravindra Kumar GR (1987) Arrested charnockite formation in South India and Sri Lanka. Contrib Mineral Petrol 96:225–244

    Article  Google Scholar 

  • Harley SL (1989) The origins of granulites: a metamorphic perspective. Geol Mag 126:215–247

    CAS  Google Scholar 

  • Harley SL, Thompson P, Hensen BJ, Buick IS (2002) Cordierite as a sensor of fluid conditions in high-grade metamorphism and crustal anatexis. J Metamorph Geol 20:71–86

    Google Scholar 

  • Hollister LS (1988) On the origin of CO2-rich fluid inclusions in migmatites. J Metamorph Geol 6:467–474

    Google Scholar 

  • Holtz F, Johannes W, Tamic N, Behrens H (2001) Maximum and minimum water contents of granitic melts generated in the crust; a reevaluation and implications. Lithos 56:1–14

    Google Scholar 

  • Kawakami T, Ikeda T (2003) Depletion of whole-rock boron controlled by the breakdown of tourmaline and retrograde formation of borosilicates in the Yanai area, Ryoke metamorphic belt, SW Japan. Contrib Mineral Petrol 145:131–150

    Google Scholar 

  • Kerrick DM (2001) Present and past non-anthropogenic CO2 degassing from the solid Earth. Rev Geophys 39:565–585

    Article  Google Scholar 

  • Khomenko VM, Langer K, Geiger CM (2001) Structural locations of the iron ions in cordierite: a spectroscopic study. Contrib Mineral Petrol 141:381–396

    Google Scholar 

  • Korja T, Tuisku P, Pernu T, Karhu J (1996) Field, petrophysical and carbon isotope studies on the Lapland granulite belt: implications for deep continental crust. Terra Nova 8:48–58

    Google Scholar 

  • Kretz R (1983) Symbols for rock-forming minerals. Am Mineral 68: 277–279

    Google Scholar 

  • Kriegsman LM (2001) Quantitative field methods for estimating melt production and melt loss. Phys Chem Earth A 26:247–253

    Article  Google Scholar 

  • Lamb WM, Valley JW, Brown PE (1987) Post-metamorphic CO2-rich fluid inclusions in granulites. Contrib Mineral Petrol 96:485–495

    Google Scholar 

  • Mörner N-A, Etiope G (2002) Carbon degassing from the lithosphere. Global Planet Change 33:185–203

    Article  Google Scholar 

  • Newton RC, Smith JV, Windley BF (1980) Carbonic metamorphism, granulites and crustal growth. Nature 288:45–50

    Article  Google Scholar 

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

    Article  Google Scholar 

  • Patiño Douce AE, Beard JS (1995) Dehydration melting of biotite gneiss and quartz amphibolite from 3 to 15 kbar. J Petrol 36:707–738

    CAS  Google Scholar 

  • Peterson JW, Newton RC (1989) CO2-enhanced melting of biotite-bearing rocks at deep-crustal pressure-temperature conditions. Nature 340:378–380

    Article  Google Scholar 

  • Pineau F, Javoy M, Behar F, Touret J (1981) La geochimie isotopique du facies granulite du Bamble (Norvege) et l’origine des fluides carbones dans la croute profonde. Bull Mineral 104:630–641

    Google Scholar 

  • Radhika UP, Santosh M (1995) A comparative study of graphite occurrences in South India, Sri Lanka and Madagascar within East Gondwana. Gondwana Res Group Memoir No 2. Field Sci Pub, Osaka, pp 143–158

  • Rancourt DG, Ping JY (1991) Voigt-based methods for arbitrary-shape static hyperfine parameter distributions in Mössbauer spectroscopy. Nucl Instr Meth B 58:85–97

    Google Scholar 

  • Roedder E (1984) Fluid inclusions. MSA Rev Min 12:644

    Google Scholar 

  • Santosh M (1992) Carbonic fluids in granulites: Cause or consequence? J Geol Soc of India 39:375–399

    Google Scholar 

  • Sarkar S, Santosh M, Dasgupta S, Fukuoka M (2003) Very high density CO2 associated with ultrahigh-temperature metamorphism in the Eastern Ghats granulite belt, India. Geology 31:51–54

    Article  CAS  Google Scholar 

  • Schmid R, Wood BJ (1976) Phase relationships in granulitic metapelites from the Ivrea-Verbano zone (Northern Italy). Contrib Mineral Petrol 54:255–279

    Article  Google Scholar 

  • Shchipanski AA, Bogdanova SV (1996) The Sarmatian crustal segment: Precambrian correlation between the Voronezh Massif and the Ukrainian Shield across the Dniepr-Donets Aulacogen. Tectonophysics 268:109–125

    Article  Google Scholar 

  • Sighinolfi GP (1968) Rapporto di ossidazione del ferro in una serie metamorfica della Valle Strona (Novara). Schweiz Mineral Petrogr Mitt 48:31–39

    Google Scholar 

  • Skogby H, Annersten H, Domeneghetti M-C, Molin G, Tazzoli V (1992) Iron distribution in orthopyroxene: A comparison of Mössbauer spectroscopy and X-ray refinement results. Eur J Mineral 4:441–452

    Google Scholar 

  • Stevens G, (1997) Melting, carbonic fluids and water recycling in thee deep crust: An example from the Limpopo belt, South Africa. J Metamorphic Geol 15:141–154

    Google Scholar 

  • Stevens G, Clemens JD, Droop TR (1997) Melt production during granulite-facies anatexis: experimental data from ‘primitive’ metasedimentary protoliths. Contrib Mineral Petrol 128:352–370

    Article  CAS  Google Scholar 

  • Stevens JG, Khasanov AM, Miller JW, Pollak H, Li Z (1998) Mössbauer mineral handbook, Mössbauer Effect Data Center

  • 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 174:333–347

    Article  Google Scholar 

  • Thompson AB (1982) Dehydration melting of pelitic rocks and the generation of H2O-undersaturated granitic liquids. Am J Sci 282:1567–1595

    CAS  Google Scholar 

  • Touret JLR (1971) Le faciès granulite en Norvège méridionale. II Les inclusions fluides. Lithos 4:423–436

    Article  Google Scholar 

  • Touret JLR (1981) Fluid inclusions in high grade metamorphic rocks. In: Short Course in fluid inclusions: applications to petrology, Hollister, LS, Crawford, ML, Min. Assoc. Canada, Calgary, 182–208

  • Touret JLR, Dietvorst P (1984) Fluid inclusions in high-grade anatectic metamorphites. J Geol Soc London 140:635–649

    Google Scholar 

  • Touret JLR, Hartel THD (1990) Synmetamorphic fluid inclusions in granulites. In: Vielzeuf D, Vidal P (eds) Granulites and Crustal Differentiation, Kluwer Academic Publishers, Dordrecht, pp 397–417

    Google Scholar 

  • Touret JLR, Huizenga JM (1999) Precambrian intraplate magmatism: high temperature, low pressure crustal granulites. J Afr Earth Sci 28:367–382

    Article  CAS  Google Scholar 

  • Tsunogae T, Santosh M, Osanai Y, Owada M, Toyoshima T, Hokada T (2002) Very high-density carbonic fluid inclusions in sapphirine-bearing granulites from Tonagh Island in the Archean Napier Complex, East Antarctica: implications for CO2 infiltration during ultrahigh-temperature (T>1100°C) metamorphism. Contrib Mineral Petrol 143:279–299

    CAS  Google Scholar 

  • Valley JW, McLelland J, Essene EJ, Lamb WM (1983) Metamorphic fluids in the deep crust: evidence from the Adirondacks. Nature 20:226–228

    Article  Google Scholar 

  • Vielzeuf D, Holloway JR (1988) Experimental determination of the fluid-absent melting relations in the pelitic system. Consequences for crustal differentiation. Contrib Mineral Petrol 98:257–276

    Article  CAS  Google Scholar 

  • Vielzeuf D, Schmidt MW (2001) – Melting relations in hydrous systems revisited. Applications to metapelites, metagreywackes and metabasalts. Contrib Mineral Petrol 141:251–267

    Google Scholar 

  • Vielzeuf D, Clemens JC, Pin C, Moinet E (1990) Granites, granulites and crustal differentiation. In: Vielzeuf D, Vidal P (eds) Granulites and Crustal Differentiation. Kluwer Academic Publishers, Dordrecht, pp 59–85

    Google Scholar 

  • Virgo D, Luth WR, Moats MA, Ulmer GC (1988) Constrains on the oxidation state of the mantle: An electrochemical and 57Fe Mössbauer study of mantle-derived ilmenite. Geochim Cosmochim Acta 52:1781–1794

    Google Scholar 

  • Vry J, Brown PE, Valley JW, Morrison J (1988) Constraints on granulite genesis from carbon isotope compositions of cordierite and graphite. Nature 332:66–68

    Article  Google Scholar 

  • Waerenborgh JC, Figueiras J, Mateus A, Gonçalves M (2002) Nature and mechanism of ilmenite alteration: a Mössbauer and X-ray diffraction study of oxidised ilmenite from the Beja-Acebuches Ophiolite Complex (SE Portugal). Mineral Mag 66:421–430

    Article  Google Scholar 

  • Watson EB, Brenan JM (1987) Fluids in the lithosphere, 1 Experimentally determined wetting characteristics of CO2-H2O fluids, their implications for fluid transport, host-rock physical properties, and fluid inclusion formation. Earth Planet Sci Lett 85:497–515

    Article  Google Scholar 

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Acknowledgements

Funding was provided by the University of Padova (Fondi Progetti Ricerca 2002) and Consiglio Nazionale delle Ricerche (Westmed Euromargins European Science Foundation Eurocore). We thank S. Harley and J. Touret for their thoughtful reviews, J. Connolly, E. Essene, L. Hollister, S. Intento, P. Nimis, and M. Satish-Kumar for comments on an earlier version of the manuscript, R. Carampin and F. Zorzi for assistance with microprobe analysis and X-ray diffractometry, respectively.

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  1. Dipartimento di Mineralogia e Petrologia, Università di Padova, Corso Garibaldi, 37, 35137, Padova, Italy

    Bernardo Cesare

  2. CNR, Istituto di Geoscienze e Georisorse, Sezione di Padova, Corso Garibaldi, 37, 35137, Padova, Italy

    Bernardo Cesare

  3. Dipartimento di Scienze della Terra, Università di Parma, Parco Area delle Scienze 157a, 43100, Parma, Italy

    Sandro Meli

  4. Dipartimento di Scienze Chimiche, Università di Padova, Via Marzolo, 1, 35131, Padova, Italy

    Luca Nodari & Umberto Russo

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Correspondence to Bernardo Cesare.

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J.L.R. Touret

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Cesare, B., Meli, S., Nodari, L. et al. Fe3+ reduction during biotite melting in graphitic metapelites: another origin of CO2 in granulites. Contrib Mineral Petrol 149, 129–140 (2005). https://doi.org/10.1007/s00410-004-0646-3

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