Background Information on Ilvaite

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References (supplement)

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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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.

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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 CaFe_2−x²⁺Mn_xFe³⁺ [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.

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