Background Information on Ilvaite



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Background Information on Ilvaite

Ilvaite is a mixed-valence Ca-Fe sorosilicate which was named for Ilva, the latin name of the Elba island, where the type locality (Capo Calamita) is located. In the older literature, ilvaite is also known as lievrite, due to its discoverer (M. Lelièvre, in 1802) and yenite (or jenite), in commemoration of the Jena battle (Lelièvre, 1807; Brongniart, 1807; Webster, 1828; Thomson, 1837; Dana, 1854). Although it is not a common mineral, it is has been described in a wide variety of geological environments (Table S1). However, the most typical occurrence of ilvaite is iron-rich skarns, where it uses to be associated to hedenbergite, andradite, magnetite, quartz and calcite.


The composition of ilvaite can be represented by the formula CaFe22+Fe3+Si2O8(OH) and its structure was first resolved by Belov & Mokeeva (1954) and later confirmed by Beran & Bittner (1972, 1974) and Haga & Takéuchi (1976). Fe2+ and Fe3+ ions occur in octahedral (A sites) double chains parallel to the c axis. Larger octahedral (B sites) containing only Fe2+ ions are attached above and below these chains, which are cross-linked to the calcium atoms (in seven-fold coordination) and dimer [Si2O7] groups (Herzenberg & Riley, 1969; Yamanaka & Takéuchi, 1979; Xuemin et al., 1988). At room temperature ilvaite has a monoclinic crystal structure (space group P21/a; Ghose et al., 1984; Schmidbauer et al.,

2005) but between 333 and 343 K it switches (crystallographic phase transition) into an


orthorhombic structure (space group Pnam; Ghose et al., 1985, 1989). It is well known that ilvaite becomes antiferromagnetic below 120 K (Yamanaka & Takéuchi, 1979; Coey et al., 1984; Ghose et al., 1984; Xuemin et al., 1988). It also undergoes magnetic phase transitions at 40 and 120 K (Coey et al., 1984; Ghosh et al., 1987) and a thermal phase transition between 300 and 400 K due to electron delocalization (Gerard & Grandjean, 1971; Grandjean & Gerard, 1975; Nolet & Burns, 1979; Evans & Amthauer, 1980; Litterst & Amthauer, 1984; Ghose et al., 1990; Güttlher et al., 1989). A summary of the studies aimed at characterizing different physical properties of ilvaite is given in Table S2.

.

Table S1. Occurrence of ilvaite in different geologic contexts and related minerals, according to a literature review. Mineral symbols according to recommendations of the Mineralogical Association of Canada (http://www.canmin.org/), except ilvaite (Ilv), howieite (Hw), deerite (De), julgoldite (Jul) and babingtonite (Bab).





Occurrences

References

Related minerals

Comments

Skarn and skarnoids

Bartholomé & Dimanche (1967), Bartholomé et al. (1968), Burt (1971b), Plimer & Ashley (1978), Verkaeren & Bartholomé (1979), Bratus (1979), Gole (1981), Kwak & Askins (1981), Einaudi et al. (1981), Galley et al. (1993), Kwak (1983), Meinert, (1984, 1987), Vivallo (1985), Pesquera & Velasco (1986), Tornos (1989), Delgado (1993), Capitani & Mellini (2000), Logan (2000), Franchini et al. (2002), Larsen & Dahlgren (2002), Damian (2003), Bonev et al. (2005), Simanenko (2006), Levresse et al. (2006)

Fac, Hd, Adr, Gru, Stp, Chl, Qtz, Cal, Mgt, Po, Ep, Py, Sp

Typically associated to retrograde stages replacing the Adr/Hd prograde assemblages

Alteration of mafic rocks and serpentinites

Wager et al. (1957), Ramdohr (1967), Dietrich (1972), Graesser (1975), Naslund et al. (1983), Barton & Bergen (1984), Agata & Adachi (1995), Larsen & Dahlgren (2002)

Fac, Cum, Chl, Bt, Prh, Ep, Pl, Srp, Qtz, Cal

Fe-rich veins,

Cu-Ni ores associated to ultrabasic rocks

cited by Bartholomé & Dimanche (1967)





Metarodingites

Lucchetti (1989)

granditic garnets, diopsidic Cpx, Chl, Amp, Mgt

Metarodingitic lenses within Atg-Srp schists

Metasomatism of alkaline igneous rocks

Soen & Sørensen (1964), Graser & Markl (2008)

Ab, Kfs, Adr (Adr44-Ad100) Ap, Ae

Endoskarns developed over persodic (agpaitic) magmatic rocks. Unusual Qtz-absent assemblages

Igneous

Mücke (2003)

Gru, Ch, Stp

Mafic clots within granitic rocks

Hydrothermal/metasomatic alteration of volcanogenic massive sulfides

Plimer & Ashley (1978), Galley et al. (2000)

Hd, Adr, Fac, Mgt, Gru, Gre, Min, Stp

Associated to a Mgt-rich calcsilicate alteration

Iron-rich blueschists facies metamorphism

Muir-Wood (1982)

Hw, Rbk, Ae, Aug, Stp, De, Act



Sub-seafloor metalliferous sediments with calcsilicates (Atlantis II Deep, Red Sea)

Weiss et al. (1980), Zierenberg & Shanks (1983), Singer & Stoffers (1987), Ramboz et al. (1988)

Hem, Mgt, Grt, Cpx, Act, Vrm



Low temperature hydrothermal veins and cavities

Wise & Moller (1990)

Prh, Chl, Lmt, Qtz, Cal, Jul, Bab, Adr, Hem

Filled vugs in altered basalts. ~200 ºC and 50 MPa

Venus surface

Burns & Straub (1992)

Hypothetical occurrence


Table S2. Summary of studies involving ilvaite.



Study

References

Optical properties

Beran (1980), Bonazzi et al. (2001)

Thermal behavior and spectrometry

Nolet & Burns (1979), Güttlher et al. (1989), Bonazzi & Bindi (1999, 2002)

Structural characterization

Belov & Mokeeva (1954), Bartholomé et al. (1968), Herzenberg & Riley (1969), Takéuchi et al. (1983),

Finger & Hazen (1987), Ghose et al. (1989), Ghazi-Bayat et al. (1993), Carrozzini (1994),

Bonazzi & Bindi (1999, 2002), Bonev (2005)


Isothermal compression

Finger & Hazen (1987), Ghazi-Bayat et al. (1993)

Isobaric thermal expansion

Robie et al. (1988)

Magnetic properties

Beran & Bittner (1974),Nolet (1978), Yamanaka & Takéuchi (1979), Coey et al. (1984), Xuemin et al. (1988),

Cesena et al. (1995), Fehr et al. (2005)



Electrical properties

Coey et al. (1984), Schmidbauer et al. (1998, 2005)

Synthesis

Gustafson (1974), Ghazi-Bayat et al. (1987), Ghazi-Bayat et al. (1989), Jenkins & Bozhilov (2003)

Thermodynamic properties

Robie et al. (1988)

Phase equilibria

Bartholomé & Dimanche (1967), Burt (1971a and c)

Stable isotopes fractionation factor

Yaqian & Jibao (1993)



References (supplement)


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Bartholomé, P. & Dimanche, F. (1967) : On the paragenesis of ilvaite in italian skarns. Ann. Soc. Géol. Belgique, 90, 533-565

―, Duchesne, J.C., van der Plas, L. (1968): Sur une forme monoclinique de l'ilvaite. Ann. Soc. Géol. Belgique, 90, 779-788

Barton, M. & Bergen, M.J. (1984): Secondary ilvaite in a dolerite dyke from Rogaland, SW Norway. Mineral. Mag., 48, 449-456

Belov, N.V. & Mokeeva, V.I. (1954): Kristallicheskaya struktura ilvaita. Trudy Inst. Kristallogr. Akad. Nauk. SSSR, 9, 47-102 (in Russian)

Beran, A. (1980): A reflected light investigation of ilvaite. Miner. Petrol., 27, 225-230

― & Bittner, H. (1972): Verfeinerung der Kristallstruktur von Ilvait und Messung der Protonenresonanz. Neues.Jb. Miner. Monat., 1972, 551–553

― & ― (1974): Untersuchungen zur Kristallchemie des Ilvaits. Tscher. Miner. Petrog. Mitt., 21, 11-29

Bonazzi, P., Bindi, L. (1999): Structural adjustments induced by heat treatment in ilvaite. Am. Mineral., 84, 1604-1612

―, ― (2002): Structural properties and heat-induced oxidation-dehydrogenation of manganoan ilvaite from Perda Niedda mine, Sardinia, Italy. Am. Mineral., 87, 845-852

―, ―, Olmi, F. (2001): Reflectance variations in heat-treated ilvaite. Miner. Petrol., 72, 249-257

Bonev, I.K., Vassileva, R.D., Zotov, N., Kouzmanov, K. (2005): Manganilvaite, CaFe2+Fe3+(Mn,Fe2+)(Si2O7)O(OH), a new mineral of the ilvaite group from Pb-Zn skarn deposits in the Rhodope mountains (Bulgaria). Can. Mineral. 43, 1027-1042

Bratus, M.D., Drschakovskaia, K.A., Platonova, E.L., Sasin, G.G., Terleckij, A.V. (1979): The mineralogy of the Beregovo deposit. Miner. Sbornik, 33, 44-53

Brongniart, A. (1807): Traité élémentaire de minéralogie avec des applications aux arts. Imprimerie de Crapelet. Paris, 442 p.

Burns, R. G. & Straub, D. W. (1992): Mixed-valence iron minerals on Venus: Fe2+- Fe3+ oxides and oxy-silicates formed by surface–atmosphere interactions. Int. Conf. on Venus [abstr.], 15-17

Burt, D.M. (1971a): Some phase equilibria in the system Ca-Fe-Si-C-O. Carn. Inst. Washington Yearbook, 70, 178-184.

― (1971b): The facies of some Ca-Fe-Si skarns in Japan. Carn. Inst. Washington Yearbook, 70, 185-188.

― (1971c): Multisystems analysis of the relative stabilities of babingtonite and ilvaite. Carn. Inst. Washington Yearbook, 70, 189-197

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Carrozzini, B. (1994): Crystal structure refinements of ilvaite: new relationships between chemical composition and crystallographic parameters. Eur. J. Mineral., 6, 465-479

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Coey, J.M.D., Allan, J., Xuemin, K., Dang, K.V., Ghose, S. (1984): Magnetic and electrical properties of ilvaite. J. Appl. Phys., 55, 1963-1965

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Dietrich, V.V. (1972): Ilvait, ferroantigorit und greenalith als Begleiter oxidisch-sulfidichen venerzurgen in den Oberhalbsteiner serpentiniten. Schweiz. Miner. Petrog. Mitt., 52, 57-78

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Evans, B.J. & Amthauer, G. (1980): The electronic structure of ilvaite and the pressure and temperature dependence of its 57Fe Mössbauer spectrum. J. Phys. Chem. Solids, 41, 985-1001

Fehr, K.T., Schneider, J., Hochleitner, R., Schmidbauer, E. (2005): Structure and physical property relations of Mn ilvaite Part 1: Compositional, structural and Mössbauer data. Phys. Chem. Minerals, 32, 388-399

Finger, L.W. & Hazen, R.M. (1987): Crystal structure of monoclinic ilvaite and the nature of the monoclinic-orthorhombic transition at high pressure. Z. Kristallogr., 179, 415-430

Franchini, M.B., Meinert, L.D., Vallés, J.M. (2002): First occurrence of ilvaite in a gold skarn deposit. Econ. Geol., 97, 1119-1126

Galley, A.G., Bailes, A.H., Kitzler, G. (1993): Geological setting and hydrothermal evolution of the Chisel Lake and North Chisel Zn-Pb-Ag-Au massive sulphide deposit, Snow Lake, Manitoba. Explor. Min. Geol., 2, 271-295.

―, Jonasson, I.R., Watkinson, D.H. (2000): Magnetite-rich calc-silicate alteration in relation to synvolcanic intrusion at the Ansil volcanogenic massive sulfide deposit, Rouyn–Noranda, Quebec, Canada. Mineral. Dep., 35, 619-637

Gerard, A. & Grandjean, F. (1971): Observation by Mössbauer effect of an electron hopping process in ilvaite. Solid State Commun., 9, 1845-1849

Ghazi-Bayat, B.; Amthauer, G., Ahsbahs, H. (1993): High pressure X-ray diffraction study of ilvaite CaFe22+Fe3+[Si2O7/O/(OH)]. Phys. Chem. Minerals, 20, 402-406

―, ―, Hellner, E. (1989): Synthesis and characterization of Mn-bearing ilvaite CaFe2−x2+MnxFe3+ [Si2O7/O/(OH)]. Miner. Petrol., 40, 101-109

―, ―, Schürmann, K.; Hellner, E. (1987): Synthesis and characterization of the mixed valent iron silicate ilvaite, CaFe3[Si2O7/O/(OH)]: Miner. Petrol., 37, 97-108

Ghose, S., Hewatt, A.W., Marezio, M. (1984): A neutron powder diffraction study of the crystal and magnetic structures of ilvaite from 305 K to 5 K — a mixed valence iron silicate with an electronic transition. Phys. Chem. Minerals, 11, 67-74.

―, ― , Pinkney, M. (1990): A powder neutron diffraction study of magnetic phase transitions and spin frustration in ilvaite, a mixed-valence iron silicate showing a semiconductor-insulator transition. Solid State Commun., 74, 413-418

―, Sen Gupta, P.K., Schlemper, E.O. (1985): Electron ordering in ilvaite, a mixed-valence iron silicate: crystal structure refinement at 138 K. Am. Mineral., 70, 1248-1252

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Gole, M.J. (1981): Ca-Fe-Si skarns containing babingtonite: first known occurrence in Australia. Can. Mineral., 29, 269-277

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Herzenberg, C.L. & Riley, D.L. (1969): Oxidation states and site symmetries of iron in ilvaite using Mössbauer spectrometry. Acta Crystallogr., A25, 389-391

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