Anerican Mineralogist Vol. 57, pp. 1109-7114 (7972)

A MOSSBAUEREFFECT STUDY OF TRIPLITE AND RELATED MINERALS EowennKosttnon,l Baher Laboratorg of ChemistryCornellUniuersitg Ithaca,New Yorlt14850

Arsrnaqr

Mdssbauer parameters are reported for the phosphate minerals triplite, zwieselite, triploidite, and wolfeite. Analysis of the absorption data confirms the existence of non-equivalent ferrous ions. The broadening of the resonance peaks is rationalized on the basis of a microscopic disorder due to half-occupied fluorine sites in the fluoride minerals and to sets of closelv related metal sites in the hydroxy minerals.

INrnonucrroN Recently the crystal structures of triplite (Waldrop, 1969) and triploidite (Waldrop,1970), two relatedphosphate minerals, have been determined.This paperreports the 5?FeMijssbauer effect spectroscopy of triplite and three relatedminerals-swieselite, wolfeiter, and triploi- dite.

ExppntlrnNrar, The mineral samples were generously zupplied by L. Waldrop. A description of each follows.

Triplite-(Mn,Ie)"PO.F, from Mica Lode pegmatite, Eight Mile Park, Fre- mont County, Colorado, Mno *Feo TCao1PO4F. Composition and "-Mgo mineralogy described by, Heinrich (1951). The crystal structure is mono- clinic with two equally populated metal sites M(1) and M(2), each octahedrally coordinated by four oxygen and two fluorine atoms. The occupancy of the two metal sites is (Waldrop, 1969)

M(l): 0.717Mn, Fe + 0.231Mg f 0.052Ca

M(2):0.a$ Mn, Fe + 0.469Mg * 0.048Ca Zwieselite-(Fe,Mn)fOnF, from Zwiesel,Bavaria. Describedin Palache et aI. (1944),p.851. The atomic ratio of iron to manganeseis 2.00; trace amounts of calcium and magnesium are present. Precession photographs show these specimensto be isotypic with triplite (Waldrop, 1970). Triploidite-(Mn,Fe)"PO"Otl, from Bra,nchville, Connecticut. Described, in Palache et al. (1944), p. 853. The crystal structure is related to that of triplite, with the b-axis doubled. There are a total of eight metal atom sites, belonging to two very similar groups of four octahedral and four trigonal bipyramidirl atoms (Waldiop, f970). Wolfeite-(Fe,Mn),PO'OH, from Palermo pegmatite, North Groton, New ' Present address: Department of Chemistry, University of Connecticut, Storrs, Connecticut 06268.

1109 1110 EDWARD KOSTINER

Hampshire. Described by Frondel (1949); the iron to manganese ratio is 3.39. Precession photographs show the specimen to be isotypic wiih triploidite (Waldrop, 1970).

The room temperature lFe Miissbauer efiect was measured with a Model NS-1 Miissbauer Speetrometer (Nuclear Science and Engineering Corporation, Pittsburgh, Pennsylvania) operating in the constant acceleration mode. The 14.4 qOo keV gamma radiation from a source of (10 mCi) diffused into palladium wa.Sdetected with a gas proportional counter and collected with a 400 channel ana)yzer operating in time sequence scaling mode. Typically, lff counts per channel were recorded. Sample thickness was 25-30 mg/cm' (corresponding to on the order of 8-10 mg Fe/cm'), The source and drive were calibrated against a single crystal of sodium nitroprusside (National Bureau of Standards, Standard Reference Material No. 725). The quadrupole splitting for sodium nitroprusside was taken as 1.7048-F 0.0025 mm/sec (Grant et al., 1969). All isomer shifts are reported with respect to the zero position of this standard. The data were reduced by a computer program which performed a non-linear least-squares fit to the product of a series of absorption peaks having Lorentzian shapes superposed on a parabolic baseline, a result of our pa.rtieular drive geometry. All of the variables (peak height, position, and half-width) were allowed to vary independently. Although the mineral specimens did not show preferred orientation, the angle of the sample relative to the direction of ry-radiation was varied to determine if there was any resonance anisotropy due to sample preparation. None was ob- served.

Rnsur,rs ANDDrscussroN The assignmentof the quadrupole-splitpairs is unambiguousin hiplite since there is a good peak separation and a large definite dif- ferencein peak areas (seeFigure la) in addition to the factors men- tioned below. The other three minerals present a problem in assign- ment. If one considerspeak area as a, criterion for assignment (the quadrupole-splitpair should have the more nearly equal areas) then peaks one and three (numbering from left to right) result from one iron ion, peaks two and four from the other. This, however,gives un- usually low values for the isomer shift for half of the ferrous ions (<1.30 mm/sec),implying a rather large degreeof covalency(Walker et aI., 196I); an effectwhich one would not expectto find in a phos- phatemineral. The Miissbauerparameters summarized in the table are arrived at by following the assignmentin triplite and show isomer shifts and quadrupolesplittings characteristicof high-spin (ionic) di- valent iron. As is to be expected,the isomershifts are nearly the same for non-equivalent sites with similar coordination in a particular com- pound.Figures la and lb illustratethe least-squaresfit (solidlines) to the experimentaldata (circles)for triplite and triploidite, respectively. The dashedcurves indicate the individual peaks. Another point of interest is the relatively high values for the line widths observedfor theseminerals. The natural line width (full-width MASSBAUEN STUDY OF TRIPLITE l111

o 9^ = E cn

F

0.

Velocily(mm/s€cl (a)

Velocify(mm /sec) (b)

Frc. 1: Mijssbauer spectra of a) triplite b) triploidite. Velocity scale is relative to sodium nitroprusside. Solid line is a least-squares fit, dashed lines are the individual peaks, and circles indicate the normalized data. at half-maximum-FWHM) for 57Feis approximately 0.2 mm/sec (Wertheim,1964). (The experimentalline width of our sourceis 0.23 mm/sec.) In the caseof the hydroxy mineralstriploidite and wolfeite, this can be easily explainedby recallingthat the two differently co- ordinatedsites arbitrarily labeledM(7) andM(2) acttally eachrepre- sentfour closelyrelated but crystallographicallyunique atom positions, the broadenedpeaks representingsets of four unresolvablepeaks. The tttz EDIVARD KOSTINER asymmetryof the quadrupolesplit peaksobserved in triploidite (Fig- ure lb) could alsobe due to this effect. A more subtleeffect is observedin the fluorideminerals triplite and zwieselite.The inner set of peaksin particular are markedly broaderin triplite (Figure la) and still remain broad in zwieselite,with a higher iron to manganeseratio. A possiblerationalization of this phenomenon becomesevident when one considersan unusual aspectof the crystal structure of triplite-the splitting of the single fluorine position into two half-occupiedsites at a distanceof 0.62A to eachother (Waldrop, 1970).The fluorinedoes not occupya singlecrystallographic site with occupancyof 1.00in triplite but partially occupiestwo distinct sites with averageoccupancy 0.50. This effect allows highly distorted six- coordinationabout both of the unique metal atom sites.However, if one considersthe dissimilar metals which occupy these sites in the mineral (uide supra), one can visualizea fair amount of microscopic disorderoccurring from a degreeof randomizationof the fluoride ion betweenthese two partiatly occupiedpositions which is reflectedin the substantialbroadening of the resonancepeaks. Although the structural analysisof triplite is undoubtedlycorrect on a macroscopicbasis, a more accuratedetermination of the effect of the partially occupied

T,relo 1. Mdssseuon EnPBct Pen,luptpns

(a11 values ln m/sec uith an esti@ted error of *0.005 m/sec)

latio of Isomer* Quadropole AIEAS (M1 Mineral 5lt e nmt /M2\

Mrrl 1.484 z.7ao 1.11 (Mn,Fe)2PO4T M(2) r.57r 2.010

ZweiE elite 1.500 2.622 o,40 Ri lle,!m.J2rU4! Mr'2\ r.543 1.95L o.68 Mfr \ 1.448 2.148

(lh,Fe ) aP0aOH Ml)\ r.)06 r.776 o.72

'Wolf elte 1.415 2.2]-5 .92 (Fe, Mn ) eP0a OH M(2) r.415 r.757

* Relatlve to sodtw nltroprussLde.

i !'u11-rldth at haff-mriEw. MASSBAUER STUDY OF TRIPLITE 1U3 fluorinepositions on the metal atom sitesseems worth undertaking.A furiher point of information is the completestructural determination of one of the syntheticend membersof this solid solution,manganese fluorophosphateMns(POa)F (Rea and Kostiner, 1972),which places the full fluorineatom essentiallybetween the half-occupiedsites postu- lated for triplite with no randomizationat all. The Miissbauereffect can allow oneto determinethe distribution of iron atomsover crystallographicallyunique sites in a particular crystal structureproviding that the recoil-freefraction (/) is the samefor all cationsites under consideration. However, it hasbeen shown (Sawatzky et aL,7969) that a room temperaturedetermination of occupancyfac- tors is not necessarilyaccurate and that an error of 5-10 percentis to be expected.The last columnin the table givesthe ratio of iron atoms overthe two sites (M (1) andM (2) ) in eachof the minerals.Note that in the caseof triploidite and wolfeite the eight metal sites are con- sideredto be subgroupsof the two distinct sitesin triplite. This approx- imation can be justified on the basisthat in both structurestwo groups of sites are each similar in coordinationto the two different sites in triplite and that the spectra cannot be analytically resolvedinto any more than two setsof overlappingdoublets. Because of the errors involved and the lack of any distinguishingtrend, no definite con- clusionsregarding site preferences can be considered. The following trends in the data can be observed.First, the isomer shifts for the fluorideminerals are greaterthan for the hydroxidemin- erals.This can be explainedby noting that the cation polyhedra are made up of four oxygen atoms and two fluorine ions in the fluoride mineralsand two hydroxidesreplacing the fluorideions in the hydrox- ide minerals.Fluorine, with a higher electronegativitythan oxygen,is more effectivein withdrawings-electron density from the iron nucleus, causingthe higherisomer shift (Wertheim,1964). Second, differences in quadrupolesplittings are greaterfor the fluoridesthan the hydroxides, undoubtedlydue to the greatereffect that fluorinehas on the net elec- tric field gradient.Since a ferrousion occupyinga moredistorted lattice site normally has a smaller quadrupolesplitting (Ingalls, 1964),the resonancelabeled M (2) for triploidite and wolfeite is assignedto the trigonal bipyramidal siteswith a slight but inconclusivepreference of the iron atomsfor this site.

AcItNowLEDGMENTS

Thanks are due to J. Steger for developing the curve fitting program. This work was zupported in part by the Advanced Research Projects Agency through the Materials Science Center, Cornell University. ll14 EDWARD KOSTINER

RurpnnNcos trhoNnrr, C. (1949) Wolfeite, xanthoxenite, and whitlockite from the Palersro Mine, New I{a,mpshire. Amer. M'ineral. 34, 692=705. Gn.lwr, R. W., R. M. Housrny, AND U. GoNsnn (1969) Nuclear electric field gradient and mean square displacement of the iron sites in sodium nitro- prusside.Phgs. Reu. L78,523-530. Ifnrwnrcn, E. W. (1951) Mineralogy of triplite. Amer. M'ineral. 36,256-271. INcer.r,s, R. (1964) Electric-field gradient tensor in ferrous compounds. Phgls. Reu.733, A787-A795. Par,ecrrn,C,, E. Bnnrvreu,lNn C. FnoNnnr, (1944) Sastem of Mi'neralogg ol Dana, TtlLEd.,VoI.z, John Wiley and Sons,New York. Rre, J, R., axo E. Kosrrwon, (1972) The crystal structure of Mn"(PO)F. Acta Crystallng. Bz8, (in press). Sawerzry, G. A., F. vAN DER W'orme, awo A. H. Monnrss (1969) Recoilless- fraction ratios for Fe'in octahedral and tetrahedral sites of a spinel and a garnet. P hgs. R eu. 783,3&3-386. Wernnor, L. (1969) The crystal structure of triplite, (Mn,Fe),FPOn. Z. KristaL Iogr. t,3O,L-14. - (1970) The crystal structure of triploidite and its relation to the structures of other minerals of the triplite and triploidite group. Z. Kristallogr. 131' l-20. WAr,rnn, J. C., G. K. Wnnrrrnrru, aun V. JeccenrNo (1961) Interpretation of the Fe" isomer shift. Phgs. Reu. Lett.6, 98-101. Wonruntu, G. K. (1964) Miissbauer EffecL: Pri,nciples and,Appl:i'cati,ons, Academic Press,New York.

Manuscri,pt receiued,,February 6, 1912; accepted'tor publicatinm, Apri.l' 18, 1912.