American Mineralogist, Volume61, pages260-265, 1976
Miissbauer effect study of 57Feand lreSnin stannite, stannoidite,and mawsonite
Tnrlurrsu YnvnNnrn
Mineralogical Institute, Faculty of Science
Uniuersityof Tokyo, Il3 Hongo, Tokyo, Japan
nNp Arrne Ke.ro
Departmentof Geology,National ScienceMuseum
Tokyo, Japan
Abstract
The valencyformulaeof mineralsin the systemCu-Fe-Sn-Sweredeterminedwith the aid
of electronprobe microanalysis
and of the Mdssbauereffectstudy of s?Feand rleSnat
temperatures
of 80"K and 293'K. The formulaeof stannite,stannoidite,
and mawsonite
can
be expressed
as Cu!+(Fe2+,
Zn"*) Sno*S?-,Cul+Fe!+(Fe,*,Znt*1Sn!+S!r-,
and Cul+FeB+
Sno+S3respectively.
Zn wasfoundto substitute
only for thefeirousion. Mawsonitecontains
no zlnc.
The quadrupolesplittingsand isomershiftscould be rationalizedwith crystalfield effects
causedby the differences
in sitesymmetryaroundthe Fe and Sn atoms.Quadrupole
splittings
and isomershiftso[ ""Sn indicatethat the (SnSo)-tetrahedron
of thesespecimens
is strongly
covanentlybonded,and that it may be regardedas a chemicalradical bearingspt hybrid
orbitals.Sitesymmetries
around tin atomsin thesestructuresare similar.
The most probablespacegroup of mawsoniteis I42m, l4mm, 1422,or 14,22,basedon its
X-ray powderdiffractionpatternand the sitesymmetries
of tin and iron ionsdetermined
from
the Miissbauereffectstudy.
Introduction
Mawsonite, stannoidite, stannite, and rhodostannite are mineralsin the systemCu-Fe-Sn-S. Some of
their crystal structuresare said to be similar to that of
chalcopyrite. Markham and Lawrence (1965) stated
that mawsonite was pseudocubic,with the chemical
f o r m u l a C u r F e r S n S , oK
. ato and Fujiki (1969) described stannoidite as orthorhombic with chemical
composition CuuFerSnSr. Boorman and Abbott
( 1 9 6 7 ) ,S p r i n g e r ( 1 9 6 8 ) ,a n d P e t r u k ( 1 9 7 3 ) r e e x a m ined the chemical compositions of these specimens
and defined stannoidite as Cur(Zn,Fe)rSnrS, and
mawsonite as Cu.FerSnS..
Springer(1972) showed in his work on phaseequilibrium diagram for CurFeSnSn-CurZnSnSo
that at a
temperatureabove 680oC synthetic stannite forms a
solid solution with synthetic kesterite in the whole
range of zinc-iron substitution; that the former has
polymorphic structuresof a-phase and B-phase;and
that the increasedZn substitution in stannite will
reducethe temperatureof transition betweenthe two
phases.
The crystal structure of stannite analyzed by
Brockway ( 1934)is closely analogousto that of chalcopyrite. Further, the crystal structure of stannoidite
has recently been analyzed by Kudoh and Tak6uchi
(1974\. This structure indeed resemblesthat of chalcopyrite, but is more delormed compared to stannite
because of the presence of additional interstitial
cations. Stannoidite has four copper sites, two iron
sites,and one tin site. The structuresof other minerals
in the above-mentionedsystemare still not defined.
The cation valencesof these minerals are still ambiguous, becausechemical analyseshave not been
conducted in consideration of the valency states of
cations. Since iron, copper, and tin may all have
severalvalenciesin crystalline phases,complications
arise in defining the valenciesof thesecations.
Pauling and Brockway (1932) and Hall and Stewart ( 1973)discussedthe valencyformula of chalcopyrite from the bond lengthsdeterminedby X-ray crystal analysis,and they reported that chalcopyrite is a
m i x t u r e o f t w o s t a t e sC u ' + F e 3 + S 3a- n d C u 2 + F e 2 + S ! - .
But the neutron diffraction study by Donnay et al.
260
261
,L9SNIN STANNITE
MOSSBAUER EFFECT STUDY OF 57FCAND
specimens
T l s L e 2 . C e l l d i m e n s i o no f
(1958) and Mdssbauer effect study by Chandra and
Puri ( 1968)show that the iron ion in chalcopyritehas
l"lawsonite
Stannoidite
Stannite
a s i n g l et r i v a l e n ts t a t e .
a=70.?45+0.00I
a= 10.789+ 0.009
5.461+0.002
The M6ssbauer effect can determine the charge
5.413 + 0.004
valenciesof iron ions. The cation valence of Fe in
c=10.711+0.006
c= I6.155 + 0.009
10.726+0.007
stannite has been determinedby severalinvestigators
Eibschutz et al. (1967), Marfunin and Mkrtchyan
PTeswable S.G.
S.G.
S ,G .
( 1 9 6 7 ) ,a n d G r e e n w o o da n d W h i t f i e l d ( 1 9 6 8 ) .
r42n, r+*(3)
rzzzQ)
742n(7)
The presentstudy eliminatesthe ambiguity about
1422, 14r22
the valencyformulae of stannoiditeand mawsoniteas (1)
Brocl<'tay (1934)
well as stannitewith the aid of the Miissbauerspectra (2)
(1.974)
ktdoh ml lakeuchi
of both u'Fe and 1leSn.It also discussesthe site sym- (3) Present assmrptLon
metriesof iron and tin and of the characterof Fe-S
and Sn-S bonds in thesemineralsin comparisonwith
synthetic samples and some other sulfides such as 1970), stannoidite (Petruk, 1973) and mawsonite
( P e t r u k , 1 9 7 3 ;K u l i c h i k h i n a a n d V y a l ' s o v , 1 9 6 9 ) .
chalcopyriteand sphalerite.
Cell dimensionsof stannite,stannoidite,and mawsonitewere obtained by X-ray powder diffractometry
Material and experimentalmethod
and were calculated with the aid of least-squares
Stannite from Gyojayama, Kyoto Prefecture,and method using UNICS computer program. The cell
stannoidite and mawsonite from the Akenobe mine, dimensionsof the samplesare presentedin Table 2.
Hyogo Prefecture,were separatedfrom the ores un- Mawsonite was reported to be pseudocubicby Markder the ore microscopeand by the subsequentcrush- h a m a n d L a w r e n c e( 1 9 6 5 ) , L e v y ( 1 9 6 7 ) , a n d K u l i ing, magnetic, and specificgravity separations.The chikhina and Vyal'sov (1969)' Better indexing of the
occurrence and paragenesisof these minerals were mawsonitepattern usingthe computer program writreported by Lee et al. (1974). Synthetic CuzFeSnSa ten by Evans et al. (1963) implied tetragonal symmewere prepared in an evacuatedsil- t r y a s s h o w n i n T a b l e 3 .
and CurFeaSn2Sl2
u'Fe and r'eSnin the natural
ica tube and identifiedby the ore microscopicand XMdssbauerspectraof
obtained at 80'K and at
Their
homogeneities
were
ray powder diffraction methods.
and syntheticmaterials
Chalcopyrite
wereconfirmed by electronmicroprobe.
room temperature (293"K) by using a HITACHI/
u'Co diffused in
cubaAkita
Prefecture,
and
from the Arakawa mine,
RAH/-403, 400 channel analyser.
llemsndoped in
were
Prefecture,
Kyoto
Kohmori
mine,
and
from
the
nite
metallic copper (10 millicuries)
employed for reference.Some of the natural samples BaSnOs (2 millicuries) were used as sources.These
were analyzed by the electron microprobe method, y-ray sources have fairly large recoilless fractions
using a computer program modified on the basis of and give absorption peaks with very narrow-line
the correction formula devised by Sweetman and widths. The line widths of the inner two lines of the
Long (1969), as shown in Table l. Their recalcula- spectrum of "Fe in metallic iron and those of the
tions gave an empirical formula for each specimen. spectrumof treSnin SnOzmeasuredat room temperaThese were in good agreementwith the previously ture were 0.30 mm/sec and 0.83 mm/sec, respecreported formula of stannite (Ramdohr, 1960;Oen, tively, with these sources.
Spectra were taken by the mechanismof moving
Teslr I . Chemical analysis of specimensin the system
the source at both temperatures.Measurement at
Cu-Fe-Sn-S
80oK was conducted with both source and absorber
in a cryostat.
Mailsonite
Stannite
Stannoidite
The intensity of the 14.4 keV 7-ray emitted from
wt%
nol?
ut?
mol%
wtt
rclt
u'Co and the 23.8 keV 7-ray from "'*Sn were de44.15 35.48
38.49 31.69
30.11 24.77
Cu
1 2 . 9 5 1 1 .8 4
12.58
10.04
9 4r
t3 44
tected by a Nal scintillation counter. The spectraof
'?Fe obtained at constant Doppler velocity calibrated
2 90
0.00
0 00
3,62
Zn
1.07
0.86
6.27
8.33
14.58
18.89
Sn
28 55
t2 59
by those in metallic iron were analyzedwith the aid of
46.41
29,14
49.21
29.21
3 0 .l 8
47 -67
a computer program which performed least mean
100.82 100 00
100 26 100.00
t03.35 100.00
squaresfits of the experimentaldata to the Lorenthtrpirical
Cu6Fe2SnSS
C u ^( F e , z n )
Cu2(Fe, Zn) SnS4
" S n ^ s ,^
Fomula
zian function. This calculation did not employ a
T. YAMANAKA AND A. KATO
Tnalr 3. X-ray powder pattern of mawsonites from Mt. Lyell,
T a s m a n i a ,a n d t h e A k e n o b e M i n e , H y o g o p r e f e c t u r e J, a p a n
t.
2.
d(A)
5.37
20
4.37
20
3.80
r0
3.34
l0
3.09 r00
2.87s 20
2.680 50
2.395
2.287
2.I85
2.098
r. 959
l. 895
l. 788
L.739
r .618
L.s47
1. 4 6 0
l0
l0
5
s
5
80
s
5
80
10
5
r.343
20
'.
ZJZ
1
)it
JU
q
a
c
(At
d.
obs' '
d
rA)
carc' '
I.
oDs
hkl
7.62
5.38
4.38
3.80
3.378
3.099
2.868
2.684
2.462
2.401
2.29L
2.792
7.60
5.37
4.38
3.80
5.388
3.099
2.869
2.686
2.46I
2.40r
2.289
2.L92
3
l0
t5
I
4
I00
10
2s
3
8
110
200
7 7 2
220
103
222
312
400
114
402
r.962
r.899
1. 7 9 1
7.742
1.620
1 .5 4 9
L.463
r. 366
1.344
1.318
1.302
1.233
r.20t
1 .0 9 6
r.962
1.900
t.790
7.742
L.620
I .549
1.462
r. 565
L.343
1.319
7.302
1.232
1.201
l. 096
= 1 0 . 7 4A
= 1 0 . 7 4A
7. Ibuteonitu.
Mt.LyeLL,
(1965). Co radia.tion.
2. I4ausonite.
ndiabion.
J J Z
3
422
3
s2r
3
3
40
7
3
3
15
3
A
l0
5b
l5
a
=10.745J0.0013
c
=10.711r0.0063
lasnania,
After
Cmera nethod.
Akercbe nLne,
Diffractoneter
J
440
442
523
622
444
72r
651
800
tl8
644
662
804
844
l,Aukhan and tantence
Hyogo p?efecture,
Japan,
-(b
= br-oadf.
mellod.
Cu/Ni
Gaussiancomponent causinga deviation of line profile from the Lorentzian curve, although the true line
shapemay be closelyapproximatedby a combination
of Gaussian and Lorentzian functions.
T h e m i n i m i z e d v a r i a b l e sw e r e ( l ) p e a k p o s i t i o n ,
(2) full width at half-maxirnum intensity, (3) peak
intensity, and (4) off-resonancebackground count.
Various numbers of peaks assumed to be present
were tested for the best fit.
ln the analysis of the lreSnspectra, a Pd-filter (70 p
thick) having a K-absorption edge of 24.3 keV was
applied to eliminate the K-X-rays with energiesof
25.04,25.27and 28.49 keV.
Isomer shifts of 5?Fe and lleSn spectra of each
sample were measuredwith referenceto the isomer
shift of 310 stainlesssteeland SnOr, respectively.
d-electrondensity in iron ion. The orbits of p- and delectrons play the role of screeningthe s-electron
from the positive electric charge of the nuclei. Fd+
(3d), which has one more 3d-electron than Fe8+
(3d), shows a larger screeningeffect and a decreased
electron density around the iron nuclei, which causes
the larger isomer shift for Fe'+, (Walker et al., 1962;
S i m a n e ke t a l . , 1 9 6 8 ; W a t s o n , 1 9 6 0 a ,1 9 6 0 b ) .
Covalency of Fe-anion bonds also influencesthe
isomer shift. Increase in the ionic character of the
bonds causesa decreasein the density of s-electrons
around iron nuclei and raisesthe isomer shift in both
ferric and ferrous ions.
The quadrupole splitting of u?Fedepends on the
electric field gradient at the iron nuclei, which is
induced from the valency electrons and from the
surrounding anions. The electricfield gradient is also
attributed to distortion of electron orbits due to the
crystal field and the covalent bonding character,(lngalls, 1962, 1964; Sternheimer, 1963). The electron
cloud of Fe2+is more likely to be distorted and more
sensitiveto the configuration of surrounding anions
than that of Fes+and consequentlyexpectedto give a
larger value of quadrupole splitting, while Fe3+presentsa sphericallysymmetric electroncloud. It must,
however, be noted that in the casewhere the Fe2+site
symmetry is as high as cubic, Fe2+compounds would
show no or very small quadrupole splitting. The influenceon the quadrupole splitting of the deviation of
the symmetry of ligands from the cubic symmetry
(43m) in sphaleritestructure to the monoclinic (2) in
stannoidite could be recognized in this study as
shown in Table4.
t'"Sn Mbssbauer spectra
Neutral
tin has the electron configuration
Sna+has the electron configura[Kr](4d10)(5s')(5p").
tion [Kr](4d'o); Sn'* has [Kr](4/oX5s'). Since tetravalent tin is little affectedby contributions of the
(5s) electron, the isomer shift of Sno+in rleSnM6ssbauer spectrais very small. On the other hand, divalent tin ion exhibits a very pronounced isomer shift
due to a large contribution of the (5s') electrons.
Increaseofcovalent characterofSn2+ resultsin the
formation of (5s'z)(5p')or other s-p hybrids thereby
slightly reducing the isomer shift. Many covalentbonded tin compounds consist of tetrahedral fourfold structures bearing (sp3) hybrid orbitals, as do
Experimental results and discussion
carbon compounds. In some cases,the (5d) orbital
It has been proved that the isomer shift increases takes part resulting in the formation of trigonal dipywith decreasesin s-electrondensity and increasesin ramidal five-fold coordination as the (spad) hybrid
AND I,gSNIN STANNITE
MOSSBAUER EFFECT STUDY OF UTFC
Tlst-r 4.
M d s s b a u e rs p e c t r ao f 6 ? F ea t 2 9 3 ' K a n d 8 0 o K
80'K
293'K
Q .s .
Specinen
Val ency
0.53
0 .0 3 0 . L 7
0 . 0 3 0 . 5 6+ 0 . 0 3 0 . 2 8 + 0 . 0 3
Fe"'
Unknom
(i )
0.53
0 .0 3 0 . 5 4
(II)
0.76
0.06 2.86
0.03 0 . 5 6 t 0 . 0 3 0 . 3 9 t 0 . 0 3
0.06 0.87+ 0.08 3.08+ 0.08
Fe)+
Fe-
222
(r)
0.50
0.03 0.36
0.03
-tse3 +
(II)
0.76
0.08 2.86
0 .0 8
tse
222
0.78
0.03 2.80
0.03 0 . 8 4+ 0 . 0 3 3 . 0 2 i 0 . 0 3
0.76
0.03 2.86
0.03
Fe?+
Fe-
42n
chalcopyrite
0.34
0.03 0.00
Cubanite
0.50
0.03 0.88
0.67
0.06 0.8r
0 . 0 c 0 . 5 0 + 0 . 0 3 0 . 0 0+ 0 . 0 3
0 .0 3 0 . 5 3 + 0 . 0 3 1 . 0 1 + 0 . 0 3
0 .0 6 0 , 8 9 + 0 . 0 6 2 . 0 2 + 0 . 0 6
I{awsonite
Stamoidite
Synthetic
Stamoidite
2
2
1L
Stannite
Synthetic
Stmnite
Spharerite
57r"
Doppler
ir
(zr,,ru)s
oeLocity
is calibrated
taome" gnLJt 1r.5.)
by t\e
and qmdrupole
spectrm
spLttting
57Ee
of
orbit or an octahedral six-fold coordination as the
(sp'fr) hybrid. Within the same structural configuration, the isomer shift of compounds containing
{SnXol and [SnXu] groups decreaseswith the electronegativityofthe surrounding anions (Stdcklerand
S a n o ,1 9 6 8 ) .
The isomer shifts of "'Sn in stannite, stannoidite,
and mawsoniterange from 1.45 + 0.03 to 1.48+ 0.03
mm/sec (Table 5). Thesevaluessupport the assumption that the SnSo-tetrahedronof these minerals is
strongly covalent and may be regardedas a chemical
radical such as are found in sulphosalts.
The quadrupole splitting of lreSnis not an effective
means for determining the electric charge of the tin
ion. lt has been proved that Mdssbauer spectra of
ionic Sn'+ compounds have a tendency to show a
greater quadrupole splitting than those of Sna+compounds. This is becausethe latter compounds generally consist of highly symmetric coordinations
around the tin ions. Furthermore, the higher the covalency of the Sn-X bonds, the less the interaction
betweenthe quadrupole splitting and electric charge
of tin ion.
A seeminglysinglebroad peak was observedin the
lreSnspectraof stannite,stannoidite,and mawsonite.
Little or no quadrupole splitting was detectedeven
after computer processingthe data. Somequadrupole
splitting may be assumedto be presentat leastin the
spectraof stannoiditefrom the fact that the site symmetry around the four-fold coordinated tin atom is
(222), which deviates considerably from (42m) of
stannite. The absence of observable quadrupole
splitting probably results becausethe [SnSr] group
does not have a sufficiently large electric field
xo
?e Latlte
Fe'
Fe-
222
Fe-
43n
i.on.
Ln netallic
(Q.5. ) tre
42n
s 7f _e
in
3L0 stainless
eteel.
gradient around the tin ion. The minerals are each
confirmed to have only one strongly covalently
bonded four-fold coordinated Sna+ion. The fact that
the isomer shift and quadrupole splitting of "eSn is
nearly identical in all three minerals suggeststhat the
tin coordination is very similar although the site symmetry of the ion may be different.
In spiteof the anomalouslylong Fe-S bond lengths
in the system (for example, 236 A in stannite) and
the high site symmetry, u?FeMdssbauer spectra of
stannite and stannoidite show a much larger quadrupole splitting than that of other sulfidescontaining
iron atoms. This may be explainedby the fact that an
iron atom bridges two (SnSr) tetrahedra which are
strongly covalently bondedgroups, and that the Fe-S
bonds may also have largely covalent character.
57Fe Mbssbauer speclra
Slannite. The isomer-shiftsof natural and synthetic stanniteprove the iron to be divalent(3r1").The
small values compared with isomer shifts in many
other ferrous compounds confirm the existenceof
spectraof""Sn
TesLe5. M6ssbauer
r.s.
Specinen
(nn/sec)
Q.s
(m/scc)
l',la{sonite
L46
+ 0. 05
0.00
Stanoidite
1.48 + 005
Stanni te
1.45+ 005
Synthetic
Cassiteti
Is@e"
in
Sns
te
ehift
(1.5.)
the svilthetic
Valencv -
00s
(snS,)-
0.00
0.05
(SnS, )
0.00
005
(SnS,)
3 . 4 8 + 0. 03
0. 9l
005
000+
0.40
0.05
0.03
and qwdtupole
SnOz
spLitLing
Si ra
symetry
unknoM
-
- -)-
Sn'^4+
(Q,S ) ore
2
42n
n
mn
.
lls
264
T. YAMANAKA AND A. KATO
highlycovalentbonds.In spiteof the42msymmetry and isomershift are about the sameas thoseof the
of iron ions in stannite,the exceedingly
largequad- inner doublet (1) in the spectraof stannoidite,inrupole splitting also indicatesthe presenceof the dicatingthe existence
of ferric ion in an analogous
covalentbonds.This may be because
iron sharesone coordination.
of sulfur ions of (SnSn)n-group havingthe aforeThoughthe crystalstructureof mawsonitehasnot
mentioned(sps)hybrid bonds.
beenanalyzedbecauseof difficultiesin obtaininga
Syntheticstannitehavingno zinc contentshowsa singlecrystal,the presentX-ray powderdiffraction
higher absorptionpeak, a slightly smallerisomer- data and the Mdssbauerspectrumhaveconsiderably
shift and a little larger quadrupolesplitting than clarified the structure.The most probable space
thoseparametersfor natural stannitehaving 9 mole group is 142m,I4mm, 1422or 14122
to be consistent
percentof zinc. It may be concludedthat zinc sub- with site symmetriesaround the tin and iron ions
stitutesfor ferrousion and increases
the ionicity of its determinedfrom the Mcissbauereffectstudy as well
bonding.
as of the indicesof powderdiffractionpeaks.
Stannoidite. There exist two pairs of doubletsin
the Mbssbauerspectraof naturaland syntheticstanAcknowledgments
noidite.Isomershift and quadrupolesplittingof the
innerand outerdoubletsprovethe existence
The authors are very indebted to Professor R. Sadanaga,Profesof both
s
o
ferrousand ferric ions in stannoidite.
The observed r Y . T a k 6 u c h i ,a n d D r . Y . K u d o h , M i n e r a l o g i c a lI n s t i t u t e ,U n i absorptionintensity(2.38Vo)
of the inner doubletof versity of Tokyo, for their fruitful discussion and comments, and
w i s h t o t h a n k D r . M . S . L e e ,D e p a r t m e n t o f M i n e r a l D e v e l o p m e n t
zinc-freesyntheticstannoiditeis almost twice as Engineering, University of Tokyo, for his guidance in synthesizing
muchasthat of the outerone(l.2lEo).Sinceit canbe t h e s a m p l e s .
reliablyassumed
that eachrecoilless
fractionand saturationeffectis not very differentat the two iron sites
References
of stannoiditebecauseof the sameeffectivewidth of
the absorberand identicalsitesymmetries,
the ratio BoonunN,R. S., eNo D. ABBorr (1967)Indium in co-existing
mineralsfrom the Mount Pleasanttin deposit.Can.Mineral.g,
of absorptionintensities
of the inner and outerdout66-t79.
blets may be regardedas the fraction of ferric and Bnocrwnv, L. O. (1934) The crystal structureof stannite,
ferrousions in thesesites.Accordingly,the zinc-free CurFeSnS..
Z. Kristallogr. 89, 434-441.
stannoiditeis provedto containtwiceas much ferric CHeNone,R. D. K , nuo S. P. Punr(1968)Mdssbauer
studiesof
chafcopyrite.
J. Phys.Soc.Japan,24,394l.
ion as ferrous ion and can be expressedas
DoNNly,C., L. M. Conlrss,J. D. H. DoNNAy,N. Er-llorr, eNo
Cul+Fel+Fd+Snl+S?z-.
J. M. HesrrNcs(1958)Symmetryof magnetic
structures:
MagThe outerdoubletcorresponding
to the ferrousion
neticstructureof chalcopyrite.Phys Reu. ll2, l9l7-1923.
of the syntheticstannoiditehas a largerabsorption ErsscHurz,M., E. HERMoN,
eNo S. SHrnrrprnN
(1967)Determination of cation valencesin Curs?FerreSnSn
peakthan thatof thenaturalmaterialcontaining2.90
by Mdssbauereffect
and magneticsusceptibilitymeasurements.
J. Phys.Chem.Solmole percentof zinc ion, while the absorptioninids. 28. 1633-1636.
tensities
of the inner doublethasabout the samein- Everus,H. T. Jn., D
E. Appr-rueu,,cNpD. S. HnNnwenrsn
tensityin both specimens.
This suggests
that zincsub(1963)Programand Abstract42. Am. Crystallogr.Assoc.Meet.
stitutesonly on ferroussitesin stannoidite.
Theabove Cambridge.
valuesindicate70.6percentof zincsubstitution
in the Gnesnwooo, N. N., ruo H. J. Wurrnrer-o(1968)M<issbauer
effectstudieson cubanite(CuFerS.)and relatediron sulphides.
ferrousion site.Zinc substitutioncanprobablyreach
J. Chem Soc. A1968. 169'l-1699.
the ratio of Zn/(Zn * Fe) : /r at most.
Herr, S. R., lNo J. M. Srrwnnr (1973)The crystalstructure
Mawsonite. The presentanalysisshowsmawsorefinementof chalcopyrite,CuFeS,. Acta Crystallogr.8,19,
nite to have the formula Cu.FqSnSsas previously 579-585.
reportedby Petruk (1973).No substitutionof zinc lNcnr-ls, R. (1962)Variationalcalculationof the Sternheimer
factorsfor the ferrousion. Phys.Reo. 128, I 155-l 158.
for iron in mawsoniteis observed.
Mawsoniteis un- -(1964)
Electric-fieldgradienttensorin ferrouscompounds.
able to admit a divalentcation such as zinc, probPhys.Reu. 133A, 787-795.
ably becausemawsonitecontainsonly ferric iron. Knro, A. eNroY. Fulrrr (1969)The occurrence
of stannoidites
The Mdssbauereffectstudy givesthe valencyforfrom the xenothermalore depositsof the Akenobe,Ikuno, and
mula of mawsonite
as Cul+Fe!+Sno+S3-.
The quad- Taka mines,Hyogo Prefectureand the Fukoku mine, Kyoto
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Kuoou, Y., nNoY. TerEucur(1974)The structure
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similarto thoseof stanniteandstannoidite.
Only one
Crystallogr.Soc. Japan,Annual Meeting, Abstr , p. 51.
57Fedoubletis observed,
and its quadrupolesplitting Kur-rcHrxurr.rn,
R. D., lNo L. N. Vvel'sov (1969)A find of
MOSSBAUER EFFECT STUDY OF "7FeAND rsSn IN STANNITE
265
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Mineral.Mag.36, 1045-1051.
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Can Mineral. ll, 535-541
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98-t0l
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5. 59-84.
Phys Reu.l18, 1036-1045
(
1
9
3
2
)
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v
P,,,ur-rNc,
O.
-(1960b)
calculation
ll. Phys.Reo.
Iron seriesHartree-Fock
chalcopyrite CuFeS,. Z Kristallogr. 82, 188-194.
ll9. t934-1939.
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98-t0t.
L r e , M . S . , S . T , r x E N o u c H r ,A N D H . l n n t ( 1 9 7 4 ) O c c u r r e n c ea n d
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Rnvoonn, P. (1960) Die Erzmineralien und ihre Verwachsungen.
A k a d e m i e - V e r l a g ,B e r l i n , 8 2 6 p .
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Manuscript receioed,June 18, 1975; accepled
for publication, Nouember 4, 1975.