OPTICAL ANISOTROPY in PYRITE G. S. Gresons, the New South

THE AMERICAN MINERALOGIST, VOL 52, MARCH_APRIL, 1967

OPTICAL ANISOTROPY IN PYRITE

G. S. GresoNs, The New South Wales Institute of Technology,Sydney, New South Wales, Australia. Aesrnlcr

Polished surfaces of pyrite reflect light in a manner difierent from that predicted b;' accepted theories of crystal optics, although the behaviour is qualitatively compatible with crystal symmetry. The effects may be an expression of surface deformation induced by po1- ishing.

INrnonucrroN Reflectionanisotropy in pyrite has generallybeen regarded as anoma- Ious, although Stanton (1955, 1957) showed it to be a characteristic feature of the mineral. A detailed study has beenmade of the geometry of anisotropiceffects in pyrite to discover whether it is compatible with crystal symmetry. The results have been analysedin terms of classicalreflection theory and the geometry comparedwith that of crystalsof lower symmetry. The results have considerablesignificance in the field of ore-mineral identifi.cationby quantitative optical methods.As yet, Iittle is known of reflectivity variation in differently oriented crystal sections and of the effectof polishing.only careful qualitative and quantitative studieswill rectify thesedefi ciencies.

Syulrnrny oF PyRrlE The spacegroup of pyrite is Tn6: Pa3. Despite occasionalindications to the contrary (c/. Miers, Hartley and Dick, 1898; Prischl, 1911; Smolai, l9l3; Smith, 1942) the morphology and etch patterns of pyrite generally exhibit symmetry of classm3 in the cubic system; this is verified by X-ray investigations(Bragg, 1913). An important featr"rreof this symmetry class is that there are no tetrad symmetry axes.The normals to octahedralfaces are triad axes, and the normals to cube faces are diad axes only, as frequently shown by the presenceof a singleset of striations on each cube face of a pyrite crystal. In general,striations on the (001) face are parallel to the cr-axis [100](Fig. 1).

Tnpony or Rorr,ncuoN r,RoMCnvsrar- Sunneces The following summary of experimentaifacts has been more exhaus- tively reviewedby Hallimond (1953)and Cameron (1961). When normally incident, plane polariz-edlight is reflected from a polishedsurface, the intensity of the light is invariably decreased;the 359 360 G. S. GIBBONS reJlectitity of the surface is defined as the ratio of the intensity of the reflectedlight to th:rt of the incident iight' For a polishedsurface of an anisotropiccrystal, the incident light will also generally undergo a rotation of the poiarization azimuth, and a degreeof ellipticity wiil be induced in the vibration. The light wiil be reflectedw.ithowt change of polarization state or azimuth only if it is initially polarized parallel to a tL,irectionof wniradial refl,ectionwithin the surface.In general,there are two such directions at right angles,cor- respondingto the direction of maximum reflectivity and the direction

Frc. 1. Directions of uniradial reflection on a normally striated pyrite cube. Full bar: maximum rellectivity for red. Open bar: minimum reflectivity for red'

of minimum reflectivity for the surface concerned.Normally incident light which is not polarizedparallel to either of thesedirections will be rotated upon reflection toward,sthe direction of maximum reflectirtity. When the reflected ray is elliptically polarized, its apparent polarization azimuth is the major axis of the vibration ellipse. Although the eliipticity modifies the observed efiects, the polarization azimuth will still be rotated in the senseindicated above, unless ellipticity effects are far greater than any yet measuredfor ore minerals. The amount of rotation is dependent upon the wavelength of the incident ray, so that incident white light is resolved into component wavelengths,each one having a different polarization azimuth. This effect is known as d,ispersionof the apparentangle oJ rotation (DA,)'In ANISOTROPYIN PYRITE 361

general'just one color will be extinguished(or nearly extinguished)for a given setting of the analyserwhen this effectis studied with a reflecting microscope. The polarization color then observed consists essentially oi a mixture of the remaining colors;the intensity of eachbeing a complex function of the incident light composition,reflectivity variation with wavelength, and final polarization azimuth (relative to the analyser). The generaleffect is that of a color complementaryto that which has been extinguished. Cissarz (1931) studied surfacesin the zones[100], [010], [001j of the orthorhombic mineral stibnite. one uniradial direction in such surfaces is parallel to the zone axis, and for each zone, this direction has a constant reflectivity value. The value for the other uniradial directionvaries continuously with the position of the surface in the zone. The two uniradial reflectivities are equar for just one surface in each quadrant of the zone [100].The normals to thesesurfaces are the axesof refeclion isotropy. Berek (1931b) published a theoretical treatment of these results, which incorporated cissarz's conclusion that for alr surfaces within a principal zone, the reflectivity parallel to the zone axis is a constanr. This result was predictedby Drude (1ss7), Voigt (190g) and others in theoretical discussionsof pleochroic crystals.

RBnrpcrroN Oprrcs on pvnrrp Polarization effectsin pyrite were studied in some detail by stanton (1955, 1957) and surnmarizedas follows: (1) Optical anisotropy is a generalfeature of pyrite. Polarization colorsare pink and blue-grey. They

plane of the incident light, and (3) No anisotropy is apparent in sections cu1palallel io octahedralfaces I ttt l. Klemm (1961)studied a large number of very carefuily polishedsec- tions of pyrite and concludedthat anisotropyis a widespread,but by no means universal,property of pyrite. Klemm concludedthat the anisotropy is probably a manifestationof crystarrattice distortion causedby impurities. Pyrite producedfrom very pure reagentsat the washington GeophysicalLaboratory, however, shows normal reflection anisotroDv (R. L. Stanton,pers. comm.). 362 G. S, GIBBONS

Cameron and Green (1950) studied the conoscopicoptics of pyrite' They state that slight rotation of the analyser from the crossedposition causesthe polarization crossin white light to break into isogyreshaving red fringes on the convex side and blue fringes on the concave side. This effect is attributed by Cameron and Green to dispersion of the reflection rotation, i.e. to an effect of varying angle of incidence of the conoscopic light.

APPenarus ANDTECHNTQUES The stud.ies presented here attempt to establish the geometry of reflection anisotropism in different crystals of pyrite, and to discover whether the optical anisotropism has a similar nature wherever it occurs. Differences in strengthof anisotropism from crystal to crystal were not investigated. observationswere made with a cooke, Troughton and simms "Meta- lore,' reflecting microsope fitted with a Wright ocular. A tungsten-fila- ment lamp with condenserlens was used with red or blue glass filters fitted to this lamp for most of the monochromatic work. Some observations were made using a sodium vapor Iamp but these were few, as pyrite is almost isotropic for yellow light. The directions of maximum and minimum reflectivity were identified by determining the senseof rotation of light reflected from the surface in the 45oposition. Many sectionsof pyrite show only very weak polarization effects,and determination of the rotation was greatly facilitated by use of a Nakamura accessoryplate in the slotted ocular. The two halves of this plate have the effect of equal, small rotations of the analyser in respectively clockwise and counterclockwise directions. For monochromatic iight the two halves are equally illuminated when the analyser is set at the extinction position. If the polars are precisely crossedand rotation has occurred,one or other of the halves (depending on the senseof rotation) will be distinctly brighter than its fellow. Thus if the microscope is set up for orthoscopic examination, the polars precisely crossedand the Nakamura plate inserted, the uniradial directions and the senseof rotation at the 45oposition can be readily determined. Used similarly with white light, the plate gives a sensitivetest for the presenceof dispersion of the apparent angle of rotation' conoscopic observations were made in the manner described by Cameronand Green (1950). Becauseof the small rotation anglesinvolved, observationswere almost completelyqualitative. However, this has not hindered analysisof the results in terms of optical geometry. ANISOTROPYIN PYRITD 363

MatBnrar- Sruorpo

RBsur,rs orthoscopiceramination The resurtsof stanton (1955, 1957)have been verified for pyrite crystals of various habit and origin from several localities in New South wales. These results may be restated as follows: 1' carefully polished sections of pyrite generalry exhibit polarization effects. 2. rf a surface parallels a principar crystailographic axis, this will be one of the directions of uniradial reflection. 3' For octahedral faces there is no discernibre dispersion of the apparent angle of rotation (DA,:0); indeed, such surfacesare ap_ parently quite isotropic.

The following additional information, summarized diagrammaticalry in Figures I and 2, was gained from supplementary studies: 4. DA' is essentially zero for surfacesparallel to negative pentagonal dodecahedralfaces I tzo], and for surfacesin the zone sectorsbe- tween any such face and the two adjacent octahedralfaces. How_ ever, the exact position of surfacesfor which DA,:g could not be determined with the apparatus used.

5' For surfaces in the principal crystalrographic zones, the folowing relations hold for red light: (a) rn surfacesparallel to cube ana {zro} faces, the uniradial direction of maximum reflectivity is peipendicular to the na_ tural striations on thesefaces (Fig. 1). (b) For surfacesin the major sectors between negative pentagonal 364 G. S. GIBBONS

,//' z' /rt ,l \ i ,,4.. '\ \ t/ t tt I t t \ I I I I I ------il-----i-ill -t,-L ul I I j I '. 1 I _t\-__ I -. .'t I L I \\'-,- ,; \---<---- -,/--t

---" hi*tPal zonesf ilE crYstal' '----- 7orc,of, aPgartnt isottoPY'

# OfccUonsof unbadialrtflcction for red lryhL.Fullbarmarimum ref lecLiviLY; oPen bar'minimum rcflectivitY.

Fic. 2. Optical relations in pyrite, shown in spherical projection (Uniradial reflection directions are shown for surfaces parallel to faces of cube and rhombic dodecohedron forms.)

dodecahedralfaces in the principal zones,the uniradial direction of maximum reflectivity is parallel to the zone axis. For surfaces in the minor sectors,it is perpendicularto the zoneaxis (Fig' 2)'

6. Rotation of blue light is oppositein senseto that of red light for all sectionsshowing sufficient anisotropy for satisfactory determination of theseproperties. Thus the uniradial direction of maximum reflectivity for blue corresponds to the direction of minimum reflectivity for red. No dispersionof the axesof apparent isotropv in the principal sectionscould be detected' ANISOTROPVIN PYRITE 365

7. The qualitative relations shown in Figures ! and 2 are fully compatible, geometrically,with morphologicalcrystal symmetry. 8. No anisotropy was observedin sodium light (5g90A). Becauseof the iow sensitivity of the apparatus, this means only that plrite shor,vslass marhed.anisotropic effects in yellow light than in light from the red and blue portions of the spectrum.

conoscopicetamination. The conoscopicfigures for pyrite which are described by cameron and Green (1950) are fully explainedby them in terms of dispersionof the reflectionrotation. However, by using quite strongly anisotropic pyrite and small rotations of the analyser,rather differentresults may be obtained. rn such cases,if slight clockwiserotation of the analyserproduces an effectsimilar to that describedby cameron and Green,then the disposi- tion of the color fringes may be reversed.by either (1.) uncrossingthe analyser ln a counter-clockwisesense, or (2.) rotating the specimen through 90oon the microscopestage. rI bothoperations are carried out, the originai color distribution will be restored. Theseeffects can be explainedonly by a dispersionof apparentangles of rotation with red and biue light rotated in oppositesenses. The effect is explained diagrammaticallf ill Figure 3.

ColrpenrsoN wrrn pnpvrous CowcBprs optical symmetryares. rt has been found by experiment that if a polished surface of pyrite parallels a crystal axis, that axis will always be parallel to a direction of uniradial reflection in the surface.This is one of the specialproperties used by Berek (1931a) and others to define optical s-\'mmetryaxes in crystalsof lowersymmetr_v. The lawso[ crystaloptics require the reflectivity parallel to such symmetry axes to be constant. This doesnot apply ;t'orpyrite. For red light, the direction [001] (seeFig. 1) is the direction of mini- num reflectivity'on (100),but of maximum reflectivity on (010).Assum_ ing that the actual reflectivity values are identical on each cube face (as is required by crystal symmetry), the reflectivity of direction [001] must be less on (100) than on (010). That is, the unirad,ial reflect,itity parallel to a crystallographicax.is is not constanr. The low degreeof anisotropy in pyrite shows that the variation in reflectivitl' with which we are dealing is not great. rt is onry the high s).mmetry rvhich permits read1,-recognition of the departure from constancl-.The fact remains that pyrite doesnot obey the normal laws of crystal optics; it follows that considerationof conventionalelements of optical geometr)rmust be of a purely comparativenature. Frc. 3. Diagrammatic explanation of conoscopicfigures for pyrite' (a), (b):-Isotropic mineral; colour fringes caused by dispersion of the reflection rotation. (c)-(f) : pyrite; colour fringes causedby dispersion of the apparent angle of rotation. (Arrows indicate uniradial direction of maximum reflectivity for red )

Close stippiing:-Red fringe (i.e. blue extinction). Open stippling:-Blue fringe (i e. red extinction). PPf , AA': Plane of polarizer, analyser respectively. /: Plane of polarization of reflected blue ray. ,.':-Plane of polarization of reflected red ray' ANISOTROPY IN PYRITE

Ares oJ reflect'ionisotropy. For red light, the direction [001] is the direction of minimum reflectivity on faces (100) and (110), but of maximum reflectivity on (010). It may be assumedthat the uniradial reflectivities change their values continuously with change of surface orientation, as Cissarz(1931) found to be the casewith stibnite. Thereforethere exists a surfacelying between (110) and (010) in the zone [001]such that the reflectivity for direction [001]is neither greater nor less than the other uniradial reflectivity, and the surface appears isotropic in red light. In fact, surfacesparallel to I i20j show no observableanisotropy in either red or blue light. There are two important distinctionsbetween thesesurfaces and the corresponding planes (normal to axes of reflection isotropy) in orthorhombic stibnite. First, when Cissarzstudied surfacesin the principal zone in stibnite, only one uniradial reflectivity varied, while the other remained constant; in pyrite, both reflectivities vary. Secondly, the planes in stibnite occur as a pair within just one principal crystallographic zone; in pyrite, there are three such pairs, corresponding to the three identical principal zones. Because of this second distinction, pyrite cannot be consideredas either "positive" or "negative" in the sensedefined by Berek (1931b).

Windungsachsen. In translucent (moderately absorbent) crystals of lower symmetry, there exist just four specialtransmission directions for which all rays of light behave identically, as regards both velocity and absorption; these were defined by Voigt (1908) as Windungsachsen (gyroid or rotation axes). Surfacesnormal to the Windungsachsenreflect light without change of polarization state, and with reflectivity independent of azimuth (Berek, l93Ia). In other words,such sections behave isotropically in normally incident Iight; and there is no pair of special directions (either principal vibration directions or directions of uniradial reflection) associatedwith them. In translucent crystals of lower symmetry, these two conditions apply onl,yto planes normal to the Windungsachsen. The resultsdescribed in the presentpaper suggest that theseconditions are satisfied by surfacesin pyrite parallel to the octahedra. As far as is known, such surfacesbehave isotropically; and if optical relationships are truly compatiblewith crystal symmetry (as presentresults suggest) then there cannot exist a pair of special directions normal to a triad symmetry axis. There are four Windungsachsenin crystals of lower symmetry; there are four normals to the octahedra in pyrite. Moreover, relative to each G S. GIBBONS principal plane, thesenormals may be consideredas two pairs, eachpair being svmmetricalll' disposedabout that plane. This is precisell-the arrangement observedrelative to the single optic plane in crr.stalsof lower svmmetrl'. Despite these similarities, however, the normals to the octahedra should be consideredat best comparablewith, and certainly not equiva- lent to, Windungsachsen;first becausethere is no evidencethat these are the only directtonsin pyrite satisffing the conditions outlined above; and secondlybecause, since p.vrite does not obey normal laws of optics, the significanceof these directions is probabll' diflerent frorn that in lower-svmmetrycr1'stals.

Sulrulnv oF THE ExpntrlrBNral Rnsur,rs 1. In general,when a polishedsurface of pyrite reflectsplane polarized, normally incident light, the plane of polarization undergoes a slight rotation. The senseof rotation for blue light is oppositeto that for red light. 2. When pvrite is studiedin white light, this dispersionof the apparent angle of rotation causespolarization colorsin orthoscopicexamination, and fringed isogyresin conoscopicexamination. 3. The geometry of the reflectionanisotropy in pyrite is qualitatively compatiblewith the morphologicsymmetry of the mineral. 4. In a pyrite surface parallel to a principal crystallographic axis, the axis direction is a direction of uniradial reflection.However, the reflectivity value of this direction is not a constant for all such surfaces.

TuB DrscnBpANCyBETwEEN Tunonv axo OlsenverroN The fact that the reflectionanisotropy of pyrite is not compatiblewith acceptedtheories of crystai optics is proven by the variation in reflectivity for directionsparallei to crystal axes.Previous work (e.g.,Berek, 1931b)would indicate that this reflectivity should be constant.Indeed, completeoptical isotropy is indicated for any isometric crystal. The explanationof the discrepancymay be that we are concernedhere oni.v with polishedsurJaces of an opaque material. Klemm (1961) found that perfect cr1'stalfaces of pyrite do not exhibit poiarization effects. Cissarz(1931) found that the reflectivity valuesoI polishedcleavage surfacesin stibnite are almost 20 percent lower than correspondingvalues measuredon unpol'ished,cleavage surfaces. Observed anisotropy in pyrite may thereforebe a result of polishing, and not inherent in the actual crystal Iattice. If this were so, the effectsobserved might well be compatible with crystal symmetry, yet still be outside the scopeof conventional theories of optical geometry. ANISOTROPY IN PVRITI] 369

C.q.usBoF THE ANrsornopy Four possiblecauses of anisotropicelTects may be considered. 1. Internal strains, perhaps set up during crystallization, might be responsible.Opticai geometry would require such strains to be at once compatible with crystal symmetry, and homogeneousthroughout the crystal; the lattice symmetry would be unaltered,and the problem would remain as before. 2. Oriented inclusions of some other mineral of lower crystal symmetry might be present.Such inclusions,if present,must be quite uni- form, sincepyrite polarizationcolors are always similar. Inclusionshave not been detected in X-ray investigations,while trace-elementcontent in pyrite varies greatl,v (e.g.,F-ischer and Hiller, 1956); hence this explanation seemsunlikelr'. 3. Directional hardnesseffects are well-known in cubic crystals (a.g., Giardini, 1958), and these might give rise to submicroscopic,oriented pits, scratches,or ridges in polishedsurfaces. However, Stanton (1957) has shown that such irregularitiesare not responsiblefor pyrite anisotropy. 4. The most probable explanation of anisotropy in pyrite is that reflection takes place within a sort of Beilby layer of crystal-latticedis- tortion at the crlrstal surface. This layer is visualized, not as a zone of flow, but as a very thin skin having a nonisometriccrystalline structure partially controlied by the orientation of the underlying lattice. The suggestedlayer, being extremely thin, might be caused by even the gentlestpolishing, and indeedma.v be destroyedby harsh grinding. The optical geometryobserved as a result of such surfacedeformation would necessarilyconform with crystal symmetrv, while individual polished surfaceswould behave anisotropically,like polished sectionsof lower- symmetry crlrstals.

AcrNowrBlGEMEN'r's The author expressesthanks to Mr. K. R. Glasson and Associate ProfessorL. J. Lawrencefor advice during the investigation and to Dr. T. G. Vallanceand Dr. I. M. Threadgoldfor constructivecriticism of the manuscrrpt. The work was supportedby a Deas-ThomsonScholarship in Geologl', and was carried out in The University of Sydney during preparation of a M.Sc. thesis.

Rrpnnlscos

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Monuscript receired.,May 27, 1966; accepted.Jor lublication, August 12, 1966.