Titanium, Fluorine, and Hydroxyl in the Hrrmite Minerals
AmericanMineralogist, Volume 64, pages 1027-1035, 1979 Titanium, fluorine, and hydroxyl in the hrrmiteminerals Paul H. RBns Department of Geological Sciences Virginia Polytechnic Institute and State University Blacksburg, Virginia 24061 Abstract In the humite homologousseries, nMrSiO 4' M F,TL,(F,OH)2-2,O2,(where n : I for nor- bergite, 2 for chondrodite, 3 for humite, and 4 for clinohumite, M : Mg >> Fe > Mn > Ca,Zn,Ni and 0 < x < l), x appearsnever to exceed-0.5 Ti atomsper formula unit, because local electrostaticcharge imbalances at the 3-coordinated(F,OH,O) anion and the 4-coordi- nated oxygen atoms increasevery rapidly as Tia* substitutesfor trP*, even with the con- comitant substitutionof 3-coordinated02- for (F,OH)'-. Both electrostaticand geometricar- gumentssuggest that Ti ordersinto the M(F,OH)O "layer" of the humite structures,t.e., into the M(3)OIV(F,OH,O)|I octahedron,which is the smallestof all octahedrain all the humite minerals(cl Fujino and Tak€uchi, 1978). Refractive indices, density, unit-cell dimensions, and volume are dramatically affected by the substitution of OH for F, and this has been studied as chemistry varies from 1.0 < (F,oH)'ill[(F,oH)"' + o''] = 0.0and 0.0< silv/2(F,oH,o) < l,/8 from sellaiteMg(F'oH), (n : 0) through the humitesto forsterite(r : o1. The volume per anion increasesmuch more rapidly as OH substitutesfor F in theseminerals than would be expectedon the basisof ob- serveddifferences in individual M-(F,OH) distances.As Yamamoto (1977)noted, the effec- tive radius of OHIII would be -0.06A larger
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