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The Atomic Arrangement of Cr-rich Tourmaline from the #1 Mine, Balmat, St. Lawrence County, New York, USA

TitleThe Atomic Arrangement of Cr-rich Tourmaline from the #1 Mine, Balmat, St. Lawrence County, New York, USA
Publication TypeJournal Article
Year of Publication2019
AuthorsDannenberg, SG, Di Paolo, D, Ehlers, AM, McCarthy, KP, Mancini, MT, Reuter, MB, Seth, DM, Song, Z, Valladares, MI, Zhu, X, Hughes, JM, Lupulescu, MV
JournalMinerals
Volume9
Issue7
Pagination398
Date Published06/2019
KeywordsBalmat mine, chromium-dravite, New York, St. Lawrence County, tourmaline
Abstract

Chromium-bearing tourmalines are rare. Chromium-rich tourmaline from the northwestern part of the Adirondack Mountains in the Adirondack Lowlands is among the most chromium-rich tourmalines found to date. The mineral, with >21.0 wt. % Cr2O3, is from the marble-hosted talc–tremolite–cummingtonite schist in the #1 mine in Balmat, St. Lawrence County, New York. The atomic arrangement of the sample (a = 16.0242(3) Å, c = 7.3002(2) Å) was refined to R1 = 0.0139. The composition, from chemical analyses and optimization of the formula, is X(Ca0.22Na0.69K0.01) Y(Cr3+1.68Mg0.80Ti0.13V0.06Mn0.02Fe0.02Li0.29) Z(Al3.11Cr3+1.18Mg1.70Fe0.01) T(Si5.93Al0.07) B3O27 OH3.99 F0.01. There has been extensive debate over the ordering of Cr3+ between the tourmaline Y and Z octahedral sites. Recent work has suggested that, at low concentrations (<~1.03 apfu), the substituent Cr3+ is ordered into the Y-site, whereas, at greater concentrations, the substituent is disordered over both octahedral sites. An analysis of nine recently published, high-precision structures of chromium-bearing tourmaline, in combination with the Adirondack tourmaline, suggests that structural changes to the Y-site at low concentrations of Cr3+ induce changes in the Z-site that make it more amenable to incorporation of the Cr3+ substituents by increasing <Z–O>. The bond lengths change to lower the bond-valence sum of Cr3+ in the Z-site of the chromium-dravite, making that site more amenable to the substituent. Calculations suggest that the Z-site begins to accept substituent Cr3+ when the bond valence sum of that ion in Z reduces to a value of ~3.36 valence units.

URLhttps://www.mdpi.com/2075-163X/9/7/398https://www.mdpi.com/2075-163X/9/7/398/pdf
DOI10.3390/min9070398
Short TitleMinerals