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American Mineralogist, Volume 65, pages 1263-1269, 1980 The forsterite-tephroite series:I. Crystal structure refinements Cenr A. FReNcIs Mineralogical Museum,Hamard University Cambridge,M assachusetts 02I 38 AND PAUL H. RIBBE Department of Geological Sciences Virginia Polytechnic Institute and State University B lac ksbur g, Virginia 2406 I Abstract The crystal structures of the following metamorphic olivines, M;*[SiO4], in the forsteritetephroite (Fo-Te) serieswere refned in space group Pbnm: Cation compositionM Mg Mn Ca Fol Ten, 1.028 0.181 0964 1.780 0.006 0.013 Fe 0.002 0.026 a Cell parameters(A) b c 4.794 4.879 10.491 6.t23 10.589 6.234 Rfactor 0.029 0.039 Treating minql ps and Ca as though they were Mn, the refined cation distributions (esds < 0.01) and mean bond lengthsare: M(1) site Mg Mn For, Te", 0.92 O.l7 0.08 0.83 M(2) site (M(lFo) 2.116I^ 2.0294 Mg Mn 0.1I 0.00 0.89 1.00 (M(2)-o) (si-o) 2.185A r.6374 2.2274 l.6,t0A By comparison, a previously refned synthetic ForrT€o, specimen"heat-treated at l(X)0oC" is significantlymore disordered(KD : 0.196)than the naturally occurring For' (Ko: 0.011). As expected,mean M(l)-O and M(2)-O distancescorrelatelinearly with Mgl(Mg+Mn) occupancy. Introduction However, the crystal structures of only two MgMn olivines have previously been refined. One of With the widespread availability of automated Xcontains I I mole percent of Zn SiOo, thereby them ray di-ffractometeruand least-squaresrefinement prothe octahedral site refinement (Brown, complicating grams, order-disorder has become a principal theme The is synthetic ForrTeo, which was 1970). other of contemporary crystal chemical investigations (Ghoseand Weidneg 1974; l000oc" "heat treated at (Burnham, 1973).Both natural and synthetic com1976) and thus doesnot representa natet al., Ghose pounds with the olivine structure have been inThe present Mg/Mn distribution. equilibrated urally tensivelystudied(for a review,seeGanguli,1977).At Mg/Mn orexamine were undertaken to refinements least 25 different room-temperature refinements of uncomplicated by addinatural olivines in dering the geologically-importantMg-Fe olivineshave been substituents. tional carried out and 13 additional refinements extend the observationalconditionsto temperaturesof - l000oC Experimental proceduresand structure refinenent and pressuresof -50 kbar @assoet al., 1979;Birle er al., 1968; Brown and Prewitt, 1973; Finger, 1970; The crystals used for refinement were selected Finger and Virgo, l97l; Hazen, 1976;Smyth, 1975; from the suite of specimensdescribed in Part II of Smyth and Hazen, 1973;Wenk and Raymond,1973). this study (in preparation). The manganoanforsterite w03-.004X/80/ l I 12-1263$02.00 t264 FRANCIS AND KIBBE: FORSTERITE-TEPHROITE S.ERIES from Lingban, Sweden (Harvard University Te' were carried out using the program RFINE 4 #116463) has the compositioo Mg,orrMno"u4 (Finger and Prince, 1975).Scatteringfactorsfor neuCa"*uFeooouSio4. It occurs with fine-grained haus- tral atoms with corrections for anomalous dispersion mannite in a calcite skarn. In hausmannite-free were taken frort the International Tablesfor Crystalbands anhedralforsterite crystalsrange from 0.1-1.0 lography(1974,p.99, 149).The refinementswere inicm in size.The tephroite, from an unspecifiedloca- tiated using the positional parametersof forsterite tion in Madagascar(Harvard University #108206) (Hazen, 1976),fully orderedcation distributions [Mg hasthe compositionMn, rroMgo,r,Feoo""Ca.o,rsiO4. It concentratedon M(l)], and reasonableisotropic temoccurs as discreterounded crystals l-2 mm in diame- perature factors. After several cycles varying the ter associatedwith rhodonite, yellow spinel, and blue scale factor and positional parameters, the convenapatite in a calcite marble. For the purposesof site tional R factor dropped to -0.10. Site occupancyreoccupancy refinement these compositionswere ap- finements were undertaken by varying the Mg conproximated as Fo'Teon and Te",Fonand are denoted tent of M(l) while constraining the total cation below as Fo' and Ter,. chemistriesto agreewith the observedcompositions. Refinements were carried out in the conventional Site occupancies were refined alternately with isobut nonstandard spacegroup Pbnm. Unit-c.ell dinentropic temperature factors, and the R factors desions (Table l) were calculatedfrom the orientation creasedto R : 0.038for Fo' and R : 0.056for Ten,; matrices and are identical to within three estimated all positional parameters were identical within thlee standard deviations of those obtained by least- estimated standard deviations to those of the final squaresrefinement of powder data as reported in anisotropic model. Anisotropic thermal parameters Part II. The crystalsusedfor data collectionare tabu- and an isotropic extinction correction were applied in lar with dimensions0.24 x 0.24 x 0.07 mm for Fo' the final rycles of both refinements, leading to unand 0.30 x 0.30 x 0.20 mm for Ter,. Intensity data weighted R factors for all data of 0.029for Fo' and were collectedin two octants(20 < 70") at l SoCon a 0.038for Ten,. Picker FAcs-l four-circle di-ffractometer,using NbStructure factors for which F"o"< 2oF"* were confiltered MoKc radiation (I : 0.70926A)and ttLeo:-20 sidered unobserved and were excluded from the rescanning technique at a rate of l" 20 per rrinute. finement. These are indicated in the structure factor Twenty-second background measurementswere tables(Tables2a,b)' by asterisks.Atomic coordinates made at either end of dispersion-corrected scan are listed in Table 3, anisotropic temperature factors, ranges. Two standard diffractions were monitored equivalent isotropic temperature factors, and their during data collection and used to calibrate the in- root-mean-squareequivalentsare listed in Table 4, tensities by interpolation. The data were corrected and interatomic distanc.esand interbond angles are for background, Lorentz, and polarization effects. recordedin Table 5. Crystal shapeswere approximatedby polyhedral enThe olivine structure velopesin the absorption correction. Linear absorption coefficients(p) for MoKa are 47.7 cm-' for Fo' The olivine structure is so well-known that only a and 77.2 cm-' for Ten,.Finally, the data were aver- brief description is given here. [For structure diaaged to yield sets of 731 and 773 unique structure grams the reader is referred to Birle et al. (1968) and factors for For, and Ten,respectively. Hazen (1976).1It consistsof a slightly distorted hexFull-matrix least-squaresrefinementsof Fo' and agonal closest-packedarray of oxygen anions with one-half of the octahedral sites filled with divalent cations and one-eighth of the tetrahedral sites occuTable L Crystal data pied by silicon. The key structural feature is the serrated chain, parallel to c, of two symmetrically-indeto5, YI pendent, edge-sharing octahedra. The M(l) Langban, Sweden Madagascar octahedron is at the interior of the chain and the 4 . 7 9 4 ( 2 )* A 4.879(2) A b 10.491(4) 1 0 . s 8 9( 4 ) M(2) octahedron forms the "elbows" of the chain. c Vol Density ^Numbers deviation 6.r23(2) 3 o az. ( z ) n 3 (ca1c. ) ln 3.67 glcc parentheses represent (14) and refer to the 6.234(3) -aa )zz. 'zar L\z) .3 A 4.UO g/cc es!imated standard last decimal olace. I To obtain a copy of Table 2, order Document AM-80-141 from the BusinessOffice, Mineralogical Society of America, 2000 Florida Avenue, NW, Washington" DC 20009.Pleaserenit $1.00 in advance for ttre microfiche. 1265 FRANCIS AND RIBBE: FORS TERI TE-TEP H ROI TE SERI'S Table 3. Atomic coordinates t", )l Atom x M(1) M(2) v 0.9870(1) o . 4 2 2 6( 2 ) b1 0 .7 s 8 (ss ) 0 .2 3 0 (1s) 0(1) 0(2) 0(3) t- 0 . 2 78 2( 3 ) o . 2 79 0( r ) 0.0910(1) 0 . 0 8 6 (72 ) 0 . 4 4 8 9( 2 ) 0.1590(2) Atom v M(1) M(2) 0 . 9 8 7 7( 2 ) o . 4 2 6 5( 4 ) o . 7 s 74 ( L O ) 0 . 2 1 6 2( r r ) 0 . 2 8 s7 ( 8 ) 5a 0( 1 ) 0(2) 0(3) , t4 ,,4 o . 0 3 74 ( 2 ) z 0.2801(1) 0 . 0 9 5 (12 ) 0.0914(5) o . 452s(5) 0 . 1 6 2 (53 ) ,4 t4 ,4 \ 0 . 0 4 0 1( s ) The [SiO.] tetrahedron sharesits basal edgeswith two M(l) and one M(2) octahedra.Its apex links to the adjacentchain, which is related to the first by Dglide planes. Cation ordering Consideration of cation ordering in non-calcium olivines began with the prediction of Ghose (1962) that becausethe effective ionic radius of Fe (r : 0.78A) is larger than that of Mg (r : 0.72A) it should be preferentially ordered into the larger M(2) site. Refinementsof four compositionsacrossthe forsterite-fayalite seriesby Birle et al. (1968) and refine- mentsby Brown (1970)failed to detectMglFe order. Subsequentrefinementsby Finger (1970),Finger and Virgo (1971),Brown and Prewitt (1972),Wenk and Raymond (1973),Ghoseet aI. (1976),and Basseer a/. (1979) have shown small but signfficant degreesof ordering of Fe onto M(l) rather than M(2). This unexpected result, termed anti-ordering by Brown and Prewitt (1973),has generally been attributed to the greater distortion from ideal Oo symmetry of the [M(l)O6] octahedron which results in a slightly greater crystal field stabilization energy for Fe2* on M(l) (Walsh et al.,1974) [althoughfor someMg-rich olivines, Fe'* may show a slight preferencefor M(2) (Wenk and Rayrrond, 1973). In general,site preference of divalent transition-metal cations relative to Mg in olivine is determined by two competing factors: cation sizeand crystal field etrects(Rajamani et al., 1975). Divalent manganesetras t high spin d' 6snfiguration which is unaffected by crystal field effects.Thus cation ordering in Mg-Mn olivines is predicted (Brown, 1970;Burns, 1970,p.118)to be governedby the size criterion with Mg (r : 0.72L) preferring M(l) and Mn (r : 0.834) preferring M(2). The cation distributions determined in the present refinements and an earlier refinement of a synthetic manganoanforsterite(ForrTen) "heat treatedat 1000"C" by Ghose and Weidner (1974)genfirm the predicted preferences(Table 6). Another refinement, that of from Franklin, New Mn, r*MgororZnorrrFeo..r"SiOo Jersey(Brown, 1970)is consistentwith but is not a Table 4. Anisotropic temperaturefactors(Bi;),equivalentisotropictemperaturefactors(Beq) and their root-mean-square equivalents(p) Btz R - 1* 1 R -22 R -33 3.r(4) 6.L(2) 3.1(3) 2 , 2( 7 ) 4.o(8) 3 .e ( 6 ) r.35(8) 1.16(4) 0 . 9 6( 6 ) L . 7( 2 ) 2.s(z) - o .r ( 2 ) 3 . 6 6( 9 ) 0.24(8) 0.0(r) -0.2(3) -0.5(3) 0.0(2) 5.8(4) 6. 7( 4 ) s . 4 ( 7) 2.9(18) 5 . 7( 1 8 ) 7 .s ( 1 3 ) 2. 2 ( L ) r . 3 7( 7 ) 1 .4 ( 1 ) 2.s(4) 1 .4( 4 ) 1.9(3) Brg R -23 se q ( e ' ) u(A) to5r M(1) M(2) Si o(r) o( 2 ) o(3) r.r(2) 1.3(r) 2.s(2) 3 . 1( 4 ) 3.8(4) 3 .6( 3 ) - 0 .s ( 2 ) 0.0 0.0 0.0 o.o 0.0(3) -0.34(9) 0.0 0.0 0 .0 0.0 0 . 4( 2 ) 0.42 0.54 0.36 0.50 0.48 0.50 0.073 0. 083 0. 058 0.079 0.078 0.079 -0.7(3) 0.0 0.0 0.0 0.0 0.0(8) -0.7(1) 0.0 0.0 0 .0 0.0 0.4(3) 0.76 0.68 0.61 0.81 0.59 O.77 0.098 0.093 0.089 0.r01 0.094 0.099 T"91 M(1) M(2) 5a o(1) o(2) o(3) *8.. 4.8(2) s.0(2) 4.s(3) 5.7(10) s.6(e) 4 . 9( 6 ) 0.0(2) 0.1(2) 0.1(3) o.r(8) -o.2(7) 0.2(s) ls in the expression exp-(Brrt.2+3rr<2+9r/'2+gL|2hK+g]2h!+g1x2K9.) and values are quoted x103 1266 FRANCIS AND RIBBE: FORSTERITE-TEPHROITE Table 5A. Interatomic distances(A) and angles (o) of Fo' Table 5B. Interatomic distances (A) and angles (o) of Tecr Isioo1 tetrahedron si-o(1)[1] o ( 2 )[ 1 ] o ( 3 )[ 2 ] Mea Isiool tetrahedron 1.611(3)* 1.651(2) 1.638(2) 1.637 O...O dlstaces sr-o(1)[1] 1.613(5)* o ( 2 )[ 1 ] 1 . 6 6 3 ( 6 ) o ( 3 )[ 2 ] r . 6 4 1 ( 4 ) M e a n1 . 6 4 0 Angles at Sl o ( 1 ) - o ( 2[)r ] z . z s s ( : ) o ( 1 ) - o ( 3l)z l - 2 .t s z ( z ) o ( 2 ) - o ( 3[)2] ? . 5 5 0 ( 3 ) o ( 3 ) - o ( 3[)r l ' 2 . o o + ( g ) [M(1)06 ] ocrahedron o ( 1 ) - o ( 2 )[ 2 ] b o ( 1 )- o ( 2 ) [ 2 ] o(1)-o(3)2 [ ] o ( 1 ) - o ( 3 ) [2 ] o ( 2 ) - o ( 3 ) [2 ] o(2)-o(3) 2 I'Iean I u ( 1 ) o uJ o c t a h e d r o n M ( 1 ) - o ( 1 )[ 2 ] 2 . 1 8 3 ( 4 ) o(2)12) 2.L44(4) o(3)12) 2.228<4) M e a n2 . 1 8 5 Angles at M(1) 2.753(3) 3 . 0 8 7( 1 ) 2 . 75 2 ( 3 ) 3 . r . 2 6( 3 ) 2 . s 5 0( 3 ) 3 . 3 s 9( 3 ) 2.940 bz,ttt(t) 8s.35(7) 94.65(7) 8 s .9 3( 8 ) 9 4 .0 7( 8 ) ros.38(8) 74 . 6 2 ( 8 ) 90.0 s6.26(1s) o ( 1 ) - o ( 2 )[ 2 ] 93.74(L5) o ( 1 ) - o ( 2 )[ 2 ] 1 3 , 1 5 8 ( 2 ) o(1)-o(3)[2] "2.7s0(6',) 85.20(16) 94.80(16) o ( r ) - o ( 3 )[ 2 ] J . 2 4 7 ( 5 ) -2.580(6) 107.59(16) o ( 2 ) - o ( 3 )[ 2 ] 72.3L(L6) o(2)-o(3)[2] 3.530(6) Mean 3 . 0 0 0 M e a n9 0 . 0 [M(2)06] octahedron M ( 2 ) - o ( 1l t) l z . z g o ( z ) o ( 2 ) [ 1 ]2 . r z e ( 2 ) (2) 0 ( 3 )[ 2] 2 . 2 8 7 o3)lzl 2.L26(2) u ( 2 ) - o ( r l)1 l o ( 2 )[ 1 ] 0 ( 3 )[ 2 ] 0 ( 3 )t 2 l l4ean 2.209 disteces l.lean Mean 3.L16 *Nunber ln deviation 7s.so(1) e2.53(7\ e7.28(8) eo.oe(7) 69.40(8) 89.r.2(6) r11.70(e) Uean a. Edges shared between tetrahedron b. Edge shared between octahedra. and octahedron, valid test of the prediction, becauseMg had to be assignedto M(l) in order to simplify the computation. The degreeof order for the three pure Mg-Mn olivines is illustrated in Figure l, with data for Mg-Fe olivines included for comparison. Order is frequently quantified by the use of a distribution coefficient Ko lMe/(Me+Mn)M(2)l [Mn/(Ms+ Mn)M (r)l / IMe/ (Mg+Mn)M(1)l[Mn/(Mg+Mn)M(2)] written for the ion exchange reaction Mg'z*M(l) f Mn2* M(2)SMg3*M(2) + Mn'z*M(l). For a fully ordered Angles at M(2) 80.72(14) o(1)-0(3)t2l "z.tso(o) 91.26(r2) o ( 1 ) - o ( 3 )[ 2 ] 3 , 1 7 s ( s ) 97.59(rs) o ( 2 ) - o ( 3 )[ 2 ] 3 . 3 s s ( b ) o(2)-o(3)[2] ^3.350(5) 89.84(12) ' 2 . 6 1 7( 6 ) 68.73(17) o ( 3 ) - o ( 3 )l r l 87.e4(8) o ( 3 ) - o ( 3 )[ 2 ] 3 . 1 0 2 ( 4 ) o ( 3 ) - 0 ( 3 )[ 1 ] 3 . 6 1 7 ( 6 ) ! L 4 . 7 7 ( 2 0 ) M e a n3 . 1 7 2 M e a n 8 9 ' 8 5 89,75 parentheses represents one estinated stmdard (d) and refers to the last decinal place. 2.2s2(s) 2 .r 3 9( s ) 2.318(4) 2 . r 4 7( 3 ) 2.227 0.,.O disteces Angles at M(2) o(1)-o(3)lzlb z.tsz(t) o ( 1 ) - o ( 3[)2 ] 3 . 1 e 7 ( 3 ) o(2)-0(3)[2] 3.315(3) o ( 2 ) - o ( 3 ) [ 2 ]3^ . 3 s e ( 3 ) o ( 3 ) - o ( 3[)1 ] ' 2 . 6 0 4 ( 3 ' o(3)-0(3)[2] 3.010(3) o(3)-o(3)[1] 3.s20(3) A n g 1 e sa t M ( 1 ) o...o distances IM(2)06 octahedron] 0,..O 1r.33 . (3) LLs.4(2) L 0 2 . 7( 2 ) 105.8(3) tog.2 o ( 1 ) - o ( 2 )[ r ] 2 . 7 3 7 ( 7 ) o ( 1 ) - o ( 3 ) [ 2 ] ^ 2. 75 0( 6 ) o ( 2 ) - o ( 3 )[ 2 ] : 2 . 5 8 0 ( 6 ) ' 2 . 6 1 7( 6 ) o ( 3 ) - o ( 3 )[ 1 ] Mean 2 . 6 6 9 M ( 1 ) - o ( 1 )l 2 l 2 . L 2 4 ( 2 ) o(2)l2l 2.o7s(2) 0(3)t2l 2.L48(2) M e a n2 . 1 L 6 O.,.O distances A n g l e sa t S l 0...O distmces 1 1 4 .6 ( 1 ) 115.8(1) 101.8(1) r . o s . 3( 1 ) 1o9.2 llean 2.664 S,ERIES *Number in Darentheses reDresents refers to last devlation i6) ""a a, Edge shared between tetrahedron b. Edge shared between octahedra, one estimated standard decimal place. and octahedron. distribution Ko : 0, for a completely random distribution Ko : l, and for an anti-ordered distribution KD : @. These define the top and right edges,the long diagonal, and the left and bottom edgesof the parallelogramin Figure l. The Mg-Mn olivines are strongly ordered by comparison with Mg-Fe olivines. The contrast between 'the heat-treatedsynthetic crystal (Ko : 0.196) and the metamorphiccrystals(Ko : 0.000,0.01l) demonstratesthat the degreeof Mg/Mn order is dependent 1267 FRANCI S A N D RI BBE: FORSTERITE-TEPH ROITE SER/ES Table 6. Refined site occupanciesof Mg-Mn olivines M(1) ConDoslEion l4n 4C Fo53Tt47 * o.124 Fo51Tt49 0.921(5) 0.079 roo9Tt91 o.172(9) 0.828 Mg O.276(4) Mn K-** 0.339 0.661 0.196 0.110 0.890 0.011 1.000 0.000 radii (Brown,1970).This relationshipis illustrated in Figure 2 for (Mg-Mn)-containing octahedra. The data (Table 7) fall into two distinct populations describedby the following regressionequations: (M(l)-0) :2.200 - 0.096VoMg; R : 0.997 (M(2) -0) :2.223 - 0.097VoMs; R:0.998 reflecting the inherent size differencebetweenM(l) and M(2) octahedra due to the difference in number **K-= [ Ms/ (Mg+lrn)M(2) ] [Mn/ (Ms+Mn)M(I ) ] (Ms+Mn)M(1) of sharededges. lMs/ I IMn/ (Ms+un)M(2) ] Quadratic elongation,a measureof distortion of_t are in square brackets and refer to Estimated standard deviations the last decimal place. ten used in the analysis of finite homogenousstrain, correlates linearly with bond angle variance for a large number of coordination polyhedra in minerals on a specimen'sthermal history. However, the rarity which show variations in both bond length and bond of Mg-Mn olivines seemsto precludetheir wide use angle (Robinson et al., l97l). as petrogeneticindicators. Using the bond anglevarianceparameteras a convenient measureof polyhedral distortion, Robinson Stereochemistry et al. (1971) have shown that distortions of olivine The steric details of non-calcium olivine structures. [SiO.] tetrahedra decreasewith the weighted mean which arise from cation-cation repulsions across M-O distance.whereas distortions of olivine octashared polyhedral edges,have been thoroughly discussedby Birle et al. (1968)and Brown (1970).One 1976) Effectivelonic Rodius( Shonnon, surprisingresult of the latter study is the constancyof Si-O distancesirrespective of octahedral cation 2.24 chemistry.The Si-O distancesobservedin this study (Table 5) are typical, being statistically indistinguishablefrom the correspondingvalues for ten oli2.22 vines studiedby Brown. In contrast,mean M-O distancesare a linear function ofthe calculated effective *chose & weidner (1974). o42 E -ordered \ ( K-n = O O O ) r \ F o 5 1, K 9 = 9 . 6 1 1 r*\ \a.. 6z.te .-^\. V.i c|) "" t'ii. .iuay) t !, c --synthetic Foo3 KD=O 199 ( G h o s eI W e i < l n e r1,9 7 4) oo 2.r6 o I q -50 or 82.t4 = (D ;e I o Fo - Te series Fo - Fo series roo 50 Mole % Forsterite 2 .t o o Fig. l. Plot of percent magnesiumon M(l) as a function of mole percent forsterite component, which illustrates the degree of cation order-disorder in the forsterite-tephroite series (squares) and the forsterite-fayalite series (dots). Data from Table 7. Rr^ to0 Mole 7" Forslerile Fig. 2. Plot of mean M(l)-O (dots) and M(2FO (squares) distances as a function of refined site occupancy in percent magnesium (lower abscissa) and effective ionic radius (upper abscissa).Lines represent regressionequations given in the text. 1268 FRANC I S AN D RI BBE: FORSTERITE-TEPH ROITE SERI'S Table 7. Mean M-O distancesfor (Mg,Mn)-containing octahedra Mineral. Site Occupancy <M-O> (A) Reference Forsterite M(1) Mo 2. 10r 2. L26 tlazen (1976) 2.116 2.209 Thls study z. Ld) This study ' 00 ;;1 ---1.00 M(t\ M(r) Fo--Te.)r 49 $|o.szf;o.oa ^"'0.89"60. M/'\ 11 M(1) tt91to9 sr"so. rz fo. '..'1. 00 u(2) Manganhumite M(1) . ro zoMso f;0. "'r. oo r.r(2) o Table 8. Polyhedral distortions as measured by the bond angle variance parameter (o)2 ofRobinson et al. (1971\ totoot Fo- - -'91 Isio. ]x 42.4 4 8 .3 38.0 l- M ( 1 ) o _l * * 98.7 99.9 L 2 7. 3 [M/?)n']** o 9 0 .1 rr4.7 r24.1 Polyhedron 6- )l tHazen (1976) 25 *o(tet) = X (o.-!09.47o)2 / 5 l2 xxO(oct) 2= t i=t 2.227 2.r70 2.222 Francls & Rtbbe (1978) hedra increase with increasing M-O distance. Polyhedral distortions of the present structures (Table 8) conform to these general trends, but the distortions of Fo' are somewhatanomalous.The M(2) octahedron is more distorted than M(l), reversing the general rule for end members and disordered compositions. The tetrahedron in Fo' is also significantly more distorted than in either end member. These anomalies, which also hold for monticellite (Lager and Meaghet, 1978), are attributed to the large size di-fferencebetween M(l) and M(2) cations. Reinterpretation of cation distribution in Zn,Mg tephroite (0.-90o)2/rr Brown (1970)reported the M(2) site occupancyof the Franklin, New Jersey tephroite to be Table 9. Com.parison of site occupancy models for (Mn' 36sMgs3a5Zna225Fes r28)SiO4 Occupancy Scatterlng Powerx Electrons Effective Radius Tonlc (A) <M-O> obs. (A) pred. Brown (1970) M(1) ho. M(2) 43zu8o. 345Zto.l8oFto. 043 ho.86Bt"o. oB5zoo.o45 zL .40 0.774 2.r48 25.32 0.821 2,224 M8o. 345h0. ro oznn-zzlF"o.tza ht, oo 2 t . 78 o.765 2.L5+ 2 5 .0 0 0. 830 2.223+l Reinterpretat ion M(1) M(2) *Lnr"i **In.r. (radii from Shannon(I976)) ItO) tPrecllctecl from 0.755 + 1.38 (radtus of f tPredicted f r o m < M (2) - 0 > = 2 . 2 2 3 - 0 . 0 9 7" / " V i g FRANCI S A N D RI BBE: FORSTERITE-TEPH ROITE SER/ES Mn *"rFeoo.rZno*r,with a mean M(2)-O distanceof 2.2244. Qsmparison of this mean bond length with the observedvaluesot 2.2294 for (M(2)-O) in Ten, and 2.2224 for (M(2).-O) in manganhumite (Francis and Ribbe, 1978),both of which are completely occupiedby Mn, suggeststhat the M(2) site in the Franklin tephroite is also completelyoccupiedby Mn. The plausibility of a fully ordered distribution may be tested by comparing the effective X-ray scattering factorsand ionic radii of the compositeoctahedrally coordinated atoms of the refined model with those of the fully ordered model. Only if these parametersare nearly equal can the ordered model be realistic. This comparisonis made in Table 9. Scattering factors were approximated by summing the products of the atom fractions times their respective atomic numbers, which equal the number of electrons in neutral atoms. The scattering factors of both modelsare identical within the limits of resolution of X-rays for both M(l) and M(2). Similarly the mean effectiveradii ofthe divalent cationsare nearly identical. Thus the intensity data are equally satisfiedby the model reportedby Brown (1970)and the fully orderedmodel. In further supportof the orderedmodel may be cited the strong preferenceof Mg for M(l) observedin this study, the preferenceof Fe for M(l) discussedabove, and the preferenceof Zn for M(l) relative to Mg (Ghose and Weidner, 1974).The ordered model therefore is not only possiblebut appearsto be crystal-chemicallypreferable. Acknowledgments We are grateful to ProfessorCharlesW. Burnham and Dr. David L. Bish of Harvard University, who assistedgenerouslywith data collection, and to the ResearchDivision of Virginia Polytechnic Institute and State University which provided funds for computing. Partial financial support was provided under NSF grant EAR77-21114 (Earth SciencesSection) to P.H.R. and G. V. Gibbs. References Basso,R., A. Dal Negro, A. Della Giusta and G. Rossi(1979)Fe/ Mg distributions in the olivine of ultrafemic nodules from Assab (Ethiopia). NeuesJahrb. Mineral. Monatsh., l9'l-2O2. Birle, J. D., G. V. Gibbs, P. B. Moore and J. V. Smith (1968)Crystal structuresof natural olivines.Am. Mineral., 53, 807-824. Brown, G. E. (1970) Crystal Chemistry of the Olivines. Ph.D. Thesis, Virginia Polytechnic Institute and State University, Blacksburg, Virginia. and C. T. Prewitt (1973)High-temperaturecrystalchemistry of hortonolite. Am. Mineral., 58, 577-587. 1269 Burnham, C. W. (1973) Order-disorder relationships in some rock-forming minerals.Annual Rev.Earth Planet. Sci.,I,3lf338. Burns, R. G. (1970) Mineralogical Applications of Crystal Field Theory. Cam.bidge University Press,Cambridge, England. Finger, L. W. (1970) FelMg ordering in olivines. CarnegieInst. lAash. Year Book, 69,302-305. and E. Prince (1975) A systemof Fortran IV computer programs for crystal structure computations. U.S. Natl. Bur. Stand. Tech. Note 854. and D. 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