G. H. Faye A/-D E' H' Nickel "

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ON THE PLEOCHROISM OF VANADIUM-BEARING

ZOISITEFROM TANZANIA

G. H. FAYE A\-D E' H' NICKEL "

AsstRAcr

optical absorptionspectra of both blue and tan-coloured'


-teuealed
A stuily of the polarized .;*ff;;
a numb-erof spectral
vanadium-bearingzoisite I;'?;;ia,
ilo;;f -these are attributed to \I+ substituting
featuresbetweenrg,aoou"i?,060^;;' schemeo{ the blue (heated)
on the At3 site o{ zois*e # $".ai"Utoic X (violet)): An-additional
";;;;igr9}i,f z--<al"q'-E'//
varietvof zoisite(i.e. E fi?" J'87/
;il;""t"221;t';r:l'tr'""stt;' b" d";to ri"i' o'.v"' occursin theE // z spectrum
ififfi:fr;;i oi-t"" -itit., thus producing a trichroic scheme'

Recentlygemmologistshaveshorrnccnsiderableinterstinv'anadium-
b""Jrrg ,oiril - (Andenon 1968; Liddicoat & Crowning-
lro^ i^n' nia
and^ phvsical
shield 1968; Meen ir6tt, til crystallographic' "I-ti"* (1969)'
ptrp""i"t which h"u" b"t t describedrecently by Hurlbut
"1 it itt pleochroism which
The most strikinf property of this materiai
several of the
from trichroi"'i" ai"f'roic on heating' Although (Ander-
"ft"nf,
;;;ft ;trorption bands have been located*itt " spectroscope
for each principal optical
son 1968), the details of the absorptionspectrum knowledge
only through a
direction do not seemto have been reported.
ofthepolarizationpropertiesofthespectralfeaturescanthepleochroism
oltheuntreatedandheatedzoisitebeunderstood.Thisnoteisdevoted
to that end.
were obtainedthrough
A number of specimensof the Tanzanian zoisite
the courtesy H. R.;;;y,-"urator of the.referenceseneso{ the National
"f Canada' Of the two specimens
Mineral Collection, GeologicalSurvey of
(eaih conchoidallyfr;;:d), whore'detailed spectraare reported in this
study, one was tan i; J";; in ordinary white light and trichroic in
white light' and dichroic in
pJ""r""J itgftt, *t it" t1"" other was blue in
the tan crystal Y-0'26/e'
polarized light. Microprobe analysis-gave.for
Ti-0.04%, Fe and ff;t; detot"d;-a"d for the blue crystal V-0'18%'
of two other'specimens
Fe, Mn and Ti not detected'Microprobe analysis
sliowed their V contents to be 0'24 to
ol the trichroic u"ri"t/ J 'oisite
The -V and Ti contents
O-.g0%,and their Ti content to be 0'024/o'
of a secondbl,r" ie'e 0'20% and 4 0'U% respectively'Thus'
"rystai-
--l
scientists, Mineral sciences Division, Mines Branch Department of
n*u"r.r,
Energy, Mines and Resources'Ottawa' Canada'
PLE@HROISM OF ZOISITE FROM TANZANIA
813

there. is an apparent correlation between


cstain spectral properties of
the Tanzanian zoisite and its titanium
content.
Using an iterative procedure of cutting
with a wire saw, and orienting
by means of optical interference
d;; radonal sections were obtained
from the tan- crystal. After polishi"i
tlr*" sections were used to measure
the polarized absorption spectra
Jo*' in Figure r. The unpolarized.
spectrum of Figure 2 was obtained
from a rand,om section of the blue
crystal.
All spectra were measured at room
temperature with a Cary_I4
recording spectrophotometer. The
- standard ,"rrrpl" was
replaced special- housing which permitted "o_f"*_"nt
_\y_^ the mounting of a
Unitronl\^Pf micrlcope in eacl of the sample-urri
f"g*lTc
beams (in either ,uf"."rr."
the infrared or visibre mode) in a manner
that of Burns (1g66). The mineral simirar to
,pu"i-ur; mounted. on the stage
of the sample-beammicroscope,was
oriented in the porarized light
beam so as to measur" q-u. aurir"a
,p*r**, i.e., parallel to a given
crystallographicdirection. GIan prisms'wuru
,rrud as polarizers.Because
the polarizers cannot be used aiovu
-' 25,000-cm-runpolarized spectra
were measuredin the ultraviolet region (e.g.
spectra marked UN in
Figure la and lc).
The trichroic schemeof the untreated.
tan zoisite can be appreciated
through a study of the spectra of Figu;
1. when the electri"'vector E,
of the polarizedlight is paralletto Z J
i e."., E // Z:;t;" mineral
has a yellow-greencorour due to ta"
:-""jiol to brue
light by the rather intense band centered "rrorpti" "riii",
at 22,sb0-cm-.Although the
16,800-cm-1band does^absorbsome
-n*uto*
,"ff"* hght, it ir,*;;il is weak
relative to that at 22,sa0-crrrt,
tre net resurt is the rans-
""a
*o:91^:f yellow-greenlight. Because
the specrralfeatureswith maxima
at 27'000-crn1 and 13,400-cm{ aru both
outside trru uiri'u ,ug ion, i.e.,
,-25,000-crr1 (400nm) to _t 14,000-cm-r(700
nm), ;t;; not in-
fluence the colour.
y : c spectrum,the
"^ ]1fru E // two-componentenvelope(16,700_
19,000cm-') abnorbsvelow-green tight-ana
rh" ,*,;-ilurJtf tr"rrr-it,
blue,light. The trough o, u"il"y
at-- 22,000_cm-1 (._450
\'- nm)
can be thought of as a .,window,, "erriu."d
for the blue light.
Similarly, in the b spectrum, blue-green to yellow-green
light is absorbedin the 1 //"!^^=
12,000t" ibro-oo region, and, the minerar
section derives its red-vioret corour from "--.
the combined transmission of
violet.light through the shallow 'window"
on the r'sh*"d side of
the abso.rptionenvelope,and of ,"d ilil;
on its low-energy side.
814 TITE CANADIAN MINERAIOGIST

4oo 5oo 600 7oo q---999

0.8

0.7

o.6

ul
(,
z
cl
E
o
o
o

+:'_Z-;N

\ .r-{t
PLEOCHNOISMOF ZOIIIITE FROM TANZANIA 8I5

Frc, la. Spectra of an a-c section of tan zoisitg tlickness: 0.32 cm.
A E // Z : a spectrun of qntreated zoisite.
B E // Z : a spectmm of zoisite after heating to 600"C.
_ C Unpolatized spectrum of zoisite after heaiing-to 600.C.
Frc. lb. Spectra of an a-c section of tan zoisite
A E // Y : a spectmm of untreated zoisite.
B E // Y :,a spectrum of untreated zoisite after heating to 600"C.
Frc. lc. Spectra ol an a-b section of tan zoisite, thi&ness : 0.1g cm. "
A E // X : b spectrum of untreaied tan zoisite.
B E // X : b, spectnmr of untreated tan zoisite after heating to 600.C.
(_-_- C Unpolarized spectnrm of tan zoisite after being heated ti 600.C.

As reported previously (Liddicoat & crowningshield rg68; Hurlbut


1969), the trichroic tan zoisite becomesblue on heating; the spectral
chlnses induced by such treatment are shown in Figure 1. Experiments
indicated that tlere is no appreciablechange on heating below 2s0oc.
However, on heating the vanadium-zoisitg in either or hydrogen,
"it indicated in
in the range ^-450 to 650oc, spectralchangessuch as those
Figure I are produced. It is evident that the colour change is primarily

lll
(J
z
.D
E,
o
at,
gt

zs?o|!to
cnil x lo-5
Frc. 2. Unpolarized spectnrm ol a random section of untreated
blue zoisite, thickness: 026 cm.
816 THE caNADIAN MINEnALocrsr

the result oi the disappearance of the 22'500-crr1 band from the E / / Z


: o spectrum of the originally tan-coloured mineral. Figure I also shows
that the E // Z : a sp€ctrum of the heat-treated zoisite is essentially
the same as E / / Y : c spectrum of the untreated material, and this
accounts for the change in the pleochroic scheme from trichroic to dichroic.
On the basis of the foregoing, then, the blue colour of the untreated
zoisite, whose unpolarized spectrum is shown in Figure 2, can be attributed
to the absence of the 22,500-cm-r band. These observations also suggest
the possibility that the natural blue variety of zoisite may have been
subjected to thermal conditions not experienced by the tan material'
Having described the polarized absorption-spectra of the vanadium-
zoisite it is desirable now to attempt to explain the origin of the spectral
features.
Analysis indicates that vanadium and titanium (in the trichoic variety)
are the principal transition-metal ion impurities in zoisite, and it is
reasonable to assume that the spectra are due to one, or both, of these
ions substituting for aluminium on one, or both, of the two kinds of
octahedral sites (Figure 3). However, the spectra should be dominated
by features due to vanadium ions because of its much higher concentration
in the mineral.
Because V5 is a do ion, it cannot give rise to intra-cationic electronic
transitions; therefore, the spectra must be due to one or more of the
chromogenic ions Vz+o V3+ and V4+.
Although V'* (d) theoretically has a complex absorption spectrum
in the visible region, it is seldom observed and it is unlikely that this ion
is present in zoisite because of its relatively large size (0.884) and low
stability in an oxygen environment (Cotton & Wilkinson 1966, p. 817;
Sturge,1963).
As we will see, the prcsence o.f va+ in the Tanzanian zoisite cannot
be completely discounted; howevero it is probable that most of the spectral
features of fhe spectra can be attributed to V'+, an ion whose iharge alone
makes it a likely substitute for A13+. However, it will be evident that the
trichroism of the tan variety of the mineral cannot be explained on the
basis of this ion alone.
' It is well known that the absorption sp€ctrum of Vu+ (d'?) has three
'Tr(F) -->uTr(F)'
principal bands due to the spin-allowed transitions
-'Tr(P) and sT, -> uAr(F) (for example see Cotton & Wilkinson
"7,
1966, p. 677), It is convenient to designate the spectral bands associated
with these transitions as v1, \r2 and vu respectively, in order of increasing
energy. In the spectrum of Vu+-bearing corundum, for examplq v1' v2
PLEOCHROISM OF ZOISTTE FROM TANZANIA 8I7

and vs are found at 17,500,25,000 and 31,000 to 34,000 cm-1 respectively


(McClure 1962; McFarlane 1964).
Although the intensity of the background absorption, due to charge-
transfer processes, increases rapidly in the ultraviolet region, it was
possible to resolve the unpolarized spectrum of a thin a(z)-c(y) secrion
of the tan zoisite to -,39,000 cm-1. Because a signiflcant shoulds was not
found between 27,000 and 39,000 cm-1, it is considered that the entire
d-d spectrum of Tanzanian zoisite is in the range a;13,000 to 27,000 cm-a,
and that all the features present in the spectra are shown in Figure 1.
Because the 22,500-cm-1 band is the only one afiected by heating the
tan zoisite (in air or hydrogen), it is unlikely that the band is part
of the d-d spectrum of V'+. As we have seen, the spectrum of Vs+ is
complex and it would be expected that more than one band would
disappear or change in intensity during the heat treatment. Thus, it
seems necessary to assign the 22,500-crca band to either Va+ or Tis+.
Both of these ions have a d' confi.guration, and in octahedral coordination
can give rise to the 27, --> ,E(D) transition. This point will be taken up
in more detail below.

Frc. 3. The struchrre of zoisite as viewed nearly along the


0 axis, (after Dollase 1968).
818 THE CANADIAN MINERALOGIST

On the basis of the foregoing, it can be concluded that the spectra


of the heatedtan zoisiteand the natural blue material (Figure 2) are due
to V3+ alone, and that the broad, multi-component envelopescentered
at ^-13,500 and ^r18,000-cm-r can be assignedto the v, and v, transitions
respectively,while the 27,000 cm'1 band is the result of the !a transition.
Becauseof its size (0.74A) and the fact that a d' ion gains considerable
crystal-field stabilization energ:yon entering a distorted octahedral site
(Schwarz 1967), it is probable that most of the Vs+ is located in the
larger and more distortedAl, site of zoisite (Figure 3). The relatively low
symmetry (Cr,) of the Alu site may also account for the splittings of the
v, and r, absorptionenvelopesin the spectraof Figures 1 and 2.,Attempts
to work out selectionrules basd on Cru symmetry (using correctly chosen
axes) were unsuccessfulin explaining the polarization p'roperties of all
the spectral bands. However, it is worth noting that the polarization of
the vu band (Figure 3a), which is present only in the E // Z : a
spectrum, can be accounted for on this basis with the ground state
of Vu+ in the Al, site being BAr.
Figure 4 is a simplified energy-level diagram tor a d' ion in an
octahedral fleld (after Berkes 1968) when the Racah parameter, B, is
630 cm'1.It is apparentthat a good fit is obtainedfor the spectralfeatures
of Vt+-bearing corundum when the crystal-field parameter, Dq is
-,1,800 cm'1. To achieve a fit for the vr and v: bands of the zoisite
specra, D4 must be reduced to .-I,400 cm'1; however, this places v,
at ,u20,000 cm-1,a value that is high by 2,000 cm'1.If the Racah para-
meter B, which is a measure of the separation ol the free-ion terms
3F and 3P, is less for the zoisite spectrum that for the corundum spectrum'
then v, for the former could be placed closer to the observedvalue of
^118,000 cnr'1.
That the crystal field experiencedby V3+ in the Tanzanian zoisite
is appreciably lower than in corundum may well reflecto in part, the
difielence in the size of the sites in the two minerals : the averageAl-O
bond distancesfor corundum and zoisite (Al,) are 1.92A and 1.974
respectively. Nevertheless,the strength of the crystal field is rather low;
in this connection it is noteworthy that the averagePauling bond strength
for the Al, oxygensis 1.96 and that of the A1r,, oxygensis 2.06 (Dollase
1e68).
It was suggestedabove that the highly polarized band at 22,500 crr'
was due to either Vo+ or Tie+. However,Ti'+ is to be favouredbecauseof
its chargg and becausethe presenceof the 22,500-cm-1band in the spectra
of the tric.hroic variety of the Tanzanian zoisite seemsto correlate directly
with the presenceof a significant conc€ntration of titanium in the mineral.
PLEOC}IROISM OF ZOISITE FROM TANZANIA
819

Basing the calculationson totar titanium concentration,


the efiinction
coefficientfor the 22,500-cm''band is in the range 50 r00
to litre/more-cm,
which.is appreciablyhigher than for rhe vs+ spectr"r r""ar.,"rrich
are
generally in the range2 to 15 litr"e/mole_cm.
rI the 22,500-cm{band is-due to the
"7" -> 'E"(D) transition of ris+,
its energy is appreciablyhigher than for AlrO.,fii*.
Ir, thu
transition is found at ^,19,000 cmo (Mccluru looz;. "o*rrdrr_,
Tentatively, the
higher elergy can be accountedfor by assumingthat Tir+
is ordered on
AI,., sites of zoisite, altiough it is not evident why
*: :Tir"r this
snoulcl beso.
A; bro3d,
-highly polarizedband at ,*2L,000 cm-1,which is responsible
" the pleochroism
for of andalusite,has recentry been ascribedttTi"* -

'&(F), (oa)

,5r,tpl

40
)qtr),$4el
35
B<630 sn''l
30
lrit

b 25
x
t
E
o
o
!

t
3p o
E
5
g
3
E
o
3T,lF),raz
o 500 t0@ F@ aooozgoo30oo3500
Dq(cm-r)
E r*gy level diagram fo,r d electronic conflgura_
..Frc..4.
tion in an octahedral field; B : 630 cm. (after BLkes
1968).
820 TrrE cANADIAN MTNERALoGIST

can-
Tia+ charge transfer (Faye and Harris 1969). However, this process
of the Tanzanian zoisite because the polariza'
not be invoked for the
"asu band cannot be related to the Alr,r-,tlr,,
tion properties of the 22'5}0-crvtt
possibility
or the Al. .-Al. vectors, i.e. the directions in which there is the
ot overlap or tzs or)Lrals of titanium ions on adjacent octahedral sites.
1 .-

Whether thi'" 22,500-"*-1 band is attributed to either Tia+ or Va*,


theoretical
its polarization properties can be accounted for by using-group
bari tn its site having C2o symmetry' In such calculations the
"rgrr*"nt axes (see Figure 3) arJ taiien to be essentially coincident with
,yt*utry
with c.
tle crystallographic axl, and the unique twofold axis is coincident
'Trn t.2En transition
In the C"r, poittt grouP, the Trn and',Enof t"
in o' tr"rrrflrfu i, + A, + rt" andA, * f,, t"tq*tively (wilson'
", (or Va+)
Decius & Cross lg55). if a, ir"taken as the ground state for-Tis+
when E // Z
then it is found that a tr*ririti"r, (A, + Br) is allowed only
: o., a calculation that is in accori witli observation (Figure 1a). The
porribiliay that this agreement is coincidental cannot be discounted, how-
ever.
process
That the 22,500-cm'r band disappears on heating suggests a
with
in which Tis+ (or Va+) is oxidized to ti** (or V6+) i.e.o to a state
a do configuration, which does not give rise to a d-d absorption spmtrum.
However, i"""t"" the spectral band disappears on heating in hydrogen
as well as in air, it is difficult to rationalize a mechanism that accounts
for this proposal.

AcrNowr,rnctvlENTs
analyses'
The authors are grateful to Dr. D. C. Harris lor microprobe
mineral sections'
and to Mr. P. O'Donovan for assistance in preparing
for helpful discussions'
Special thanks are due to Dr. M. G. Townsend

RErrnpNcrs

Anornsor,B.W.(1963):Triplebill:Threeitemsofinteresttogemmologists.l.Gem
moL ll' 1-3.
So"Es"-i.S.ifg68) : Energylevel4iagrarns-for
-*-tvti;istipt transitionmetalionsin cubiccrlstal fields'
i, tvt"toTiU-nii"ri6 Laboratory"The PennssluaninStateUniu'" Uni'
uersitgPark,Penn. small
Buws, RG. (1966): Apparatusfor measuringpolarizedabsorptionspectraof
crystals.l. Sci.Instrum, 43, 58-6Jli, -
corro'u FJ. * w"*fr;*,-'c.- irs66l : Ad,uanced.inorganit chetnistrg"Semnd Ed.
IntersciencePubtishers,brc., New York.
Dor;;; W.e. (1SOS) r-nun"u**t and comparisonof the structuresof zoisite and
clinozoisite.Amer.Mineral.53' 1882-1898.
PLEOCHROISM OF ZOISTTE FROM TANZANIA 821
Fau,
$'H.- & Hannrs,-D.c. (1969) : on the origin of corour and preochroism in anda-
Iusite from Brazil. Can. Mineral. 10, 47-56:
Hunrrur, (19ry) : Gem zoisite from Tanzania. Amer. Mineral, 54,702-709.
LrDDr@ATr 9.1
ILl. if CRowNrNGsHrEL4 G.R. (1969): More about zoisite, Lapida,rA1.,22n
736-740.
McC-r.unn,
P:S.^1196?) : Optical spectra of transition-metal ions in corundum. !. Chem.
Phss., 36,2757-2729.
MecFanr-enr, Rjl'!- (1964) : opticar and magnetic properties of trivalent
vanadium
- mmplexes.l. Chern. phys., 40,323_327.
Mrrm,^V^3. (1968): Zoisite - a newly found gem from Tanzania.
Lapidarg !.,22,
636-637.
Scnwanz,. H.P. (1967)_: The efiect of crystal fleld stabilization
on the distribution of
transition metals between metamorphic minera\ Geochfun. cosmochii-,
Acta, 3r,
503-517.
!T*"* M.D. (1963) : Oplicgl spectrum of divalent vanadium. phgs. Reu.130, 639-646.
*"i?I: Drcrus,1.e.& cnoss,p.C. (tgttj ; Mobcutariiniiii^.'i"<;raw_Hiil,
l\ew 9.tl
lork.
Manuscript receivedApril 1910"emendeil Mag lgl0.

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