Mn-bearing "oxy-rossmanite" with tetrahedrally coordinated Al and B from Austria: Structure, chemistry, and infrared and optical spectroscopic study

Ertl, Andreas

doi:10.2138/am.2005.1683

Cited by 41 publications

(40 citation statements)

References 21 publications

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“…Schreyer et al (2000) and Marler and Ertl (2002) reported low-field 11 B MAS NMR spectra of a synthetic olenite with a nominal T-site content of Si 3 B 3 , and a [4] B-bearing olenite from a granitic pegmatite. Ertl et al (1997) and Hughes et al (2000Hughes et al ( , 2001 have shown that <T-O> distances in the tourmaline examined by Marler and Ertl (2002) are in accord with the presence of [4] B, and similar stereochemical results have been reported (Hughes et al 2004;Kalt et al 2001;Ertl et al 2005Ertl et al , 2006Ertl et al , 2007 indicating the presence of [4] B in Li-bearing tourmaline.…”

Section: Previous Worksupporting

confidence: 57%

The occurrence of tetrahedrally coordinated Al and B in tourmaline: An 11B and 27Al MAS NMR study

Lussier

Aguiar

Michaelis

et al. 2009

American Mineralogist

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Considerable uncertainty has surrounded the occurrence of tetrahedrally coordinated Al and B at the T site in tourmaline. Although previously detected in several tourmaline specimens, the frequency of these substitutions in nature, as well as the extent to which they occur in the tourmaline structure, is not known. Using 11 B and 27 Al MAS NMR spectroscopy, we have investigated the presence of B and Al at the T site in 50 inclusion-free tourmaline specimens of low transition-metal content and different species (elbaite, "fluor-elbaite," liddicoatite, dravite, uvite, olenite, and magnesiofoitite) from different localities worldwide. Chemical shifts of [4] B and [3] B in 11 B spectra, and [4] Al and [6] Al in 27 Al spectra, are well resolved, allowing detection of even small amounts of T-site constituents. In the observed spectra, [4] B and [3] B peaks are located at 0 and 18-20 ppm, respectively, with the greatest intensity corresponding to [3] B (=3 apfu). In 27 Al spectra, [4] Al and [6] Al bands are located at 68-72 and 0 ppm, respectively, with the greater intensity corresponding to [6] Al. However, inadequate separation of Y Al and Z Al precludes resolution of these two bands. Simulation of 11 B MAS NMR spectra shows that tetrahedrally and trigonally coordinated B can be readily distinguished at 14.1 T and that a [4] B content of 0.0-0.5 apfu is common in tourmaline containing low amounts of paramagnetic species. 27 Al MAS NMR spectra show that Al is also a common constituent of the T site in tourmaline. Determination of [4] Al content by peak-area integration commonly shows values of 0.0-0.5 apfu. Furthermore, the chemical shift of the 27 Al tetrahedral peak is sensitive to local order at the adjacent Y and Z octahedra, where [4] Al-Y Mg 3 and [4] Al-Y (Al,Li) 3 arrangements result in peaks located at ~65 and ~75 ppm, respectively. Both 11 B MAS NMR and 27 Al MAS NMR spectra show peak broadening as a function of transition-metal content (i.e., Mn 2+ + Fe 2+ = 0.01-0.30 apfu) in the host tourmaline. In 11 B spectra, broadening and loss of intensity of the [3] B signal ultimately obscures the signal corresponding to [4] B, increasing the limit of detection of [4] B in tourmaline. Our results clearly show that all combinations of Si, Al, and B: T = (Al, Si) 6 , T = (B, Si) 6 , T = (Al, B, Si) 6 , and T = Si 6 apfu, are common in natural tourmalines.

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Section: Previous Worksupporting

confidence: 57%

The occurrence of tetrahedrally coordinated Al and B in tourmaline: An 11B and 27Al MAS NMR study

Lussier

Aguiar

Michaelis

et al. 2009

American Mineralogist

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“…There has been considerable work done on the characterization (e.g. Hawthorne et al, 1993;Burns et al, 1994;Taylor et al, 1995;Dyar et al, 1998;Francis et al, 1999;Bloodaxe et al, 1999;Kalt et al, 2001;Cámara et al, 2002;Schreyer et al, 2002;Ertl and Hughes, 2002;Ertl et al, 2003aErtl et al, ,b, 2004Ertl et al, , 2005Hughes et al, 2000Marschall et al, 2004;Bosi et al, , 2005 and understanding (Hawthorne, 1996(Hawthorne, , 2002 of site occupancy in tourmaline. However, the complete derivation of site populations (and accurate bulk compositions) is not trivial, and our knowledge of the crystal chemistry of all the tourmaline minerals is still far from complete.…”

Section: Introductionmentioning

confidence: 99%

Mushroom elbaite from the Kat Chay mine, Momeik, near Mogok, Myanmar: I. Crystal chemistry by SREF, EMPA, MAS NMR and Mössbauer spectroscopy

et al. 2008

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Tourmaline from the Kat Chay mine, Momeik, near Mogok, Shan state, Myanmar, shows a variety of habits that resemble mushrooms, and it is commonly referred to as 'mushroom tourmaline'. The structure of nine single crystals of elbaite, ranging in colour from pink to white to black and purple, extracted from two samples of mushroom tourmaline from Mogok, have been refined (SREF) to R indices of~2.5% using graphite-monochromated Mo-Ka X-radiation. 11 B and 27 Al Magic Angle Spinning Nuclear Magnetic Resonance spectroscopy shows the presence of [4] B and the absence of [4] Al in samples with transition-metal content low enough to prevent paramagnetic quenching of the signal. Site populations were assigned from refined site-scattering values and unit formulae derived from electron-microprobe analyses of the crystals used for X-ray data collection. 57 Fe Mössbauer spectroscopy shows that both Fe 2+ and Fe 3+ are present, and the site populations derived by structure refinement show that there is no Fe at the Z site; hence all Fe 2+ and Fe 3+ occurs at the Y site. The 57 Fe Mössbauer spectra also show peaks due to intervalence charge-transfer involving Fe 2+ and Fe 3+ at adjacent Y sites. Calculation of the probability of the total amount of Fe occurring as Fe 2+ ÀFe 3+ pairs for a random short-range distribution is in close accord with the observed amount of Fe involved in Fe 2+ ÀFe 3+ , indicating that there is no short-range order involving Fe 2+ and Fe 3+ in these tourmalines.

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“…Aluminum-rich tourmalines with a mixed occupation of Si, B, and Al at the T site are common (Ertl et al 2005, 2012a, Lussier et al 2009), but for the first time are described here for Cu-rich tourmalines. The sum of [3] B and [4] B as determined by SREF is within an error of~1-10%, in very good agreement with the chemistry (SIMS data; Table 1).…”

Section: +mentioning

confidence: 98%

STRUCTURAL AND CHEMICAL INVESTIGATION OF A ZONED SYNTHETIC Cu-RICH TOURMALINE

et al. 2015

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A synthetic Cu-rich tourmaline crystal (Lebedev et al. 1988) consists of three different zones. Each zone was characterized by EMPA, SIMS, and single-crystal structure refinement (SREF). The first zone (which crystallized directly on the seed crystal) has the formula~X(Na 0. (1), c 7.087(1) Å (R = 2.5%). While [4] Al decreases from zone 1 to zone 3, [4] B increases (by chemistry and SREF), which could be explained by a decreasing temperature during tourmaline crystallization. Such a T-site occupancy is in agreement with the distance, which strictly monotonically decreases from 1.625(1) to 1.616(1) Å. We suggest that very small amounts of Cu are present at the Z site of all investigated tourmaline samples, but only in the Cu-richest zone (~14 wt.% CuO) is the refined value for Cu at the Z site (~1% of the total Cu) higher than the 3σ error. The YO 6 octahedron of this Cu-richest known tourmaline is mainly occupied by Cu. Two of the six (Cu,Al)-O distances are significantly enlarged: Y-O1 with 2.031(2) Å and Y-O3 with 2.170(2) Å, while the other distances Y-O2 and Y-O6 with~1.951(2) Å are significantly smaller. The proportion of the average of the two enlarged distances to the average of the other distances in the Cu-richest zone gives a value of~1.08, which is the highest value known so far for Cu-bearing tourmalines. We conclude that for the Cu-richest zone the Jahn-Teller effect appears to be verified.

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Mn-bearing "oxy-rossmanite" with tetrahedrally coordinated Al and B from Austria: Structure, chemistry, and infrared and optical spectroscopic study

Cited by 41 publications

References 21 publications

The occurrence of tetrahedrally coordinated Al and B in tourmaline: An 11B and 27Al MAS NMR study

The occurrence of tetrahedrally coordinated Al and B in tourmaline: An 11B and 27Al MAS NMR study

Mushroom elbaite from the Kat Chay mine, Momeik, near Mogok, Myanmar: I. Crystal chemistry by SREF, EMPA, MAS NMR and Mössbauer spectroscopy

STRUCTURAL AND CHEMICAL INVESTIGATION OF A ZONED SYNTHETIC Cu-RICH TOURMALINE

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