1323
Thz Canadian M ineralo gist
Vol. 34, pp.1323-1327 (1996)

PAVONITE
FROMTHEIKUNOMINE,
HYOGOPREFECTURE,
JAPANMASAAKI SHIMIZUI
Depar*vnt of PetrologyandMineralDeposits,
Universiry
Musewn,Universityof Tolqo,
7-3-1 Hongo, Bunlqo, Tolqo 113,JapanAKIRAKATO
Depanmentof Geology,
NationalScience
Museum,
3-23-1Hyal,.unin-cho,Shinjuku,
Tokyo169,Japan
ABSTRACT

A chemicalanalysisof pavoniteftom theIkunomine,HyogoPrefecture,
Japan,givesAg 11.14,Cu 0.40,Fe 0.08,Mn 0.01,
Pb 0.16, Bi 69.43, S 18.05,for a total of 99.2i7wt.7o, correspondingto (Ago.rrCur.ouFeo.or)>o.qe(Bi2.e5Pbo.or):z.soSs@asis:S = 5). This allows recognition of AgBirS, as the ideal formula of pavonite, a composition which now acquires"end-membey''status.The X-ray powderpattem is identical to thoseof Cu-Pb-substitutedmaterials,and was indexedon themonoclinic cell with a 13.34(1),b 4.036(5),c 16.42(l) A, p 94.25(5)".Pavoniteoccursas an accessorymemberin a ferberite- cassiterite- chalcopyrite- quartz- calcite vein accompaniedby microscopicscheelite,bismuthinite,native bismutl, pyrite,
and a sulfosaltof approximateformula Ag6.rPbrBirn.rS32,
a possiblederivativeof treasurite.This assemblage
is different fromthosein which pavonitehad previouslybeenfound. The occurence is nearthe centerof a systemof concentricallydistributed
veins involving Au-Ag,PVZn,Zn, Clu-Zr, Cu, and Sn-W zones;it lies in the Sn-W zone,whereneitherAg nor Pb minerals
were previouslyknown.
Keywords:pavonite,new association,ideal chemicalcomposition,X-ray powderpatiem,Ikuno mine, Japan.
SoMMans
Une analysechimique de la pavonite de la mine Ikuno, dans la pr6fecturede Hyogo, au Japon,a donn6 (en 7o,poids)
Ag Ll.l4, Cu 0.40, Fe 0.08, Mn 0.01, Pb 0.16, Bi 69.43, S 18.05,pour un total de 99.2i77o,
ce qui correspondi(Ago.s2Ctb.o6Ffo.01L0.e(Bi2.e5Pb0.ot)>z.soSs.00(sur une base de cinq atomes de soufre). Cette d6couvertenous pennet deproposerAgBi3Sr commeformule id6ale de la pavonitepure, c'est-d-dire,non substitu6e.le clich6 de diffraction (m6thodedespoudres)en est identiqueaux matdriauxd6jl connus,dont la compositiond6vie vers un p6le riche en Cu-Pb. le spectre
de diffraction X a 6td index6 avec une maille monocliniqueayant a 13.34(l), b 4.036(5), c 16.42(l) A, et F 94.25(5)'. La
pavonitede la mine Ikuno est un accessoiredansune veine l ferberite- cassiterite- chalcopyrite- quartz- calcite; elle est
accompagn6e,i l'6chelle microscopique,de scheelite,bismuthinite,bismuthnatif, pyrite, ainsi qu'un sulfosel dont la formule
serapprochede Ag6.5Pb78i14.5S32,
et qui seraitpossiblementun d6riv6dela treasurite.Un tel assemblage
sedistinguedesautres
danslesquelson a trouv6 la pavonite.Nous I'avons rep6r6prbs du centred'un systdmede veinesconcentriquesimFliquantdes
zonesenrichiesen Au-Ag, PVZn, Zn" Cu-Zn, Cu, et Sn-W; la pavonitese trouve dansla zone A Sn-W zone,jusqu'ici sansmin6ral d Ag et Pb.
(Traduit par la R6daction)
Mots-cl6s:pavonite,associationnouvelle,cornpositionchimiqueiddale,spectrede diffraction X, m6thodedespoudres,mine deIkuno, Japon.

IrrnotucttoN

the Alaska mine, Colorado (Karup-Mpller &Makovicky 1979).Nl of them havehighly substituted
Descriptionsof pavonite exist in the literature; for chemical compositions, leading to the proposal ofex,unple, pavonite has been documentedfrom the structural formulae such as [(Bi,Sb)1-fb,]ePorvenirmine, Bolivia (Nuffteld 1954,Hanis & Chen Ag2CuS15-a.5r,where; 3 0.1 (Karup-M4ller1972)and1975),the Silver Bell mine (Karup-M6ller L972) and Cur"PbrrAgl_uBi3_nS5o
where 5r = 2y and 0.18
3 y 3 0.32 (Kirup-MOller & Makovicky 1979).Typelocality pavonite is a Cu- and Pb-substitutedmaterial(Harris & Chen 1975).Although the formula AgBi3S5
1E-mail address.'mshimizu@um.u-tokyo.acjp
has been assignedto ideal pavonite in light of the1324

TI{E CANADIAN(e.9.,Van Hook 1960,Makovicky
resultsof syntheses
et al.1977), the validity of sucha formulahas neverbeen tested.The presentwork reviews this proposal,
namely, that pavonite has an ooend-membet''
formulaAgBi3S5;in other words, Pb and Sb would have tobe regarded as non-essentialif that hypothesis isconfirmed.
The first occurrence of pavonite in Japan wasreportedorally by Kato (1964), who found that its
composition is close to the above formula, and its
X-ray powder-diffractionpattern agreesclosely withthat for the syntheticmaterialof Van Hook (1960).The
same material is here re-examined in order todocumentthe chemical composition and the refined
X-ray powder pattern. In the material examined,wefound anotherAg-Ptr-Bi sulfosaltwith an approximate
compositionAg6.rPbrBi,o.5Q2,
which is derivedfrom
the ideal formula of treasurite after substitution ofPb for Agq.5Bio.r.It is referred to as a "treasurite
derivative" in this paper.

MINERAIOGIST

OccunnsNcr
The ore deposits of the Ikuno mine, Hyogo
Prefecture, Japan, are located approximately at
35'10'N and L3447'8, and composedof manyhydrothermalveins of subvolcanicnature. These are
famous for their polymetallic mineralization. The
elementspresentas essentialconstituentsof the ore
mineralsare Cu, Zn,Pb, Ag, Au, As, Sn, W, Sb, Bi,Co, Ni, In, and Se, in order of decreasingfrequency,
and their accessoryconstituentsare Cd, Ga, and Te.
(Kato 1959),
Two new minerals,ikunolite,Bia(S,Se)3(Kato 1965),wereandsakuraiite,(Cu,Zn,Fe)r(In,Sn)Sa
found in the ores.
The veins form in basin-structuredconformablebeds in three main groups,locally called (ftom westto east),Tasei,Kanagase,and Aokusa Gig. 1). The
distribution of the principal elementsin the ore
minerals is zonal, with the zones concenricallydevelopedin a mushroom-like structurethat has its\r';-a Mt.Konogose'r>,

ZN

<rtei

Cu-Zi"'..
Cu[-]

foult

FlveinU-^zE

IKM)
ftc. 1. Distribution of veins and zonal distribution of metalsat the Ikuno mine, Japan,
mainly afterMaruyama(1959).A marksindicatethe site of occurrence,plottedon planand in profile, respectively.

PAVONITEFROM THE IKUNO MINE" JAPAN

1325

geologicalcenterat the centerof the basin(Maruyama
Sulfur isotopic data for sulfide minerals from theL957, 1959).From top to bottom (and from margin to Ikuno minehavebeenreportedin the literature +1.4%ocenter),the zonesinclude:barren,Au-Ag,Pb-Zn,Za,(composite:Sasaki& Ishihara1980),+0.2 to +0.9%o
Cu-Zn, and Cu, with local developmentof Sn and (sphalerite:Miyoshi et al. 1.988),+0.3 to +L.Z%o
Sn-W in the central region. Pavonite occurs in the (chalcopyrite: Miyoshi et al. 1988) and.+03%ogroup,approximately (roquesite-bearing
Senju-honvein ofthe Kanagase
o1s; $himiru & Kato 1991).We
300 metersbelow sea level, within the Sn-W zone, have no data on fluid inclusions. but Shimizu &whereneitherAg nor Pb mineralshad previouslybeen Shikazono (1985) estimated the temperature offound. Here,in a well-developedquartzvein, lead-grey formation of the boundarybetweenthe Cu-Zn and Sn
minerals appear as visible but minute aggregates zonesto be 270to 260"C.on thebasisof iron andzinc
adjacent to quartz or chalcopyrite, their maximum partitioning betweensphaleriteand stannite.
dimensionbeing a few millimeters across.Unlike theassociatedbismuthinite, some grains are devoid of
Cmrurcal Aualvsps
cleavageand were finally identified as pavonite.
Ferberite, cassiterite, chalcopyrite, scheelite, native
Electron-microprobe analyses were made on
bismuth, pyrite, calcite and siderite are associated pavonite, the ootreasuritederivative" (Table 1),mineralsin the vein.
lismuthinite andnativebismuth.The latler werefound
Under the ore microscope, all aggregatesof to be nearlypureBirS, andBi, respectively.
pavonitehaveconcaveor linear outlinesagainstquartz,Pavonitecompositions
areall very closeto AgBirSr.
the maximumdimensionbeing millimetric @ig. 2), as heviously reportedcompositionshavesubstitutionsof
well as againstbismuthinite, which is optically very 2Pb for AgBi and 3Pb for 2Bi, and, turthermore,asimilar to pavonite, except for its slightly weak deficiency of S exists, according to Karup-Mgller
anisotropism and the absence of reflection (1972).An exampleof the latter substitutionis seeninpleochroism.We alsodetectedanothersulfosalt,which material from the Suttsu mine, Hokkaido, Japanis optically indistinguishablefrom pavonite. The (Shimizu et al. 1995), the empirical formula being
unknown sulfosalt includes minute cubes of pyrite, Ag1.s1(Bi2.ffi
Pbo.re)>:.oo(S:.srSe1.37Te6.66)25.ss, i.e., awhich serves to distinguish the two minerals. The selenium-bearingvariety. The results of the present
chemicaldataallowed us to identiff it as a "treasurite analysesdo include minor Cu, ranging from 0.32 toderivative",asdiscussed
below.
0.41 wt.Vo,the figure being fairly definite, despitethe

005 mmFtc. 2. Photomicrographsof pavonite (A) the "treasuritederivative" (B) from the Ikuno mine, J2p2n.A: concaveoutlines ofpavonite(pv) againstquartz,B: "feasurite derivative" (tr) containingcubesof pyrite (py).

1326

TIIE CANADIAN MINERALOGIST

X-Rev PownsR-Dnmecnou SlnYTABLE 1. REPRESENTATIVE CHEIT{ICAI, COMPOSIIIONS OF PAVOMTEAND TREASURIIE DERIVAII9E' FROM TI{E IKUNO MINE JAPAN3AS6FeIr[ocd11.140.()0.08
0.01120511.92
0.fi
0.04

1\11226

s0.t6
69t3
18.0J

10fi4
r79r

0.04
23JE
18.05
rc,8

19.6
50Jn,r9
50.90

16.4

16.66

Totd

9921

1m.0

9.6

92

PbAmic trllqt'@AsCu
F.
iiioCttPl
Bi

0.917
0.(F60.013
0.ml

s

5.m

0.07
29Jl

The X-ray powder pattem (Iable 2) is essentially
identical to that of higbly substitutedpavonite(KarupM4ller 1972). A critical comparisonreveals a veryslight contraction of a, which may be ascribed tothe influence of Cu substitutingfor Ag. The unit'cellparameterscalculatedfrom the indexed pattern are:ba€d @ S - 9 (tu D6db) @32(fodbeagib)
16,440.04

737

7TABLE 2 X-RAY POWDR-DIFFRACIION PATTBRN OF PAVONITTFROM TIIB IKUNO MINE JAPAN

0.04

3
50.03
'7.17
14.48
32'm

5.9
15.12
3zco

61532

(AgDi3SJ.
J@@ 2 C@losili@of itoalpedle
CohlI@ l:Pndreft@fren@oei@,
V@lrfi@ &e T@
dsivdirE ion &e h6 ni!e, Jst@ 4: :b@tE
3: Ttwits(Ag?PbsBssjr.
ni@, Colqa& (K6!D-Mona l9m. J: CooDGif@ of tdeal E€8erie

Il(A)

I

l&.

d*o.

hal0

16.401

406615d<ldl5
19164l
8.m
6161
5A53
5.361
4,39
4.084

ml
w2
2Nt2
85
1859
13
4
t4
t3

3.8t1
3,M
352E
3,463
3374
3.326
32f3
32tt
3.1E6

l&37
8.1i7
6,652
5.45E
5J6l
4.&
4.@4
4.074
3352
3.608
35?2
3,&
3376
3326
3n5
32t3
3.1t5

nsAX

il
10
J0

3.344
4.369
4.070

4090
l0lmmmn
4n
N
10I
10&lm

3.866
3SU
3J25
3.&3368
3323
3252
3214
3.tn
3.tA
3{ra2,Wl
LX2
2,817
2449

sm3@tn3!r0zM

M
close coexistencewith chalcopyrite,which is the only
400
m5
Cu mineral in the material examined. Upon close
30r
examination,all compositionshave a slight excessof
1 rr2
a 111
13$3
(Ag + Cu) after calculation using the basis S = 5,26
3.060
3.mE
?-9U
2.98
$0
whereasBi is slightly lower thanthe theoreticalfigure.
L963
zxt?lr
29rr
This suggeststhe existence of a substitution oft0
2301
2850
2"855lm3(Ag + Cu) for Bi provided that the relation S = 5 is1850
iz
162-759
L7&312\159
fixed. Thus. the material from the Ikuno mine is fito
€L7DL713
L1A
9p6
relatively pure, with.r = 0 in the formula proposedby m
25t2
2.92
2593
m2,x2
o2
2366
3t3
Karup-Mpller (1972); Fe as well as Pb appearonly in un
4A
2,488
o
L1A
L493
2,622M
10L4231lL462minor
substituentfor Bi.
face amounts:Sb is a2356
2.357
314
r02.35662339
2339
The chemical composition of other sulfosalts,
0p7r ta?
txa
116,46fi
224
distinguishedfrom pavoniteand bismuthiniteby their 40
22fr7
2212
l3!r646n
2.188
2.191
2-t&associationwith pyrite cubes, indicates a higher Pb 4A
2183
511
content.The stoichiomebyobtained,Agu.rPbrBi14.5S32,r0
2.ty
2.153
315
2.t49
d5t2
z.tLl
2.ul
40
Lr,omatches none of known sulfosalts, if critically 30<1zffi
316
2.019
2rt8
2M
2.047
m
2.Wl
considered. The closest analogue is treasurite, nLT]62"018w
Ag7Pb6Bi15$2(Makovicky & Karup-M@ller1977),
a1015
m
L0t2
\0r4
$3
from which the presentcompositionis derivedby the1.984
Nl,1l7
LW2
13
1983
316
1.966
ll
1366
t.!x2,
substitutionof Pb for Age.5Bie.5.
The material thus is l0
1.959
tn<l1953t.951,
M
heretentativelyreferredto as a "treasuritederivative".
1.918
t9r1
ra93
A3
1,92
l39m
JO
Also, it is worthy of notethat the chemicalcomposition r0gt
1,850
1.8J0
L&v
ooreasurite
1825
l.W
d!8of ourderivative" can be explainedby theg610
1.803
1J04ngn&
1.7/r
following reaction: 6.5AgBi3S5(pavonite) + TPbS m
t:7f391n6116
rJ6r
2440
1.76m
t0tJr/J-r("treasurite(galena) Ag6.5Pb7Biro.rSr,derivative')l:1321
rJ234m
IJTI4
It
1:t26+ 2.5BirS, (bismuthinite).However, no proof of the mt.T2l0t0421
reaction of galenawith pavonite could be found. The 10
1.769
lJV|
13$
t.6r3
dr.673$6compositional purity of the associatedbismuthinite
1.63
517
d1,63
1.648
t.63E1
1.648
may be interpretedto indicatethat the existenceof an 40r&1J63!r7gl
Ag-Bi sulfosalt exertsno compositionalinfluence on 10
ls@31-513
lj0t{1.4813
1.4E4426
1.483
it. But, if any Pb were presentin excess,a sipificant
modification of the phase to be produced may be LProi&fr@lbStlEB€lldhr,Colmdo(K@IFMdiq 1972). (hdq@mdod.
expected!o takeplace.
n fhod.
2 P6Mile t@ 6e I@ de, Jap& Cdi,{trsdld@ [tft&4@eldPAVOMIE FROM TIIE IKT'NO MINE. JAPANnn(1965):Sakuraiite,a new mineral.Geosci.Mag.,a 13.34(r),b 4.036(5),c 16.42(l)A, B 94.25(5)'.TheSakaraiVol., l-5 (in Japanese).
unit cell contains 4[AgBi3S5], giving the calculated
density 614 glcnf . Thesevalues are similar to those
Merovlcrv, E. & Kanup-Mou,rn,S. (1977):Chemistryand
obtainedby Makovickyet al. (1977).

..Etro_MnwBn',pavor.rrlE
Although studies of the synthetic products prove
AgBqS5 to be the ideal formula of pavonite, nonatural material had beenreportedto substantiatethis
composition. The compositions of pavonite in theliterature are derived from the above formula.
principally as a result oftwo kinds of substitutions,asstatedabove.The results presentedhere confirm thatthe term "end-membet''may truly be appligd to theformula AgBi3S5with respectto naturally occurringpavonite.
ACKNowmDGEN{ENTS

crystallography of the lillianite homologous series. I.
Generalpropertiesand definitions.NeucsJahrb. Mineral
Abh. 130.2tu287.

W.G. & Warrs, J.A. (1977):The crystal;l\4tnvnrrs,
structue of syntheticpavonite,AgBi3S5,and the definition of tle pavonitehomologousseries.Can Mineral. 15,339-348.
MARUvAMA,S. (1957): The relation betweenore veins andigneousintrusives.Mining Geol.7, 281-284(in Japanese).
(1959): Zonal distribution of ore deposit andprospectingat ttre Ikuno mine, Japan.J. Mining Metall.
Inst.Japan75, 673-677(in Japanese).
Mryosm,T., Naxavune, T. & Kusnrass, M. (1988):Sulfur
isotopic study of vein depositsin the Kinki district, Inner
Zone of southwest lapan. Mining Geol. 3E, 323-333(in Japanesewith English abstr.).

We thank Dr. Sadao Maruyama for helping thesecondauthorcollect the studiedmaterials"audthe late
Dr. Kin-ichi Sakurai,the original owner of the Sakurai NUFFIEI"D,E.W. (1954): Studies of mineral sulphosalts.
Mineral Collection,currentlyheld by National Science
XVI[. Pavonite, a new mineral. Atn. Mineral. 39,Museum,from which a part of the studiedmaterialwas
409415.
also included. We also thank Drs. Robert F. Marti&Alfonso G. Trudu, and two anonymousrefereesfor SAsAIa,A. & IsHu{ARA,S. (1980): Sulfur isotopecharacteristics of granitoids and related nineral deposits inincisive criticism and helpful suggestions.This study
Japaa.Proc. SthIAGOD Synp.1,325-335.
was partly supported by Ministry of Education,Science,Sportsand CultureofJapan (Nos.06302030(1991):Roquesite-bearingtin oresand 073040M) and the Japan Mining Promotive St*tzu, M. & Karo, A.
from the Omodani, Akenobe, Fukoku, and lkuno
Foundation.
polymetallic vein-type deposits in the Inner Zone ofsouthwestem
Japan.Can.Mineral. 29, 207-2I5.

RSFERENCFS
Harnrs, D.C. & Csnr, T.T. (1975):Studiesof type pavonire
material.Can.Mineral. 13. 408410.
KARrrp-MOu-;E&S. (1972)t New data on pavonite,gustavite,
and some related sulphosalt minerals. Neaes Jahrb.
Mineral. Abh. ll7. 19-38.
(1977): Mineralogy of some Ag-(Cu)-Pb-Bi
sulfideassociations.
BulL GeoI.Soc.Dmmark26.4l-68.
& Merovrcry, E. (1979): On pavonite,
cupropavonite, benjaminite and "oversubstituted"
gustavite.Bull. Minlral. L02,351,-367.

Scmrmr, S.Y., SraNrev, C.J. & Tsr,NoDA,K.
(1995): Kawazulite and unnamed Bir(Te,Se,S), in
Ag - Bi - Te - Se- S mineralizationfrom the Suttsumine,
Hokkaido, Japan,Neues Jahrb. Mineral. Abh. 169,305-308.
& Srm<azoNo,N. (1985):hon andzinc partitioning
between coexisting stannite and sphalerite: a possible
indicator of temperatureand sulfur fugacity. Mineral.
Deposita20,3l+320.
VerHoor, H.J. (1960): The ternary system
Ag2S-BirSr-PbS.Econ. Geol. 55, 759-788.

Karo, A. (1959): Ikunolite, a new bismuth mineral from theIkuno mine,Japan.Mineral.J.2,397407.
(1964): Pavonite from the Ikuno mine, Japan.
J. Mineral.Soc,Japan7,77 (abstr.inJapanese).

Received May 14, 1996, revised manuscript accepted
August 15,1996.