Povondraite. a Redefinition of the Tourmaline Ferridravite Jonr, D
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American Mineralogist, Volume 78, pages 433-436, 1993 Povondraite. a redefinition of the tourmaline ferridravite Jonr, D. Gnrcn, T. Scorr Encrr Mineral SciencesSection, Canadian Museum of Nature, Ottawa, Ontario K1P 6P4, Canada FnaNx C. HlwrHoRNE Department of Geological Sciences,University of Manitoba, Winnipeg, Manitoba R3T 2N2, Canada Assrnlcr Povondraite, previously the tourmaline ferridravite, is redefined. It is rhombohedral, R3m, with a: 16.186(2)and c:7.444\l) A. fne new chemicalformula, derived by crystal structure analysis, is (NaoroKo ru),, ou (Fel.jrFeS j,Mgo rr)",o, (FeljrMg, .uAlo.r)r,nr- B.Si5e6O2,88(OH)r,,and the ideal end-memberformula is NaFel*Fel+(BO.).(SiuO,')- (o,oH)4. INrnooucrroN nm). Thesevalues are greaterthan those given by Walen- (1979). During the investigation of a seriesof tourmaline crys- ta and Dunn model tal structureswith varying contents of Fe and Mg (Grice Povondraitewas chemicallyanalyzed using a Jeol and Ercit, 1990, 1993) the "ferridravite" structurewas 733 electronmicroprobe. Wavelength-dispersionanaly- 15 kV, refined. It was discovered that the formula proposed by sesused an operatingvoltage of a beam current Walenta and Dunn (1979) for the speciesferridravite was of 25 nA measuredwith a Faradaycup, and a beam di- pm. were incorrect. They adopted the standard schemefor assign- ameter of l0 The following standards used: gehlenite(Al), (Si, ment of cationsto the X, Y, and Z sites,i.e., with Fert synthetic almandine Mg), synthetic (Fe),microcline (K), amphibole (Na), VP,O, and Al3* assignedto the Z site and Mg2* and Fe2+to the fayalite sodic (V), (Ti). were Y site, yielding the empirical formula (NaoroKoro)- and titanite The elementsF, Mn, and Ca sought but not detected. Data reduction was performed (Mg,rrFel-i,)(Fe31nAlo,,)SiuBr (O,OH)30 (OH,F). As with the structure refinement of feruvite (Grice and Robinson, with a conventional ZAF routine in the Tracor Northern programs. 1989),it becameevident that the assumedsite assign- Task seriesof The analysesof the singlecrys- given in ments of Mg'?*and Fe3* were incorrect. The crystal struc- tals used in the crystal structure refinementsare Walenta ture refinement of "ferridravite" yielded a new empirical Table l, along with the chemical data of and ( well with present formula that bears no resemblanceto "the ferric analog Dunn I 979), which agreevery the anal- yses. of dravite" (Walenta and Dunn, 1979); therefore renam- Also in Table I are analysesof K-dominant tour- (10 pm) portion ing of the specieswas required.The new name, povon- maline that forms a thin outer rim on a draite, is in recognition ofthe extensivework on the chem- of the Royal Ontario Museum sampleno. M35899. Un- properly istry of the tourmaline group by Dr. Pavel Povondra, fortunately, there is not sufficient material to Karlovy University. The data and new name for this re- characterizethe K-dominant tourmaline as a new species, presence germane defined specieswere approved by the Commission on but its is very from a crystal-chemical New Mineralsand Mineral Names,I.M.A. Type material vrewpornt. povondraite its potassicrim is for povondraite is preservedat the National Museum of Chemical zoning of and in Natural History, SmithsonianInstitution (no. 144478)and shown in Figure l. There is a sharp discontinuity the povondraite at the Royal Ontario Museum (no. M35899). ratio K:Na between and the K-rich tour- maline at the rim; however, chemical trends established Prrysrc.q.L AND CHEMICALDATA within povondraite continue into the rim tourmaline. For + whereas The two samples used in this study (Royal Ontario the entire system,Fe,., and K/(Na K) increase, Museum no. M35899 and SmithsonianInstitution no. Al, Ti, and V decreasewith crystallization. 144478)are both type material of "ferridravite" from the SanFrancisco mine, nearVilla Tunari, Bolivia. The min- CRvsrll sTRUCTUREREFTNEMENT eral is described(Walenta and Dunn, 1979)as occurring Initially the crystal structure of povondraite was re- in metamorphosedsedimentary rocks. The schist is com- fined using a crystal fragment supplied by the Royal On- posed of quartz, potassium feldspar, alkali amphibole, tario Museum (sampleno. M35899). The quality of in- muscovite, and tourmaline (schorl and povondraite). tensity data from this crystal was such that it was evident Povondraiteis stronglypleochroic with O yellow-brown there was a problem with the empirical formula given by and E dark red-brown. It is uniaxial negative with co: Walenta and Dunn (1979), but a better crystal structure 1.820(5)and e : 1.751(3),measured with Na light (590 refinement was desirable.Five grains were obtained from 0003-004x/93/0304-o43 3$02.00 433 434 GRICE ET AL.: POVONDRAITE: FERRIDRAVITE REDEFINED TABLE1. Electronmicroprobe analyses of povondraite CORE RIM Structure Structure K-rich tourm. Walentaand Fe 144478 35899 35899 Dunn -€- sio, 30 7 31 1 29 6 31.58 F Tio, 0.0 01 0.0 AI Al,o3 1.4 4 2 0.8 2.30 -a- V,O" trace 0.1 0.0 o TI Fe.O.. 45.0 421 45 6 38.37 \ -t- FeO' 1.7 07 0.9 7.25 \ MgO 65 6.9 63 5.57 \ V K,O 10 0.9 22 0.98 z \ -l- Na,O 21 2.2 1 1 2j8 o \ B,O"'. 9.0 91 8.7 gg8 F \ H,Ot 24 2.5 23 3.5 \ TorAL 99 I 99.0 97 5 100.71 rD_ rh Number of cations on the basis ot O : 31 t Si 5.96 5JZ 5.91 6.02 F Ti 000 0.01 0.00 z AI o32 no( o.20 u.Jz IIJ 0.01 0.02 0.00 O Fe3* o.c/ 6.04 6.87 R A1 z Fe2* o27 0.11 0.15 1.16 Mg 1.89 1.95 1.87 1.58 o K 0.26 0.21 0.56 0.24 O NA 0.80 0.80 0.42 0.81 I B 2 ? 3 H 3.12 3.12 n,tz J.C r \,p Fe3+lFe2+ calculated by stoichiometry z-A-- ** B,O" from B : 3 atoms in formula. t H,O from bond valencesum H :3.12 exceptfor Walentaand Dunn r-r_ L.O.t. a o.2 o.3 0.4 0.5 0.6 the Smithsonian Institution (sample no. 144478)and the K/(Na+K) Fig. l. Chemicalzoning in povondraite(core) and K-rich best of these crystals, as determined by the quality of tourmaline(rim), Royal Ontario Museum sample no. M35899. reflections on precession films, was used to measure a Thereis a sharpdiscontinuity in the ratio K:Na (dashedline) second data set. Intensity data were obtained on a fully betweenpovondraite and the K-rich tourmaline.Scales are rel- automated Nicolet R3m four-circle diffractometer using atrve. the method of Grice and Ercit (1986).The data relevant to the structure refinement are given in Table 2. No X-ray powder diffraction data are listed here, as there rs no the Z site, and refinement gave occupancyfactors corre- changefrom that presentedby Walenta and Dunn (1979). spondingto 3.84(12)Fe atomsand 1.86(12)Mg atoms. The structure refinement of povondraite was essential These refined values agreewithin 3o of the electron mi- for the definition of the species.From the chemical data croprobe analysis of this crystal. given in Table I, the number of Fe and Mg atoms are We have found that the residual index R for a tour- known to be 6.84 and 1.89,respectively. The distribution maline crystal structure refinement usually falls between of these cations in the Y and Z sites determines the spe- 2 and 3o/o.The R index in this experiment is controlled cies. The atomic coordinates of feruvite (Grice and Rob- primarily by the poorer quality of povondraite crystals, inson, 1989)were usedto beginthe structurerefinement which tend to have alarge mosaic spread.This gives rise of povondraite. Refinement of positional and anisotropic to larger standardelTors in observedstructure factors and thermal parametersand the occupancyfactors of Fe and thus to larger uncertainties in structure parameters.AI- Mg in the Y andZ sitesgave a residualindex R : 5.06 though the standarddeviations of Fe and Mg occupancies and R* : 5.07o/o.For the Y site,refinement gave 2.52(7) in the Y and Z sites is rather large, there is no doubt Fe atoms,and 0.48(7)Mg atoms. All Al was assignedto about the partitioning preferenceof these elements be- TABLE2. Structurerefinement data for povondraite ldealformula: NaFeS*Fe3* 83Si6O,s(O,OH)3 a: 16186(2) A Space group: HJM c:7.444() A Z: 3 v : 1688.9(3)A3 Radiation/Mono: Mo/graphite no. of F. 1214 p: 47.9cm . no of F" > 5o(F) 717 Min. transmission: 0.463 FinalR: 5.06% Max. transmission: 0.552 FinalF": 5.07o/o F -- >(|F"t lF.ly2lF.l & : P w(lF"l- lF"l)'l>wlF"l"l*, w : o 2(F.) GRICE ET AL.: POVONDRAITE: FERRIDRAVITE REDEFINED 435 Tlele 3. Positionaland anisotropicthermal parameters ( x 103 A'?) for povondraite Y Z U,. U"" U"" U,, Na(x) 0 0 0.228(21 17(3) 17(3) 34(6) 0 0 8(1) 23(3) 't2(1) Fe(Y) 0.1224(2\ 0.0612(1) 0.6429(5) 4(1) 4(1) -1(1) -1(1) 2.2(61 6.5(8) Fe(z) 0.2987(1) 0.2626(1) 0.6124(s) 4(1) 4(1) s.1(8) 10(7) 5(6) 2.2(71 5.8(7) B 0.1097(7) 0.219(1) 0.456(2) 12(6) 4(7) 7(6) 1(6) 0(3) 2(3) s(5) -1(1) - 5l 0.1892(2) 0.1876(2) 0 5(1) 4(1) s(l) 1(1) 3(1) 6(1) o1 0 0 0.772(3) 7(s) 8(5) 7(s) 0 0 4(3) 7(41 02 0.0610(4) 0.1220(8) 0.4s0(2) 10(4) 4(4) 13(s) 2(41 1(2) 2(2) 10(3) o3 0.2s78(8) 0.1289(4) 0.512(1) 12(5) 7(3) e(s) -1(21 -3(4) 6(3) s(3) o4 0.0924(4) 0.1848(8) 0.069(2) 8(3) 16(6) 12(4) -2(41 -5(e) 8(3) 11(3) o5 0.1827(8) 0.0913(3) 0.086(1) 10(5) 4(3) 18(5) 0(21 0(4) 5(2) 10(3) o6 0.1922(6) 0.1829(5) 0.784(1) 12(4) 7(3) 8(3) -2(3) 0(3) 6(3) 8(3) 07 0.2811(5) 0.2814(s) 0.075(1) 8(4) 7(4) 12(3) 0(3) 0(3) 2(3) 10(3) o8 0.2069(5) 0.2678(6) 0.442(1) 5(3) 10(4) 17(41 6(3) 4(3) s(3) 10(3) H3 0.24(1) 0.120cl) 0 41(3) 20 tween the two sites.