Ameican Mineralogisl, Volume 76, pages 257-265, 1991

Crystal chemistry and crystallography of some minerals in the tetradymite group

Ptrrn Berr-rss
Department of Geology and Geophysics,The University of Calgary,Alberta T2N lN4, Canada

AssrRAcr Selen-tellurium is a mixture of the minerals selenium and tellurium. The atoms in stibarsenare ordered(completely or partially) so that the correct chemical formula is AsSb. Matildite AgBiSr, bohdanowicziteAgBiSer,and volynskite AgBiTer, show atomic ordering in space group P3ml with unit-cell dimensions similar to those of tsumoite, BiTe. The S and Te atoms are apparently disorderedin ingodite to yield the chemical formula Bi(S,Te) and in sulphotsumoite to yield the chemical formula Bi(Te,S). The unnamed mineral of The synthetic comAksenov et al. (1968) seemsto be tellurian tsumoite, (BiorrTeoor)Te. position of Godovnikov et al. (1966) is equivalent to bismuthian tsumoite, Bi(Teo"Bio,'). Platynite is possibly plumbian sulfurian nevskite, (Bio65oPbo ror). 34s)(Seo.urrSo Kawazulite, BirSeTer,is isostructural with tetradymite. Csiklovaite is a mixture of tetradymite and bismuthinite. The chemical formula of skippenite is probably Bir(Se,Te,S)r, like that oftellurian paraguanajuatite.The Se and S are disordered in laitakarite to yield As S and Te ordering was not observed in josEite or the chemical formula Bio(Se,S).. josgite-B,thereis possiblya completesolid solution series from tellurian ikunolite, Bio(S,Te)r, The unnamed mineral of Yingchen (1986) is apparently to sulfurian pilsenite, Bio(Te,S)r. tellurian ikunolite. Rucklidgeite, BirTeo, has an antipilsenite, BioTer, structure type. The unnamed mineral of Haraflczyk (1978) is rucklidgeite. INrnonucrroN in order to investigate some of the problems associated with minerals in this group. The principal objectiveswere as follows:

The narrow definition of the tetradymite group was given by Strunz (1970) to include only Bir(S * Se + Te), minerals. These hexagonalor trigonal minerals have an l. To obtain X-ray powder-diffraction data for minerals approximately cubic closest-packedlayer crystal strucwhere no published data exist, or discredit the mineral ture (Pauling, 1975) in which the five planes within the (e.g.,selen-tellurian,csiklovaite). tetradymite layer are Te-Bi-S-Bi-Te. The axis [0001] of 2. To use published X-ray powder-diffraction data to dethe hexagonal cell correspondsto [1 1l] of the approxitermine if the crystal structuresare ordered, partially mately cubic closest-packed crystal structure, where the ordered, or disordered in order to ascertain the correct planes are stackedperpendicular to [11]. The relationchemical formula (e.g.,stibarsen,volynskite, ingodite, ship between different ratios of Bi:(S + Se + Te) and sulphotsumoite, kawazulite, skippenite, laitakarite, Te:S with respectto the d-value with the strongestcorjos6ite,jos6ite-B). responding intensity in X-ray diffraction patterns was 3. To reindex the published X-ray powder-diffraction data discussedby Spiridonov (1981). The definition ofthe teand obtain refined unit-cell dimensions (e.g., matiltradymite mineral group was widened later by Bayliss et dite, bohdanowiczite). al. (1986) to include as essentialthose chemical elements 4. To identifi unnamed minerals, incorrectly named from group Va (As, Sb, and Bi) and group VIa (S, Se,and minerals, and synthetic phaseswithin the tetradymite Te) to produce eight subgroupseach with a different numgroup. ber ofplanes in the basic layer repeat unit layer. Table I 5. To review the literature and ascertain the status of lists minerals within the tetradymite group, which may platynite. be subdivided on the basis of the number of approxiMrrrroos planes in the layered repeat mately cubic closest-packed layered meIn the approximately cubic closest-packed unit, where each plane contains one chemical element or possible crystal structure of number minerals, the tallic more chemical elements. of two or a random distribution Differencesin atomic size and electronegativityallow or- types is limited. All of the crystal structure types have dered crystal structures at low temperature, but there are atoms with symmetry-fixed values of coordinates x and disordered crystal structures with extensive solid solution y, whereasthe coordinate z may or may not have a fixed value. Some atoms may have ordered, partially ordered, at high temperature. The purpose of this paper is to compare and contrast or disordereddistributions. From thesepossibleordered, the various mineral specieswithin the tetradymite group partially ordered, or disordered crystal structure types with l /0 l 024257$02.00 0003-004x/9 257

258

BAYLISS: TETRADYMITE GROUP TABLE 2. Unit-celldimensionsobtained by least-squaresrefinement

Powder diffrac_ tion file or spectChemicalformula men no. stibarsen matildite bohdanowiczite volynskite ingodite ingodite sulphotsumoite tsumoite tsumoite laitakarite ikunolite iosEite joseite joseitsB rucklidgeite rucklidgeite protoioseite aleksite

TABLE 1. Subgroups within the tetradymite group

No. of atom Space planes group
1

Subgroup name

Chemicalformula

been found naturally, even though at least five Se-Te phaseshave been synthesized.The crystal structure of both minerals (i.e., selenium, tellurium) in spacegroup P3,21 has Se or Te in 3(a) at (x,O,Yt) with x about 0.25. A complete solid-solution seriesoccursat moderate temperatures (200-450 "C) from selenium(a: 4.37,c: 4-95 values for z estimated from similar crystal structures, A, PDF 6-362)ro tellurium (a: 4.46, c : 5.93 A, pof X-ray powder-diffraction patterns were calculated with 4-554) without superstructure reflections (Lanyon and the program of Smith (Pennsylvania State University). Hockings, 1966).Appreciable segregation occursif a melt The number of crystal-structure models may vary from is not cooled instantaneously.A phasewith both Se and two for a two-plane structure type such as stibarsen,to Te in fixed proportions would require a crystal structure ten for a seven-plane structur type such as josite. type different from that of selenium and tellurium. As yet The calculated intensities for each possible crystal- such a phasehas not been synthesized,and it is unlikely structure model were compared to the observedintensi- to occur becauseof the difference in atomic radii of Se ties of the published X-ray powder-diffraction data. The and Te. observed X-ray powder-diffraction data were reindexed, Enquiries for selen-tellurium at eight large mineralogand improved unit-cell dimensions were obtained by least- ical museumsrevealedonly one specimen,NMNH Rl86 squaresrefinement of unit-cell parameters.If the calcu- (Smithsonian Museum). This specimen, from the only lated intensities are similar to the visually estimated ob- known locality, Honduras, was initially examined with a served intensities in the literature, then a qualitative Kevex solid-state detector on an SEM. Distinct grains conclusion may be made on the order-disorder to yield were identified as quartz, barite, selenium,tellurium, and probable chemical formula, structure type, and unit-cell selen-tellurium. The mineral assemblage of the specimen dimensions. The calculated X-ray powder-diftaction data is identical to that describedby Dana and Wells (1390), of the crystal-structuremodels that give the best possible so that this specimen probably comes from the type lofit to the observedX-ray powder-diffraction data are giv- cality. The spcimenitself has not been establishedconen in the tables in order to show the goodness-of-fi1. clusively to be a type specimen; however, none of the X-ray powder-diffraction patterns of the very small type specimenappearsIo exist. specimens available were obtained with a 114.6 mm The grains were too fine for mounting in a polished Gandolfi camera (Fe radiation; Mn filter). The intensities block for electron-probeanalysis.An X-ray powder-difwere measuredwith an automated densitometer. fraction photograph taken of the fine grains containing both Se and Te was identified as a mixture of selenium Tn suscnoup and tellurium. The unit-cell dimensions of selenium and Selen-tellurium, (Se,Te) with Se:Te : 2:3, was origi- tellurium are similar to those of pure Se and Te, so that nally describedfrom the El Plomo silver mine, Ojojoma negligible substitution of Te occurs in selenium and negDistrict, Tegucigalpa, Honduras by Dana and Wells ligible substitution of Se occurs in tellurium. (1890). Only one phaseconsisting of both Se and Te has Therefore, selen-tellurium may be discredited and is

selenium tellurium 2 R3m As antimony arsenic bismuth stibarsen frm1 tsumoite tsumoite sulphotsumoite nevskite platynite ingodite bohdanowiczite malildite volynskite frm tetradymite tellurantimony tellurobismuthite paraguanaiuatite skippenite tetradymite kawazulite joseite F3n ikunolite jos6ite laitakarite pilsenite ioseite-B poubaite rucklidgeite 9 frm1 protojosaite protojoseite 14(?) P3m1 aleksite aleksite 2O(?) ? hedleyite hedleyite

nel

Te

Se Te sb As Bi AsSb BiTe Bifie,S) BiSe (Bi,Pb[Se,S) (?) B(S,Te) AgBiSe, AgBiS, AgBiTe,
Sb2Te3 BiJe3 Bi2Se3 Bi,(Se,Te). Bi,sTe, BirSeTe. Bils3 Bi.(S,Te)o Bi.(Se,Te)3 BilTe3 Bi/Te,S)g (Bi,Pb)3(Se,Te)r BiJei Bis(fe,S)4 (?) BirPbSrTe,(?) Bi?Tes (?)

a (A)

c (A)

AsSb 31-80 4.025s(11) 10.837(9) AgBiS, 24-10314.0662(21) 18.958(17) AgBiSe, 29-1441 4.2049(14) 19.650(11) AgBiTe, 18-11734.468(7) 20.7s(5) Bi(So*Teo*Seoo,)37 4.2477(24) 23.075(221 Bi(Teo,.So*) 77 4.246(3) 23.26(3) Bi(Teo6?50s) 38-442 4.304s(18) 23.47q141 (Bio56Teo 22-117 4.36413) 24.32(4) n2)Te Bi(feo?sBio25) 19-176 4.4sq3) 23.90(3) j. Bi.(Seo",So 1+220 4.2239(14) 39.94(3) Bi3ss2oTel 4.258(3) 39.s4(4) s Bi3es2seo 22-364 4.2402(12) 39.77411s1 rTero Bi415, 12-735 4.241s(10)39.76906) eTe, o Bi43s' 'so Je' o 9-43s 4.3i'26(25)40.92(5) (Bi,Pb)sTe4 29-234 4.4180(13) 41.513(15) BeJe4 4.389(16) 42.0(3s) BissTe1sS16 4.3386(11) 57.804{18) Bi2PbSrTe2 29-765 4.2423(25) 79.73(5)

BAYLISS: TETRADYMITE GROUP TABLE 3. X-ray powderdiffraction data for stibarsen

Ie
,e

2s9

TABI-E 4. X-ray powder-diffractiondata for volynskite Volynskite

Tellurobismuthite l*
D
,e

Order 6 't5 t00 35 28

c

Disorder 0 0 t 1oo 39 32 0 7 0 0 17 11 0 15 13
o

/d

003 101 012 104 110 015 006 113 021 202 o24 107 116 122 018 009 214 300 125 03it 208 10.10 220 036 312 02.10 134 315 o42 21.10 11.12 10.13 045

30 10 100 60 70 10 10 10
5

40 20 10 20 40 5 10 10 10
5 5 5

10 20
5

20
5

10 10 10 10 5 5 5

6 I 4 13 8 2 10 8 4 1 6 3 3 3 2 2 2 3 3 2 3 3 2 4 4 2 2

0 10 4 0 0 3 3 3
o

6.28 4.95 2.78 3.60 3.36 3.21 3.09 2.U 2.3i] 2.28 2.21 2.15 1.98 1.82 1.73 1.61 1.55 1.45 1.42 1.41 1.37 1.30 1.27 't.29

101 012 013 104 105 107

110 018 019 o24 00.12 119 208 211 213 214 11.12 300 128 10.16

10 102 52 52 80 100 10 30 10 50 30 10 30 106 20 20 10 51 20 10 10 10 106

3.222 100 1 1 40 36 1 21 0.2 13 0.3 18 16 7 13 2.376 2192 1.8't2 1.61 1 1.490

25 25 I 6 I

6 3 6 0 3 6 7 0 0

l2 observedreflectionshave 1 : 0 with a disorderedcrystal-structure model, but thesereflectionshave 1 > 0 with a completely ordered crystal structure, stibarsen is concluded to be ordered and have the chemical formula AsSb. The visually estimated observed intensity data are not sufficiently accurate to exclude partial disorder of As and

shown to be a mixture of selenium and tellurium. A proposal to discredit selen-tellurium as a mixture has been approved by the International Mineralogical Association Commission on New Minerals and Mineral Names (IMA cNMMr{). As suncnoup Trzebiatowski and Bryjak (1938) show a continuous solid solution between As and Sb at 400 "C; however, a minimum melting point in a continuous solid solution is characteristic of a transformation in the solid state. As the unit-cell dimensions of stibarsen (PDF 3l-80) are midway between those of As (PDF 5-632) and Sb (PDF 35-732), the chemical composition should be approximately midway between As and Sb. The specimen for PDF 3l-80 contained arsenic intergrown with stibarsen, which sr ggeststhat stibarsenmay exsolve from paradocrasite, AsSb, (Ironard et al., 197l). Stibarsen rather than allemontite is the correct mineral speciesname (Hey, 1982). StibarsenX-ray powder-diffraction data from PDF 3l80 were refined in spacegroupR3m to produce the unitcell dimensions given in Table 2. X-ray powder-diftaction patterns were calculated both for an ordered AsSb crystal structure model with As at 0,0,0 and Sb at0,0,Vz, and for a disorderedcrystal-structuremodel (As,Sb).The calculated intensities are compared to the visually estimated observedintensities of PDF 3l-80 in Table 3. As

sb.
Tsuuorrn suBGRouP Matildite, AgBiSr, as described by Geller and Wernick (1959), shows ordering in space group P3ml compared to tsumoite, BiTe, which has been describedby Yamana et al. (1979). The refined unit-cell dimensions based on the matildite X-ray diffraction data (PDF 24-1031) from Harris and Thorpe (1969) are given in Table2. The value of Frn (Smith and Snyder, 1979) increases from 2(0.060,242)to 5(0.070,84),where Fiv: overall value of F,( lA, | ,NN) with i/ as the number of observed reflections. The increase in .F, reflects a significant change in unit-cell dimensions during refinement. Bohdanowiczite, AgBiSer, as described by Geller and Wernick (1959) shows ordering in space group P.3ml compared to tsumoite, BiTe. The refined unit-cell dimensions based on the X-ray diffraction data fsr bohdanowiczite (PDF 29-1441) from Pringle and Thorpe (1980) are given in Table 2. The value of .Froincreases from 4(0.045 ,162) to 10(0.051,59). Volynskite, AgBiTer, was described by Bezsrnertnaya and Soboleva(1965). The XRD data for volynskite (PDF I 8- I I 73) were indexed using spacegroup P3zel; the unitcell dimensions in Table 2 correspond to a value of Fro of2(0. I 50,78).Reflectionsthat could not be indexed were largely those of tellurobismuthite, BirTer, as shown in Table 4 (PDF 15-863),in addition to weak reflectionsfor

260

BAYLISS: TETRADYMITE GROUP TABLE 7. X-ray powder4iffraction data for ingodite, sulphotsumoite. and tsumoite
Ingodite
/e

TmLE5. Atomiccoordinates of volynskite, spacegroupPBml

Atom
Ag Ag Bi Bi Te Te Te

Equipoint
1(b) 2(d) 1(a) 2(d) 2(c) 2(d) 2(d) 0 V3 0 l/s 0 1/g t/s

0 ry3 0 0
%.

V2

+5
+5

+5 0 0.163
V4

Sulphotsumoite

(Bio*Teo4)Te ,* l*

Bi(Teo7t Bio*)

/-"
005 101 102 103 007 104 105 20 30 20 106
100 100 100

,*

l*o

,*
204 102

/*.

0.417 0.917

12 't2

303 202 108 100 100

't2 25

0.3 1

which d : 6.28 ard2.28 A. An X-ray powder-diffraction <10 1 3 <10 10 pattern was calculated for an ordered crystal-structure of <10 106 10 1 203 25 1 volynskite, as in the cases of matildite and bohdanowicz- 108 70 38 50 60 39 60 37 38 43 ite; atomic coordinates are given in Table 5. The calcu00.11 25 1 50 34 50 35 38 33 80 37 lated intensities in Table 4 are similar to the visually 1 1 0 111 104 estimatedobservedintensitiesof PDF l8-1173, indicat1 0 .0 1 102 ing an ordered crystal structure. 00.12, 115 40 14 30 308 Ingodite, BirSTe, was describedby Zav'yalov and Be10.11 <10 10 1 20 1 gizov (1981) as having spacegroup P3*1. The rangeof 117 <10 10 2 20 30 18 40 18 25 18 40 19 12 chemical analysesgiven by Zav'yalov et al. (1984) 204 206 10 1 varies from Bir 'oPbo to Bi, o2S, ,rSeo orTeo ,u ,.Pbo,oSo nr- 1 1 9 50101 Te, or. The refined unit-cell dimensions of their specimen 10.13 < 1 0 1 0 4 104 10 rn ud ) specimen77 3 7 ( B i r o o P b o o r S , , r S e o o r T oa 11 . 1 0 10 1 0.1 1 0 (Bi,.nrSo noTe, ,o)are given in Table 2. An ordered crystal- 208 20 20 11 30 11 50 12 50 12 10.14 10 1 structure model of BirSTe with atomic coordinates sim102 ilar to those of matildite, AgBiTer, produced a calculated 209 11.12 10 30 15 70 't4 30 13 38 18 X-ray powder-diffraction pattern significantly different 211 10102 10 0.3 10101 from the observed X-ray powder-diffraction pattern of 213 214 20 30 15 40 15 25 15 40 16 ingodite. A crystal-structuremodel of Bi(S,Te),similar to 10.16 405 that of tsumoite, with z atomic coordinate adjusted for 11.14 2 0 3 0 1 10 1 20.13 1 0 1 0 2 10 1 the smaller S atom has atomic coordinatesgiven in Table 218 30 20 11 30 10 25 11 30 11 6. The intensities of the calculatedX-ray powder-diffrac- 300 30205 206 106 tion pattern given in Table 7 are similar to the visually Notej The numbers37 and 77 are specimennumbersfrom Zav'yalov t estimated observed X-ray powder-diffraction intensities al. (1984). of ingodite. Therefore, the chemical formula of ingodite (specimen 37) is inferred to be Bi(S,Te), whereas specimen 77 is inferred to be tsumoite, Bi(Te,S).The visually estimated observedintensity data are not sufficiently ac- mated observed X-ray powder-diffraction intensities of sulphotsumoite. Therefore, the chemical formula of sulcurate to exclude partial ordering ofS, Se, and Te. Sulphotsumoite, BirTerS, was originally described by photsumoite is inferred to be Bi(Te,S). The visually esZav'yalov and Begizov (1982) as having space group timated observed intensity data are not sufrciently acP3ml. The refined unit-cell dimensions of sulphotsu- curate to exclude partial ordering ofS and Te. The unnamed mineral of Aksenov et al. (1968) has Bi: moite (PDF 38-442) are given in Table 2. Disordered Te and S in a crystal-structuremodel similar to that of tsu- Te : 2:5. The X-ray powder-diftaction data (PDF 22I 17) were indexed assuming space group P-3m1, as in moite, with formula Bi(TeourSorr) have atomic coordinates similar to Te * S of ingodite as given in Table 6. tsumoite. and the refined unit-cell dimensions are listed The intensities of the calculatedX-ray powder-diffraction in Table 2. Crystal-structure models were constructed with pattern given in Table 7 are similar to the visually esti- both Bi and Te ordered and disordered in the tsumoite structure type. Many of the calculated X-ray powder-diffraction intensities are similar to the visually estimated observed intensities in Table 7; however, some signifiTABLE 6. Atomiccoordinates of ingodite, spacegroupP3m1 cantly higher observed intensities are probably due to Equipoint incorrect atomic coordinates. Although the exact nature Bi 2(c) 0 0 0.124 of the Bi-Te order-disorder cannot be established,the l/a Bi 2(d) +5 0.291 mineral seemsto be a tellurian tsumoite, (BiorrTeoor)Te, Bi 2(d) +5 Yz 0.459 even though the chemical composition is far removed s+Te 2(c) 0 0 0.362 s+Te 2(dl h ry3 0.056 from BiTe. s+Te 2(d) % v3 o.2'11 A synthetic phasewith Bi:Te : 5:3 was cooled from a

25 0.1 100 100 100 100

BAYLISS: TETRADYMITE GROUP

261

molten solution at700-270 "C at 5'C/h by Godovnikov Tlau 8. X-ray powder-diffractiondata of kawazulite and skippenite et al. (1966). The X-ray powder-diffracriondata (pDF lg176) were indexed by those authors on a unit cell ofthe Skippenite hedleyite type; however, the large differencebetweenthe Kawazulite L"" observedand calculatedd-values indicates that the unitDisOrcell dimensions are incorrect. The data were reindexed /*" I* /* ordered dered on a structure of the tsumoite type and the refined unit10 3 50 16 33 cell dimensions are given in Table 2. A crystal-structure 003 006 40 10 60 11 7 model for Bi(Teo.rrBio rr) was inferred having coordinates 1 0 1 30960 10 8 similar to those of tsumoite, BiTe. The intensities of the 009, 104 10420 65 0 1 5 100 100 100 100 100 calculated X-ray powder-diffraction pattern given in Ta107 102 00 ble 7 are similar to the visually estimated observedX-ray 0 1 8 20310 710 powder-diffraction intensities of the synthetic phase (pDF 00.12 10 1 00 1 0.10 50 38 70 35 36 19-176). Therefore, the composition of the synthetic phase 01.1 1 10550 53 is equivalent to bismuthian tsumoite, Bi(TeorrBiorr). 110 50 34 80 32 32 00.15 10630 56 Platynite from Fahlun, Sweden, was originally de11 6 ,1 0 . 1 3 10930 11 10 scribed by Fink in l9l0 (Palacheet al., 1944).Although 01.14,021 10 2 208 22 the specimen has been lost, Strunz (1963) quotes from a 205 20 18 40 16 16 10.16,00.18,208 10530 cc 1933 private communication from F. E. Wickman who 11.12 61 00 statesthat the unit cell is hexagonalwith dimensions c : 02.10 10 11 40 99 0 1 . 1 7 1 0 1 8.49 and c: 20.80 A; however,the structureis not known. 00 11.15 10 13 508 10 10 As this c dimension suggests a tsumoite-type structure, 01.20 430 33 the original analysis may be recalculated without chal- 125 10 14 408 11 11 10520 55 copyrite and insolubles, and expressedas (BiouroPboror)- 0 2 . 1 6 ,11. 1 8 21.10 4 4 0 7 7 (SeourrSoro*). Therefore, platynite may be plumbian sulfurian nevskite. Berry and Thompson (1962) stated that platynite is similar to selenjosite. Ramdohr (1980) gavedata for four powder-diftaction intensities of kawazulite (PDF 29-248) X-ray powder-diffraction reflections for platynite, but he listed in Table 8. The visually estimated observedintencould not remember (Ramdohr, personal communica- sity data are not sufficiently accurate to exclude partial tion, 1983) the locality of his specimen and was unable ordering ofSe and Te. to supply either the original X-ray film or a specimen. Csiklovaite was introduced by Koch (1948) for a minThe composition of platynite by Nikitin et al. (1989) is eral from Csiklova, Rumania, with the chemical formula similar to that of poubaite; however, the X-ray powder BirSrTe. The validity of the mineral has been questioned data could not be indexed on a cell for any mineral of by somecompilers;e.9.,Fleischer(1987).To obtain X-ray the tetradymite group. Therefore, platynite remains a powder-diffraction data of csiklovaite, eight specimens questionablespecies. consistingof severalsmall grains and two small vials were obtained from G. Grasselly,who supplied the type specTnrn-lnravrrrE suBcRoup imens used by the late Sandor Koch to describe csikloTetradymite, BirSTer, has been synthesizedby Glatz vaite. (1967), Evdokimenko and Tsypin (1971), and Abrikosov In reflected light, three areas with distinctly different and Beglaryan (1973). The compositional limits of te- colors can be seenas follows: (l) creamy yellow, (2) light tradymite have been shown to be BirSTer-BirS,rTe,.rAs blue-gray, and (3) darker blue-gray. This description determined by Kuznetsov and Kanishcheva (1970) with matches that of Koch (1948). The eight specimenswere internally consistent X-ray powder-diffraction data. Pauanalyzed, for As, Bi, Pb, S, Se, and Te with an electron ling (1975) has explained why the substitution of Te by microprobe under operatingconditions of 20 kV, 15 mA, S increasesthe chemical stability. 3 pm beam size, and 5 s count times. Grains from the Kawazulite, BirSeTer,was originally describedby Kato vials were identified by X-ray powder-diffraction as a (1970) as the Se analogue of tetradymite. The crystal mixture of tetradymite, BirS, ,Seo,Te,, (creamy yellow), structure of synthetic BirSeTe, was solved by Bland and galenobismutite (light blue-gray), and bismuthinite (dark Basinski(1961), and confirmed by Nakajima (1963), in blue-gray). spacegroup R3m (166) with the atomic coordinates of Bismuthinite and galenobismutite occur as lamellar and Se 0,0,0,Te 0,0,0.211, and Bi 0,0,0.396. As Se doesnot myrmekitic intergrowths within tetradymite. These finehave a significantly greater radius than Te, there is the grained minerals are therefore difficult to separate. A possibility that the Se and Te may be disordered. The mixture of 60 wto/o tetradymite @irSTer)and 40 wto/o biscalculatedintensities of an X-ray powder-diffraction pat- muthinite (BirS.) would approximately reproduce the tern of kawazulite with the ordered tetradymite structure chemical analysisof csiklovaite reported by Koch (1948). type are similar to the visually estimated observedX-ray No evidence has been found in studies of svnthetic

262

BAYLISS: TETRADYMITE GROUP

phases(Glatz, 1967; Kuznetsov and Kanishcheva, 1970; a phasewith Evdokimenko and Tsypin, 197l) to suggest a composition near that of csiklovaite. A phasewith the composition of csiklovaite does not exist among the synthetic phasesor type specimens.A proposal to discredit csiklovaite as a mixture has been approved by the IMA CNMMN. Skippenite, BirSer(Teo ,), was describedby Johan et nSo al. (1987), and was inferred to be the Se analogueofcsiklovaite. The crystal structure determination of BirSerTe by Nakajima (1963) shows a partially disordered crystal structure with atomic coordinates for Se at 0,0,0, (Seor,Teor) in space at 0,0,0.2115, and Bi at 0,0,0.3985 group R3m, yielding a chemical formula similar to that X-ray powder-diffraction patof kawazulite, BirSe(SeTe). terns were calculated for a partially disordered crystalstructure model and an ordered crystal-structure model with the atomic coordinates Te 0,0,0, Se 0,0,0.212,and Bi 0,0,0.396in spacegroup R3m. The calculatedX-ray powder-diffraction intensities of both crystal-structure models as given in Table 8 are similar to the estimated observedX-ray powder-diffraction intensities of Johan et al. (1987). The chemical formula of skippenite is probaas is true for bly either BirSe(Se,Te,S), or Bir(Se,Te,S)r, tellurian paraguanajuatite.

coordinates of Bio(STer)were taken as Bi at 0,0,0.1447 in 0,0,0 and 0,0,0.4260 and 0,0,0.2842,and Sorr.Teouu, for spacegloup R3ru. Jos6itewith ordered S and Te has 006 strong, whereasjosdite-Bwith ordered S and Te has 003 strong. The calculatedintensities in Table 9 are similar to the visually estimatedobservedintensities ofjosEite (PDF 12-735) given by Peacock(l9al) and joseite-B (PDF 9-435) as consistent with the disordered crystal structure types, Bio(S,Te),and Bio(Te,S)r. The original X-ray powder-diffraction photographs (57.3 mm diameter Debye-Scherrer)of josite by Berry and Thompson (1962) were borrowed from the Royal Ontario Museum, and new X-ray powder-diffraction films were taken of specimens ROM Ml9602a (osite) and ROM Ml9602b (os6ite-B).As neither 003 nor 006 was observedin any ofthese photographsor reported in the literature, the S and Te are inferred to be disordered. In addition, a wide solid-solution rangebetweenBioTe, (pilby the chemical senite)and BioS,(ikunolite) is suggested formulae in Table 2 and by so-called jos6ite-C (Bio,S,,Teo,) from Godovikov et al. (1970) and josEite from Minster et al. (1968). Therefore,jos6ite, Bio(S,Te)., is inferred to have a chemical formula similar to that of tellurian ikunolite, whereasjosite-B, Bio(Te,S)', is inferred to have a chemical formula similar to that of sulfurian pilsenite. Josiirrn suBGRouP The unnamed mineral of Yingchen (1986) gave a with 8i75.42,Te 19.2,and S 6.65wto/0. was described by Vorma (1960); chemicalanalysis Laitakarite, BioSSer, however, Nakajima (1963) statedthat the Se and S could The X-ray powder-diffraction data were indexed in space group R3m as for ikunolite, and the refined unit-cell dibe either ordered or disorderedwithin spacegroup R3n. The refined unit-cell dimensions of laitakarite (PDF 14- mensions are given in Table 2. As 003 is not observed, in which the 220) are given in Table 2. An X-ray powder-diffraction a disordered crystal structure is suggested i.e., this phase pattern was calculated for a disordered crystal-structure chemical formula is (BirrTeor)(SroTe,.o); having spacegroup R3m wirthatomic coordinatessimilar is tellurian ikunolite. Rucklidgeite [(Bi,Pb)rTeo]was originally described by to those of ikunolite, (BioSr;Kato, 1959) and pilsenite, (BioTer; Yamana el al., 1979). The SorrrSeo..., occupies Zav'yalov and Begizov (1977); however, the Pb does not sites with coordinates 0,0,0 and 0,0,0.426, whereas Bi appear to be essentialso that the end-member chemical occupiessitesat 0,0,0.142and 0,0,0.287.A secondcal- formula is taken as (BirTeo). The unit-cell dimensions culated X-ray powder-diffraction pattern was calculated (PDF 29-234) were refined and are given in Table 2. An for an ordered model with the S atom at 0,0,0, and the X-ray powder-diffraction pattern was calculated using a two Se atoms at 0,0,0.426. The calculated data for both crystal-structuremodel similar to that for BioSe,of Stathe ordered and disordered crystal-structure models, which sova (1968). The model is for spacegroup R3m, $iith Bi and Te at 0,0,0.143and 0,0,0.286. are given in Table 9, can be compared to the visually at 0,0,0 and0,0,0.429, estimated observed intensities (PDF 14-220) of Vorma The intensities of the calculatedX-ray powder-diffraction (1960). The calculated data of the disordered crystal- pattern given in Table 9 are similar to the visually obstructure model are similar to the observed data (PDF served intensities of PDF 29-234 (Zav'yalov and Begi14-220), especially for 003 and 006, so that the correct zov,1977) and PDF 38-458 (Robertsand Harris, 1988). The unnamed mineral (BirTeo)of Haraflczyk (1978) is formula of laitakarite is Bio(So,S)r. Jos0itewas named after Safi Jos6,Minas Gerais, Brazil rucklidgeite. The unit-cell dimensions were refined asby Kenngott in 1853(Palache etal.,1944). The chemical suming spacegroup R3m and are given in Table 2. Wehrlite was reexamined by Ozawa and Shimazaki formula and refined unit-cell dimensions for spacegroup R3m are given in Table 2. The data in PDF 9-435 (Li, (1982) and found to be a mixture of pilsenite, BioTer,and 1957) are for a typeJocality specimen.Calculated X-ray hessite,AgrTe. The discreditation was approved by the powder-diffraction patterns were produced for ordered IMA CNMMN. and discrystal-structuremodels for BioSTe,and BioSrTe, DrscussroN ordered crystal-structure models for Bio(TerS) and The data ofBrown and Lewis (1962) show a wide range Bio(SrTe). The atomic coordinatesof Bio(S,Te) were taken Te. The at of solid-solution of Bi and Te from 32 to 600/o as Bi at 0,0,0. 1433 and 0,0,0.2856, and SouurTeor' 0,0,0 and 0,0,0.4260for spacegroup R3z. The atomic data of Godovnikov et al. (1966) for synthetic phases

BAYLISS: TETRADYMITE GROUP TABLE 9. X-ray powder-diffractiondata of laitakarite,joseite, joseite-B, and rucklidgeite
Laitakarite l^. JositeB Disordered Rucklidgeite l*

263

/*"
003 006 009 101 012 104 015,00.12 107 10.10 01.11 10.13 01.14 110 10.16 01.17 119 00.21 10.19,202 11.12,205 027 11.15 01.22 20.14 11.21 02.16 217 10.28 12.14 300 21.16 309 11.33 30.21 3 15
15 1 10 100
c

Ordered

L.
10

/*t

,*
c

le

38 30 78 21 14 12 12 100 11
41 34 34 56 88 55 77 18 00 12 17 1 15 7 11
D

4 2 I 14

10 10 54 100 10 40 50 104 5 208 30 20 10 20 10 10

3 1 6 8 100 0.1 41 35 0.2 4

I I

20 20 100
c

2 3 100 0.1 0.1 41 35 1 0.1 1 I

15 17 100

10
510 100 10

100 1 41

40 40
c

41 34

30 30
5 5

10 3 3 30 1 15 15 1 15 3 I 1 5

18

'|

1 1

3B
5

,|
6

12 17 1 15 7 11 5 1 1 1 7

10 3 3 10 5 3 10 10 10 3 10 3 10 3 3
c

4 0.1 6 I 2 3 18 1 0.2 12 '17

15 0.1 11 c 2 1 1 7

3 60 60 10 5 10 25

19 12 17 15 7 11 6 45 35 30 10 25 12 18 15 7 12

fvote.'The ws, vs, s, ms, m, mw, w, vw, and ww were taken as 100, 40, 30, 15, 10, 8, 5, 3, and 1, respectively

indicate a chemical formula of Bi, ,rTeorr, which extends the solid-solution rangefar beyond the ideal composition of BiTe. In contrast, the data of Brebrick (1968) for the Bi-Te system shovi a seriesof individual phaseswith 5060 at.o/oTe after annealing for several days at 525 "C, near the melting point. The identification of additional phasesmay be due to the useof more sophisticatedX-ray techniqueshaving better resolution. The suggesteddisorder of S-Te in the natural series BioSr-BioTe, (ikunolite-josite-C-josite-josite-B-pilsenite) is difficult to explain. Most of the relatively few observedspecimenshave approximately integer ratios of S:Te, which would favor an ordered structure at low temperatures. The unnamed mineral of Gamyanin et al. (1980) is BirTe. The X-ray powder-diffraction data were indexed with a hexagonal unit cell with a : 4.476(5) and c : 5.997(12) A; however, two reflections with d-values of 4.16 and 3.57 A could not be indexed either with this unit cell or a supercell. Imamov and Semiletov (1971) described BioSe,(c : (a : 4.27,c : 53.79A), and 4.21,c : 51.54A;, SboTe, groupP'3m1. BioTe,(a : 4.41,c: 54.9A) ashavingspace Protojos6ite was redefined by 7,av'yalov and Begizov (1983). Their X-ray powder-diffraction data were indexed using spacegroup P3ml, and the refined unit-cell

dimensions,which are listed in Table 2, imply a structure planes. with a repeat unit ofnine closest-packed Aleksite was originally described by Lipovetskii et al. (1978). Their X-ray powder-diffraction data (PDF 29765) were indexed using space group P3ml, and the refined unit-cell dimensions are listed in Table 2. Hedleyite, which was describedby Warren and Peacock(1945), was given the chemical formula BirTer; however, both BirTe, and BirTe, are in better agreementwith the chemical analyses.The hexagonal subcell has refined dimensionsa : 4.475(4)andc :5.367(3) A. Imamov and Semiletov (1971) consider that synthetic equivalents of the tetradymite-group minerals have an odd number of approximately cubic closest-packedplanes, including the structures of BirSe, BirSer, BioSer,BioSer, BiuSer,BirSer, and Bi.Ser, which have all been synthesized and characterizedby Stasova(1968). The well-documented minerals listed in Tables I and 2 basically fit the relation involving an odd number of planeq however, the crystal structures of protojos6ite (9 atom planes), or hedleyite (20 atom planes?) aleksite(14 atom planes?), have not been established(Table l). The published X-ray powder-diffraction data were obtained using a variety of kinds of equipment with different degrees ofprecision, and with intensities recorded on films with different exposuresand estimated visually by

264

BAYLISS: TETRADYMITE GROUP

different people. Published intensities tend to be very inaccurate,and are subject to preferred orientation in the phasesunder discussionbecauseof the common {0001} perfect cleavage. Most investigatorsoverestimatedthe intensity of weak reflections by using a scale of 5 to 100 instead of 2 to 100. The intensities at the lower 20 angJes often reflect the degreeoforder-disorder, whereasthe intensities at the higher 20 anglesoften appear to be independent of such effects.In contrast, the majority of wellrefined crystal structures of the tetradymite group were obtained with a carefully measuredseriesof 0001 reflections (nine to 36 of them). The discrepanciesbetween the calculated intensities and the published observedintensities may be accountedfor by the poor accuracyof the visually estimated observed reflections, the errors in estimated atomic coordinates, the possibility of partial order rather than either complete order or disorder, or the possibility that further structural complexities exist becauseof the hierarchy of subcells present in each X-ray powder-diffraction pattern. Members of the tetradymite group present complex problems, many of which remain unresolved due to incomplete data. To confirm the structure type and the degree of order-disorder in the mineral specieswithin the tetradymite group, a series of crystal-structure determinations must be undertaken either by single-crystal or Rietveld methods.

Garnyanin,G.N., Leskova N.V., Vyal'sov, L.N., and Iaputina, I.P. (1980) Bismuth tellurides-Bi,Te and BiTe-in deposits of northeastern USSR. Zapiski VsesoyuznoyeMineralogichestogo Obshchestvo, 109, 230-235 (in Russian). Geller, S., and Wernick, J.H. (1959) Ternary semiconductingcompounds with sodium chloride-like structure: AgSbSer, AgSbTer, AgDiSr, AgBiser. Acta Crystallographica,12, 46-54. Glatz, A.C. (1967) The BirTe,-BirS, systemand the synthesisof the mineral tetradymite. American Mineralogist, 52, 16l-170. Godovikov, A.A., Kochetkova, trLV., and Iawent'ev, Yu.G. (1970) Study of the bisrnuth sulfotellurides of the Sokhondo deposit. Geology and Geophysics,11, 123-127 (in Russian). Godovnikov, A.A., Fedorova, Zh.N., and Bogdanova, V.I. (1966) An artifrcial sub-telluride of bismuth similar to hedleyite. Doklady f16ademii Nauk SSSR,Earth ScienceSection, 169,142-144. Haraflczyk, C. (1978) Krakow Paleozoic telluride province. Przeglad Geology,26, 337-343 (in Polish). Harris, D.C., and Thorpe, R.I. (1969) New observations on matildite. Canadian Mineralogist, 9, 65 5-662. Hey, M.H. ( I 982) International Mineralogical Association: Commission on New Minerals and Mineral Names. Mineralogical Magazirc, 46, 513-514. Imamov, P.M., and Semiletov, S.A. (1971) The crystal structure of the phasesin the systemsBi-Se, Bi-Te, and Sb-Te. Soviet PhysicsCrystallography,I5,845-850. Johan,Z., Picot, P., and Ruhlmann, F. (1987) The ore mineralogy of the Otish Mountains uranium deposit, Quebec: Skippenite, BirSerTe, and watkinsonite, CurPbBio(Se,S),, two new mineral species. Canadian Mineralogist, 25, 625-638. Kato, A. (1959) Ikunolite, a new bismuth mineral from the Ikuno mine, Japan. Mineralogical Journal (Japan), 2, 397-4O7. Kato, A. (1970) Introduction to Japaneseminerals. Geological Survey of Japan, 87-88 (not seen; extracted from American Mineralogist, 57, 1312, 1972). AcrNowr,nocMENTS Koch, S. (1948) Bismuth minerals in the Carpathian Basin. Acta Universitatis Szegediensis, Acta Mineralogica, Petrographica,2, 17-23. Dr. E. Nickel, vice chairman of CNMMN, provided valuable advice. Kuznetsov, V.G., and Kanishcheva, A.S. (1970) X-ray investigation of Critical reviews were provided by J.E. Post, D.C- Harris and J.L. Jambor. alloys of the systemBirTer-BirS,.Inorganic Materials, 6, I I l3-l | 16. Financial assistance was provided by the National Scientific and EngiLanyon, H.P.D., and Hockings, E.F. (1966) The selenium-tellurium sysneering Research Council of Canada. tem. PhysicsStatusSolidi, 17, Kl85-K186. konard, B.F., Mead, C.W., and Finney, J.J. (1971) Paradocrasite, RrrBnrNcns crrED SbdSb,As),,a new mineral. American Mineralogist, 56, 1127-1146. Abrikosov, N.IG., and Beglaryan, M.L. (1973) The system Bi,Se3-BirTerS- Li, A.F. (1957) Tellurium minerals in north-eastern Baikal region. Zapiski Vsesoyuznoye Mineralogichestogo Obshchestvo, 86, 40-47 (in RusBirTe,. Inorganic Materials, 9, l36t-1363. Aksenov,V.S., Kosyak,Ye.A., Mergenov,Sh.IC,and Rafikov, T.IC (1968) sian). A new bismuth telluride Bi,Te,. Doklady Akademii Nauk SSSR,Earth Lipovetskii, A.G., Borodaev,Yu.S., andZav'yalov, E.N. (1978) Aleksite, PbBirTerSr, a new mineral. Zapiski Vsesoyuznoye Mineralogichestogo Science Section,181, I l3-l 15. Bayliss,P., Erd, R.C., Mrose, M.E., Sabina,A.P., and Smith, D.K. (1986) Obshchestvo,107, 315-321 (in Russian). Mineral powder diffraction file, data book. JCPDS-Intemational Cen- Minster, E.F., Mymrin, V.A., and Isayeva, ICG. (1968) JositeA from central Asia. Doklady Akadernii Nauk SSSR, Earth Science Section, tre, Swarthmore, Pennsylvania. 1 7 8 ,l t 4 - 1 1 7 . Berry, L.G., and Thompson, R.M. (1962) X-ray powder data for ore Nakajima, S. (1963) The crystal structure ofBirTer-,Se.. Journal ofthe minerals: The Peacock atlas. Geological Society of America Memoir, Physicsand Chemistry of Solids, 24, 47 9-485. 85. Bezsmertnaya, M.S., and Soboleva,L.N. (1965) Volynskite, a new tellu- Nikitin, S.A., Anderson, E.8., and Petrova, N.B. (1989) New data on platynite and the lead isotope composition in associated selenides.Zaride of bisrnuth and silver. Akademia Nauk SSSR, Eksperimental'no piski Vsesonrznoye Mineralogichestogo Obshchestvo, ll8, 22-28 (in Metodicheskie Issledovaniia Rudnykh Mineralov Moscow, 129-l4l (in Russian). Russian). Bland, J.A., and Basinski, S.J. (1961) The crystal structure of Bi,TerSe. Ozawa, T., and Shimazaki, H. (1982) Pilsenite redefned and wehrlite Canadian Joumal of Physics,39, 1040-1043. discredited. Proceedings of the Japan Academy, 58(B), 291-294. Brebrick, R.F. (1968) Characterizationof phasesin the 50-60 at. VoTe Palache,C., Berman, H., and Frondel, C. (1944) The systemof mineralregion of the Bi-Te system by X-ray powder diftaction pattems. Jourogy I (seventh edition). Wiley, New York. naf of Applied Crystallography,1, 241-246. Pauling, L. (1975) The formula, structure and chemical bonding ofteBrown, A., and kwis, B. (1962) The systemsbismuth-tellurium and antradymite Bir"Te,,Sr,and the phaseBi,oTe,rSu. American Mineralogist, timony-tellurium and the synthesis ofthe minerals hedleyite and wehr60, 994-997. lite. Physicsand Chernistry ofSolids, 23,1597-1604. Peacock,M.A. (1941) On joseite, gdinlingite, oruetite. University ToronDana, E.S., and Wells, H.L. (1890) On some selenium and tellurium to Studies,Geology Series,46, 83-105. minerals from Honduras. American Journal of Science, 40, 78-8 1. Pringle, C.J., and Thorpe, R.I. (1980) Bohdanowiczite,junoite and laiEvdokimenko, L.T., and Tsypin, M.I. (197 l) How sulfur affectsthe proptakarite from the Kidd Creek mine, Timmins, Ontario. Canadian Minerties of BirTe,-basedalloys. Inorganic Materials, 7, 515-517. eralogist, 18, 353-360. Fleischer, M. (19E7) Glossary of mineral species. Mineralogical Record, Ramdohr, P. (1980) The ore minerals and their intergrowths. Pergamon Tucson, Arizona. Press, New York.

BAYLISS: TETRADYMITE GROUP

Roberts,A.C., and Harris, D.C. (1988) Rucklidgeite. powder Diffraction File, 38, 458. Smith, G.S., and Snyder, R.L. (1979) F": A criterion for rating powder difftaction pattems and evaluating the reliability ofpowder-pattern indexing. Journal of Applied Crystallography,12, 60-65. Spiridonov, E.M. (1981) The relationshipbetweenchemical composition and certain X-ray propenies of bismuth tellurides. Mineralogicheskii Zhumal, 3(4), 76-80 (in Russian). Stasova,M.M. (1968) Crystal structure of the bismuth selenide BioSe,. Inorganic Materials, 4, 21. Strunz, H. (l 963) Homiiotypie BirSe,-BirSe,-BirSe.-Bi.Se, usw. (platynit, Ikunolith, La.itakarit). Neues Jabrbuch fiir Mineralogie Monatsheft, 154157. Strunz, H. (l 970) Mineralogische Tabellen. Akademische Verlagsgesellschaft, kipzig, Germany. Trzebiatowski, W., and Bryjak, E. (1938) Rdntgenanalyse des Systems Arsen-Antimon. Zeitschrift fiir anorganische und allgemeine Chemie, 238,255-267. Vorma, A. (1960) Iaitakarite a new Bi-Se mineral. Bulletin de la Commission g6ologiquede Finlande N:o, 188, l-10. Wanen, H.V., and Peacock,M.A. (1945) Hedleyite, a new bismuth telluride from British Columbia, with notes on wehrlite and some bismuth-tellurium alloys. University Toronto Studies,GeologySeries,49, 55-69.

265

Yamana, IC, Kihara, IC, and Matasumoto, T. (1979) Bismuth tellurides: -1 49. BiTe and Bi4Ter.Acta Crystallographica, B35, 147 Yingchen, R. (1986) Tellurobismuthinides from Pangushan, China. Geochemistry (China), 5, 277-279. Zav'yalov, E.N., and Begizov, V.D. (1977) Rucklidgeite, @i,Pb),Te", a new mineral from Zod and Kochlar gold ore deposits. Zapiski Vsesoyuznoye Mineralogichestogo Obshchestvo, 106, 62-68 (in Russian). Zav'yalov, E.N., and Begizov, V.D. (1981) The new bismuth mineral ingodite, BirTeS. Zapiski Vsesoyuznoye Mineralogichestogo Obshchestvo,I 10, 594-600 (in Russian). Zav'yalov, E.N., and Begizov, V.D. (1982) Sulphotsumoite,Bi.Te,S, a new bismuth mineral. Tapiski Vsesoyuznoye Mineralogichestogo Obshchestvo,lll, 3 16-320 (in Russian). Zav'yalov, E.N., and Begizov, V.D. (1983) New data on the constitution and nomenclature of the sulfotellurides of bismuth of the josbite group. Zapiski Vsesoyuznoye Mineralogichestogo Obshchestvo,I 12, 589-601 (in Russian). Zav'yalov, E.N., Begizov, V.D., and Tedchuk, V.Ya. (1984) Additional data on the chemical composition of ingodite. Zapiski Vsesoyuznoye Mineralogichestogo Obshchestvo,l 13, 3l-35 (in Russian).

Memrscnrp'r RrcErvED Mencr 19, 1990 Mexuscnrrr AccEprEDNowrvrsen 10, 1990