American Mineralogist, Volume 79, pages 750-762, 1994
New occurrencesand refined crystal chemistry of colusite, with
comparisonsto arsenosulYanite
Plrn
G. Spnv
Department of Geological and Atmospheric Sciences,253 ScienceI, Iowa State University, Ames, Iowa 50011-3210,U.S.A.
SrBr.lNo Mnm,rxo
Dipartimento di Scienzedella Terra, Universitd di Pisa, Via S. Maria 53, 56100 Pisa, Italy
Su WlNc*
Department of Geology, Arizona State University, Tempe, Arizona 85287-1404, U.S.A.
Xraovrlo ZuaNc**
Department of Geological and Atmospheric Sciences,253 ScienceI, Iowa State University, Ames, Iowa 50011-3210, U.S.A.
Psrrn R. Busncr
Departments of Geology and Chemistry, Arizona State University, Tempe, Arizona 85287-1404, U.S.A.
Ansrucr
Structural refinements of Sn-rich and Sn-poor colusite from the Lorano marble quarry,
Italy, revealed that the crystals are isometric and belong to spacegroup P43n. For Sn-rich
colusite, CuSoand (As,Sn)Sotetrahedraare connectedthrough corner sharingin a sphalerite
structure with the composition CuruSnrAsnS.r,
and two V atoms are stuffedinto interstitial
sites in a sulvanitelike arrangement.For Sn-poor colusite, CuSoand AsSotetrahedra are
connected in a similar arrangement through corner sharing in a sphalerite-like structure
with the composition CuroAsuS.r,with the two V atoms located in the same arrangement
as in Sn-rich colusite. The number of valence electronscontributed by metal atoms is 64
for Sn-rich and Sn-poor colusite, whereby the substitution of two Sn atoms with two As
atoms is balanced by two vacanciesin one of the Cu sites. Basedon structural and compositional considerations,a generalformula for colusite is Curn*"Vr(As,Sb)u
"(Sn,Ge),Srr,
wherex :0-2.
Selected-areaelectron diffraction (SAED) patterns and high-resolution transmission
electron microscopy (HRTEM) imaging of Sn-poor colusite with a composition of
CurrrVro(AsrrSbouFeo,)S,from the epithermal Gies gold-silver telluride deposit, Montana, revealed that it is composed of domains of ordered and disordered cations. The
ordereddomain has spacegroupP43n and a: 1.068nm and consistsofSn-poor colusite.
The disordered domain, with similar composition, has spacegroup F43m and a : 0.534
nm. Simulated imagesbasedon proposedstructural models produced an acceptablematch
to observedHRTEM images.One-dimensionalmodulations,with a wavelengthof 3.57
nm, are possibly responsiblefor the optical anisotropism and possibly for the anomalously
low Vickers hardness.
Another isometric sulfosalt, arsenosulvanite [Cur(As,V,Sb,Fe,Ge)So],with X-ray and
optical properties similar to colusite, has been introduced in the mineralogical literature.
The resultsof the presentstudy and a review of the literature on the chemical composition,
X-ray crystallography,and crystal chemistry of colusite and arsenosulvanitestrongly suggest the same identity for the two species.
1993), copper vein (Gazizova and Yarenskaya,1966),
porphyry molybdenumcopper(Strashimirov,1982),volColusite is an isometric copper vanadium sulfosalt that canogenicmassive sulfide (Bideaux, 1960; Matsukuma
forms in porphyry copper (e.g., Terziev, 1966; Springer, and Yui, 1979), and gold vein deposits (Kessler et al.,
1969; Kachalovskayaet al., 1975; Criddle and Stanley, l98l; Tourigny et al., 1993),as well as in marble (Orlandi
INrnooucrrox
I Present address:Arizona Materials Laboratory, University
ofArizona, 4715 E. Fort Lowell Road, Tucson, Airzona85712,
u.s.A.
0003-004x/94l0708-07
50$02.00
** Present address: Vijay Environmental Incorporated, 614
West Brown Deer Road, Suite 331, Milwaukee, Wisconsin53217,
U.S.A.
750
751
SPRY ET AL.: COLUSITE CRYSTAL CHEMISTRY
TABLE1. Chemicalanalysesof colusite
1.2.3.4
Cu
48.0
Vnd
Fe
nd
Ge
nd
Sn
6.9
As
6.8
sb
2.6
27.5
s
Total 94.8
Cu
Vnd
Fe
Ge
Sn
As
sb
s
46.9
nd
nd
nd
5.8
8.4
0.64
29.2
95.8
10
47.99
2.28
1.09
nd
6.71
9.54
0.19
30.65
99.71
28.182 25.933 25.281
nd
1.498
nd
nd
0.653
nd
nd
nd
2.170 1.718 1 894
3.386 3.939 4262
0.797 0 . 1 8 s 0 . 0 5 2
32.00032.000 32 000
50.8 49.5
50.1
3.2
3.0
3.3
nd
nd
nd
nd
nd
0.63
7.3
5.31
0.26
13.6
8.6
8.6
1.1
1.1
1.4
30.1 31.6
31.2
100.0 99.1 100.49
49.5 50.41 47.98 49.40
2.95
3.18
3.1
3.52
1.10
nd
0.58
0.35
4.52
1.1
2.85
0.14
nd
6.6
3.17
8.42
8.64
8.8
8.12
3.61
nd
6.59
0.34
0.92
30.2 29.69 29.77 33.13
too.22 98.69 101.06 101.24
11
48.5
2.7
nd
6.2
nd
10.0
nd
32.3
99.7
',t2
47.4
2.2
1.8
nd
7.6
7.5
1.4
31.2
99.3
13
14
15
49.3
2.7
nd
nd
5.9
12.1
nd
28.2
98.2
50.4
3.6
nd
nd
1.3
10.7
nd
31.9
97.9
49.5
3.05
1.5
nd
4.65
11.05
nd
30.55
100.30
Unit-cell content recalculated on the basis ot 32 S atoms
24 530 28.227 2 5 . 5 1 0 2 6 . 1 6 1
27.250 25.292 25927
26.464 27.414 26.022 24.075 24.2
2.011
1. 1 9 3 1. 7
1 420 1.928 2.273
2.141 1.912 2130
1.996
2.067 2.388
nd
nd
1.060 nd
0.902
nd
nd
0.194
nd
nd
0.359
0.679
nd
nd
nd
nd
1.931 2.7
nd
nd
0.067
0.286
0 515 1.358
1.317
nd
nd
2.107 1.810 0.353
2.098 1.454
2.447
0.072
1.891 0.924
4.953
1.661
3.571 4.2
3.292 5.876 4.593
3.727 3.727
5.969
3.990 3.745
nd
nd
nd
0.373 nd
nd
nd
1.661
0.087
0.293
0.378
0.257
32.000 32.000 32.000
32.000 32 000 32.000 32.000 32.000 32.000 32.000 32.000 32 000
A/ote.'columnnumbersare defined as follows: 1. Leonard mine, Butte, Montana (Landon and Mogilnor, 1933),also contains 3.0 wto/oTe; 2. Mountain
View mine, Butte, Montana (Landon and Mogilnor, 1933), also contains 0.4 wt% Te and 0.9 wt% Zn; 3. Butte, Montana (Berman and Gonyer, 1939),
a f s o c o n t a i n s ' l . 2 6 w t y o T e4; B u t t e , M o n t a n a ( L 6 v y1,9 6 7 ) ;5 . B u t t e , M o n t a n a ( S p r i n g e1r ,9 6 9 ) ;6 . a n d T . L o r a n o ,l t a l y ( O r l a n deit a 1 . ,1 9 8 1 ) ;8 . G a y
deposit, Russia (Pshenichnyyet al., 1974), also contains 0.35 wto/"Zn; 9. Kayragachdeposit, Uzbekistan(Spiridonovet al., 1984),also contains 0.07
wto/"Zn and 0.40 wt% Mo; 10. San Fernandodeposit, Cuba (Krapiva et al., 1986),also contains 0.04 wt% Ni, 0.33 wt% Zn, and 0.12 wt% Bi; 11. An
unnamedCu deposit,Kazakhstan(Mitryaevaet al., 1968); 12. Chizeuil,France(Delfouret al., 1984),also contains0.3 wt% Mo; 13. and 14. Bor
deposit, Serbia (Kachalovskayaet al., 1975); 15. Medet deposit, Bulgaria (Strashimirov,1982).
'Te derived from an intergrowth with tellurian tennantite.
first partial analysesbut not that obtained by Gross. Nelson
(1939) suggestedthat Gross'sanalysiswas not represenlative of colusite and should not be considered further. Berman and Gonyer (1939) first indicated that V is an essential component of colusite and proposed the formula
However, Livy (1967), through
Curr(As,Sn,V,Fe,Te)rSrr.
electron microprobe studies, explained the presenceof Te
in colusite from Butte as being due to impurities of a white
associatedmineral that has a compositioncorrespondingto
tellurian tennantite.krry's (1967) new and completeanalysis (Table l, analysis4) was confirmed by Springer(1969;
Table l, analysis5).
After its discovery at Butte, colusite was reported from
severalother localities, primarily copper sulfide deposits.
Table 1 showsthe chemicalcompositionsof colusitefrom
various localities; Cu, V, As, and S are essentialcomponents, whereas Sn, Sb, Fe, and Ge are often present in
significant quantities.
The first X-ray diffraction study of colusite wasby Zaunit cell
chariasen(1933),who proposeda face-centered
CHntvrrsrnv AND srRUcruRE oF colusrrE
(a : 0.5314 nm) and a sphalerite-typestructure. In a
Colusite was first noted as a probable new mineral by comprehensiveaccount of the troubled history of X-ray
Murdoch (1916)and wastermedbronzeenargite.However, crystallographicstudies of colusite, Dangel and Wuensch
the first publishedaccount ofcolusite was by Landon and (1970)pointedout that Bermanand Gonyer(1939)found
Mogilnor (1933),who presentedpartial analysesof samples that colusite had a lattice constant twice that reported by
from the konard and Mountain View mines from the Butte Zachariasen(1933). They also indicated that Murdoch
district, Montana (Table l, analysesI and 2, obtained by (1953) confirmed the larger cell, and that "many referencesassignspacegroup I43mto colusite." Their singlethe Geological Department of the Anaconda Copper Mining Company), and a new complete analysis obtained by S. crystal study corroborated the cell parameter of 1.0629
T. Gross, which gave results markedly different from the nm for colusite and proposed that it belongsto the space
precedingones. Subsequentstudiesby Berman and Gonyer gronpP43m.
(1939;Table I, analysis3) and Nelson(1939)confirmedthe
More recently, Orlandi et al. (1981), on the basis of
et al., l98l). It usually occursin minor or traceamounts
and coexists with a wide variety of sulfides (e.g., pyrite,
bornite, sphalerite, chalcopyrite, and galena), sulfosalts
(e.g., enargite,sulvanite, mawsonite, luzonite, tetrahedrite, and tennantite),and tellurides(e.g.,hessite).As a
result of similar X-ray and optical properties and chemical compositions,colusite may be confusedeasily with
another isometric copper sulfosalt, arsenosulvanite
In this paper,we review the lit[Cur(As,V,Sb,Fe,Ge)So].
erature on the chemical compositions and crystal chemistry ofcolusite and arsenosulvaniteto evaluatewhether
they can be unambiguously distinguished as two mineral
species.We presentcompositional,HRTEM, and SAED
studies of Sn-free colusite from the Gies gold-silver telluride deposit, Montana, in addition to new compositional data for colusite from marbles in the Carrara area
(Lorano and Calagio), Italy, and single-crystalstructural
refinementsof Sn-poor and Sn-rich colusite from Lorano.
752
TABLE2.
SPRY ET AL.: COLUSITE CRYSTAL CHEMISTRY
Experimentaldata for crystals of colusite from Lorano
Mineral
Space group
a (nm)
Unique reflections
F,"
Reflectionswith F. > 4o(F")
R
R*Iw : 1 llo{F.)l'.l
Sn-poor
colusite
(crystal1)
Sn-rich
colusite
(crystal 2)
P43n
1.0538(1
)
576
0.o47
467
0-059
0.048
P43n
1. 0 6 2 1 ( 1 )
590
0.051
434
0.055
0.043
systematic absencesobserved on precessionand Weissenberg photographs obtained from crystals of colusite
from the Lorano marble quarry, indicated P43n as the
correct spacegroup. Wuensch (personal communication
in Orlandi et al., 1981) independentlydetermined that
the weak reflections333,993, 77 3, and 555 (violatingthe
P43n symmetry) recognized by Dangel and Wuensch
(1970) were spuriousand that the correct spacegroup is
P43n. Orlandi et al. (1981) determinedcell edgesof a :
1.0538and 1.0621nm for Sn-poor and Sn-rich colusite
from Lorano, respectively.
The various choicesof spacegroup assignedto colusite
are understandable considering the peculiar diffraction
pattern characterizedby classesofreflections with strongly differing intensities. Short exposuretimes could result
in a full class of reflections being lost, with consequent
mistakesin the choice of the unit-cell parameter(0.530
nm, insteadof 1.060nm) and lattice centering.
Orlandi et al. (198l) also reviewed the literature on
colusite and, primarily on the basisof compositional data
and preliminary structural data, proposed that its unit
cell consistsof 66 atoms rather than the 64 atoms that
were assumedpreviously. They suggestedthat the ideal
chemical formula for colusite is CuruVr(As,Sn)uSrr,
implying fixed atom ratios for Cu:V:S of 26:2:32. Despite
the studies of Orlandi et al. (1981), the number of Cu
atoms in colusite from worldwide localities listed in Ta-
ble I (assuming32 S atoms)rangesfrom 22.471to 28.227
and does not agreewell with their proposed fixed value
of 26 Cu atoms. The Te-bearing colusite samples from
Butte (Table l, analysesl, 2, and 3) were excludedfrom
this range.If samplesof colusite from Bor (Table I , analysis l3 only) that contain anomalouslylow amounts of S
are also omitted, the range of Cu atoms in colusite is
24.015-27.414. Most compositions of colusite contain
between24 and 26 Cu atoms (Table l).
The crystal chemistry of colusite is revised and reassessedhere on the basis of structural studies carried out
on the two crystals from the Lorano quarry that were
originally studiedby Orlandi et al. (1981).The two crystals have different chemical compositions: crystal I is Snpoor colusite, and crystal 2 is Sn-rich colusite. The latter
has a composition more typical of colusite found elsewhere (Table l).
The intensity data were collected with a Philips PW
I100 single-crystalautomatic diffractometerat the following conditions: operating voltage and current of 48
kV and 28 mA (T: 298 K), MoKa radiation(I : 0.71069
A), a graphite crystal monochromator, a scan range (<o)
of 2-30", and a mode of ot-20.The absorptioncorrection
is derived from North et al. (1968).Unit-cell parameters,
reliability (R) factors, and other experimental data are
included in Table 2. The structure determination was first
carried out for crystal 2 (Sn-rich colusite), assuming a
sphalerite-like topology and distributing the metal atoms
according to the P43n spacegroup. However, the refinement failed becausethe R value did not fall below 0.20.
For our subsequentattempt, we assumedthat V atoms
were located in the structure in the same way as they are
in sulvanite(CurVSo),where the VSotetrahedrasharetheir
six edgeswith CuSotetrahedra, as found by Pauling and
Hultgren (1933) and discussedby Pauling (1965). A reliable model was obtained using this assumption, with
CuSnand (As,Sn)S"tetrahedra connectedthrough corner
sharing in a sphalerite-like scaffolding with the composition CuruSnrAsoS'and two V atoms in interstitial sites
in a sulvanite-likearrangement.
at 0,0,0, and t/z,t/z,t/z
TABLE3. Atomic positional coordinates, multiplicityfactors, and anisotropic displacementparameters in Sn-rich colusite (crystal 2)
from Lorano
Cu1
Cu2
Cu3
0.64As + 0.36Sn
S1
S2
0.0
0.0
0.2570
0.0001
0.2495
0.0002
0.25
0.0
0.25
0.0
0.1192
0.0002
0.3704
0.0002
0.0
0.0
0.0
0.0
0.2495
0.0002
0.0
0.0
0.5
0.0
0.1192
0.0002
0.3734
0.0002
0.0
0.0
0.0
0.0
0.2495
0.0002
0.5
0.0
0.0
0.0
0.1192
0.0002
0.1220
0.0002
0.089
0.0
0.5
0.0
0.333
0.0
0.25
0.0
0.25
0.0
0.333
0.0
1.0
0.0
u,.
U""
0.0096
0.0011
o.o124
0.0007
0.0264
0.0004
0.0112
0.0019
0.0173
0.0013
0.0186
0.0014
0.0140
0.0018
0.0096
0.0011
0.0152
0.001
0
0.0264
0.0004
0.0285
0.0012
0.0066
0.0006
0.0186
0.0014
0.0061
0.0015
Note: standard deviations are given in the second row for each atom.
u8
0.0096
0.0011
0.0257
0.0012
0.0264
0.0004
0.0285
0.0012
0.0066
0.0006
0.0186
0.0014
0.0207
0.0016
u4
urs
u,z
0.0
0.0
0.00s0
0.0015
0.0012
0.0005
0.0
0.0
0.0
0.0
-0.0015
0.0014
-0.0004
0.0013
0.0
0.0
0.0
0.0
0.0012
0.0005
0.0
0.0
0.0
0.0
-0.0015
0.0014
0.0001
0.0015
0.0
0.0
0.0
0.0
0.0012
0.0005
0.0
0.0
0.0
0.0
-0.0015
0.0014
-0.0020
0.0012
SPRY ET AL.: COLUSITE CRYSTAL CHEMISTRY
753
o
Fig. l The crystalstructure
of colusiteas seenalong[1I l].
Thefigurewasgenerated
usingtheprogramAtoms(Dowty,1990).
By refining this model, the R value dropped to 0.055
tor 434 reflections
with 4" > 4o(F")(refleclions
222,222,
and 440 were rejected as apparently affected by extinction), with R* : 0.043. In the last least-squares
cycles,
the occupancy factors of As and Sn in site 6c al th,t/2,0
were introduced among the refinement parameters.The
atomic parametersfor the refined model are presentedin
Table 3. The resultingformula is CuruVrAsoSnrSrr.
The
structure is representedin Figure I as seenalong I I l],
whereasFigure 2 presentsthe peculiar sulvanite-like arrangementaround the VS" tetrahedron.
A similar refinement was carried out with data collected from crystal I (Sn-poorcolusite),placingAs in site 6c,
aLt/t,t/2,0.
The refinementconvergedto R : 0.085 for 467
reflectionswith f'. > 4o(F (reflections222, 222, and 440
")
were rejected as apparently affectedby extinction). A differencein R valuesof 0.055 for the Sn-rich variety, compared with 0.085 for the Sn-poor variety, is difficult to
rationalize,consideringthat the low R value (0.055)was
obtainedfor the Sn-richvariety,which shouldpossess
the
higher structural disorder, with Sn and As distributed in
the same site. Furthermore, relatively high displacement parameter values were obtained for Cu2 in the
Sn-poorcolusite.
We refined the site-occupancyfactor (K) for Cu2 in Snpoor colusiteand obtained a value of K(Cu2) : 0.25 insteadofthe theoreticalvalue of Yr,correspondingto full
occupancyof the site. SinceK(Cul) : t/z and rK(Cu3):
Y+,the Cu contentin the unit cell of the Sn-poorcolusite
is 24 instead of 26. As a check,we also refined K(Cul)
and K(Cu3) in the Sn-poor colusite and K(Cul), K(Cu2\,
aroundthe VS4tetraheFig.2. The structuralarrangement
dron, with indicatedbond distances(nm) for V-S, Cu-S,and
V-Cu in Sn-richcolusite(top), Sn-poorcolusite(middle),and
usingthe program
sulvanite(bottom).The figurewasgenerated
Atoms(Dowty,1990).
and K(Cu3) in the Sn-rich colusite; however, all these
values remained essentially the same as the theoretical
values.
The final R value for Sn-poor colusite,with 24 Cu atoms in the unit cell, is R : 0.059 (R* : 0.048), which
compares satisfactorily with the R value of Sn-rich colusite (0.055).The atomic parametersfor Sn-poor colusite
are given in Table 4.
The ideal crystal-chemical formulae for the two varieties of colusite from Lorano are CuroVrAsuS' and
The total number of valenceelectrons
CuruVrSnrAsnS,r.
(ve) contributed by metal atoms is 64 for both formulae;
the substitution of the two Sn atoms (4 ve) for two As
atoms (5 ve) is balancedby two vacanciesin the Cu2 site.
The chemical data presentedby Orlandi et al. (198l)
do not indicate a content of 24 Cu atoms for Sn-poor
colusite (Table I, analysis6). It is possiblethat errors
were made in the determination of the chemical contents
becauseof unsuitable standards.Therefore, as an independent chemical check was necessary,three new colusite
specimens,two from Lorano and one from Calagio (also
in the Carrara area), were analyzed by electron microprobe. The results are given in Table 5, together with
analysesof colusite from the Gies gold-silver telluride
deposit, Montana. Analyses were obtained at the University of Modena (specimensfrom Lorano and Calagio)
and at Iowa State University (specimensfrom Gies), uti-
754
SPRY ET AL.: COLUSITE CRYSTAL CHEMISTRY
TABLE4. Atomic positional coordinates, multiplicityfactors, and anisotropic displacementparameters in Sn-poor colusite (crystal
1) from Lorano
0.0
0.0
0.2592
0.0001
0.2s13
0.0002
0.25
0.0
o.25
0.0
0.1209
0.0002
0.3655
0.0002
Cu1
Cu2
Cu3
As
S1
S2
0.0
0.0
0.0
0.0
0.2513
0.0002
0.0
0.0
0.5
0.0
0.1209
0.0002
o.3742
0.0002
0.0
0.0
0.0
0.0
0.2513
0.001
0.5
0.0
0.0
0.0
0.1209
0.0002
0.1208
0.0002
0.083
0.0
0.5
0.0
o.245
0.001
o.25
0.0
o.25
0.0
0.333
0.0
1.0
0.0
0.0079
0.0009
0.0136
0.0006
0.0194
0.0006
o.0262
0.0019
0.0064
0.0010
0.0088
0.0008
0.0286
0.0017
U."
u*
0.0079
0.0009
0.0228
0.0009
0.0194
0.0006
0.0269
0.0010
0.oo77
0.0006
0.0088
0.0008
0.0090
0.0015
0.0079
0.0009
0.0191
0.0009
0.0194
0.0006
0.0269
0.0010
o.0077
0.0006
0.0088
0.0008
0.0144
0.0012
U""
0.0
0.0
-0.0047
0.0011
0.0012
0.0005
0.0
0.0
0.0
0.0
-0.0004
0.0008
-0.0008
0.0009
U."
U.s
0.0
0.0
0.0
0.0
0.0012
0.0005
0.0
0.0
0.0
0.0
-0.0004
0.0008
-0.0065
0.0011
0.0
0.0
0.0
0.0
0.0012
0.0005
0.0
0.0
0.0
0.0
-0.0004
0.0008
0.0065
0.0011
Note.'standard deviations are given in the second row for each atom.
lizing ARL-SEMQ electron microprobes operating at l5
kV and a specimen current 0.20 p.A. Chalcopyrite (Cu
and S), synthetic stibnite (Sb), synthetic orpiment (As),
cassiterite(Sn),and metals (V and Ge) were usedfor standards at the University of Modena. The data were reduced using the program Magic 4 (Colby, 1968). Synthetic VrO, (V), synthetic AsrTe, (Te), Sn metal (Sn),
synthetic chalcocite (Cu and S), synthetic stibnite (Sb),
synthetic orpiment (As), synthetic pyrrhotite (Fe), and
synthetic sphalerite (Zn) were used as standardsat Iowa
StateUniversity. ZAF correctionsemployedthe PRSURP
program (Donovan et al., 1992).
The two samples from Lorano contain approximately
0.05 Sn atoms, wilh 24 Cu atoms in the unit cell, indicating the ideal crystal formula CuroVrAsuSrr.The Sn
content was higher in the sample from Calagio, with correspondingly higher Cu content (Table 5).
The geometrical features of the various tetrahedra in
Sn-poor and Sn-rich colusite are compared in Table 6.
Tlele 5. Analyticaldata on colusitesamplesfrom localitiesin
theCarraraarea,ltaly,andtheGiesdeposit,Montana
Lorano 1
(five
analyses)
Cu
Sn
Ge
As
Sb
S
Total
48.72
3.18
o.24
0.14
13.88
1.22
32.41
99.79
Lorano 2
(five
analyses)
Calagio
(four
analyses)
Gies'
(21
analyses)
Weightpercent
48.46
49.11
3.08
3.19
0.20
1.09
0.14
0.00
13.56
12.82
1.52
1.86
32.51
32.08
99.47
100.15
48.89
3,20
0.05
0.01
13.41
2.36
32.44
100.36
Unit-cell content recalculated on the basis of 32 S atoms
Cu
Sn
Ge
AS
Sb
q
24.27
1.98
0.06
0.06
5.87
o.32
32.00
24.07
1.91
0.05
0.06
5.71
0.39
32.00
. The sample
also contains 0.11 wtol" Fe
24.72
2.00
0.29
0.00
5.47
0.49
32.00
24.33
1.99
0.01
0.01
5.66
0.61
32.00
No significant differenceswere observed for corresponding tetrahedra apart from those containing (As,Sn)So,
which exhibit significantly longer metal-S distancesin the
Sn-rich variety. All tetrahedra are regular with S-metal-S
angles differing only slightly from the ideal tetrahedral
value of 109.47",except S1-Cu-Sl has the lowest value
in both varieties.It correspondsto the SI . . . SI edge,which
is significantly shortened,since it is shared between VSo
and CuSotetrahedra (Fig. 2). The peculiar arrangement
of V atoms stuffed into tetrahedral intersticesis shown in
Figure2, wherebond distancesV-Sl-' Cul-Sl, and V-Cul
in the two varieties of colusite from Lorano are given
along with those for sulvanite, in which the same structural arrangementoccurs.
The results of the structural studies suggesta general
with
formula for colusiteof Cu.o*,Vr(As,Sb)u-"(Sn,Ge),Srr,
x : 0-2. This formula cannot be tested with the analytTraw 6. Bond distances(nm) and angles("), with standard
in parentheses,
deviations
in the varioustetrahedra
for both varietiesof colusite
V - S 1( x 6 )
3 1 - V - S 1 "( x 6 )
C u 1 - S 1( x 2 )
C u l - S 2 b( x 2 )
S1-Cu1-S1"
S2o-Cu1-S2"
51 -Cu1-S2b( x 2)
5 1 - C u 1 - S 2 ' ( x2 )
Cu2-S1
Cu2-S2(x 3)
5 1 - C u 2 - S 2( x 3 )
S2-Cu2-S2d( x 3)
Cu3-S2" ( x 4)
S2d-Cu3-S2'( x 4)
S2d-Cu3-S2'( x 2)
(As,Sn)-S2( x 4)
S2-(As,Sn)-S2,( x 4)
(x 2)
S2-{As,Sn)-S2"
Sn-Doorcolusite
Sn-rich colusite
0.2207(2)
109.47(8)
0.2318(2)
0.231
6(2)
102.06(7)
113.82(7)
108.76(7)
111.41(71
0.238q3)
o.2240(3)
106.83(1
1)
111.9q12)
0.2311(21
108.70(7)
111.02(7)
o.2204(21
107.75(8)
112.97(8)
0.2193(2)
109.47(8)
0.2313(2)
0.2314(2)
101.47(8)
1't2.52(8)
't1o.12(7)
111.04(7)
0.2397(3)
0.2284(3)
108.36(1
1)
110.56(1
2)
0.2300(2)
108.94(8)
110.53(8)
0.2263(21
108.62(8)
111.19(8)
Notej symmetry codes for atoms in equivalentpositions are as follows:
a:x,-y,-zib:y2z,-lz+ y,y2- xic:V2- z,Vz- y,-y2+
x i d : y ,z , x i e : V " - - y , - V , + x i y 2 - z ; f : y , - 2 , 1 - x ; g : t 1 " x , Y 2+ z , * - , t n : x , 1 - y , - 2 .
755
SPRY ET AL.: COLUSITE CRYSTAL CHEMISTRY
TABLE7. Compositionaland structural data for some sulfides and sulfosalts with an interstitial metal atom in a tetrahedral site
Composition
lnterstitial
metal
atom
Cell edges (nm)
Space
group
MIS'
Reference
1/16
Orlandiet al. (1981);
this study
Kovalenkeret al. (1984)
Mandarino(1992)
Colusite
Cu.o*,V.(As,Sb)",(Sn,Ge),Ss,
Nekrasovite
Sb-dominant
member
Ge-dominant
member
Germanite
Cu,u(Cu,Fe,Zn)"(V,Fe),(Sn,As,Sb)653,
P43n
Cur6V2(Sb,Sn,As)6S3,
P43n
1. 0 6 2 1 1.0538
1.073
1.0705
Cur6vr(Ge,As)6S3,
P43n
1.0568
Cu26FeoGe4Ss2
P42n
1.0586
Cu
1/16
P42c
't.0622-
1.0551- Fe
1.045
1.0697
1/16
1/16
Fe
Cu
1/16
1t12
Renierite
Cu,o(Zn,,Cu,XGe.,,As,)Fes53,
P43n
V,Fe
1 1 1 6 Mandarino(1992)
1.060
1.0697
Vinciennite."
CurrFerSnrAsrS",
Tahakite
Stannoidite
Cu,.Fe,uS,u
Cur6(Fe,Zn)6Sn4S,4
l43m
f222
1.0593
1.0767
Mooihoekite
Mawsonite
Haycockite
Sulvanite
CunFe"S,u
Cu6FerSnSs
CuoFeuS"
Cu"VS,
P42m
P4m2
nr2.2r
P43m
1.0585
0.7603
1.0705
0.5391
1/16
1/16
0 . 5 4 1 1 1 . 6118
0.5383 Fe
0.5358 Fe
1.0734 3.1630 Fe
1t8
1t8
1t8
'v4
Tettenhorst and Corbat6
(1984)
Bemstein (1986);
Bernsteinet al. (1989)
Cesbron et al. (1985);
this study
Hall and Gabe (1972)
Kudoh and Takeuchi
(1s76)
Hall and Rowland (1973)
Szymanski(1976)
Rowland and Hall (1975)
Paulingand Hultgren
(1933);Troier(1966)
. M/S: number of interstitial metal
atoms per number of S atoms.
-* The structure has not
been resolved; a tetragonal lattice has been found (Cesbron et al., 1985).A new tormula is proposed by the present study.
ical data presentedin Table l. Some analyseswere carried out on impure material; however, further problems
arose when pure, or almost pure, material was used becausethe recalculation of the atomic contents(carried out
on the basisof 32 S atoms in the unit cell) may result in
relatively large errors in the number of Cu atoms if poor
determinations of S are obtained. Some of the recalculated Cu contents even appear unreliable on structural
grounds,having more than 26 Cu atoms. An unequivocal
test of this proposed formula must await a careful reexamination of compositions ranging from Sn-poor to Snrich varieties of colusite through electron microprobe
studies of specimensfrom the various localities, or of
additional samples,carried out in the same laboratory.
The structural analysis and chemical compositions
(Table l) indicate that colusite is characterizedby V atoms predominantlyin site 2a at 0,0,0 and As atoms preWhen other metals are
dominantly in site 6c at t/z,t/2,0.
dominant in the 6c site, new mineral speciesin the colusite group may be defined.All four possiblespecieshave
been reported. Apart from colusite sensustricto (As dominant), nekrasovite (the Sn-dominant analogue)has been
definedby Kovalenkeret al. ( I 984),and the Sb-dominant
and the Ge-dominant members were approved as new
Trele 8. Chemicalanalysesof arsenosulvanite
Gu
Fe
Ge
Sn
As
Sb
q
Total
Cu
Fe
Ge
Sn
AS
Sb
S
48.84
4.16
nd
nd
nd
12.80
nd
33.14
98.94
46.55
5.20
no
no
nd
11.67
nd
31.66
95.18
23.795
2.528
nd
no
no
5.289
nd
32.000
Unit-cell content calculated on the basis of 32 S atoms
23.791
24.856
25.343
24.976
3.380
2.351
2.289
2.124
nd
nd
ncl
nd
no
nd
nd
0.266
no
nd
no
nd
5.048
5.357
5.616
5.616
no
no
no
nd
32.000
32.000
32.000
32.000
48.8
3.7
no
no
nd
12.4
nd
31.7
99.96
50.6
3.4
nd
0.62
nd
't3.2
nd
32.22
100.04
50.35
3.7
nd
nd
nd
13.35
nd
32.55
99.95
46.2
3.1
3.4
nd
1.0
10.2
3.9
31.8
99.6
49.4
3.2
3r3.9
97.8
23.458
1.963
1.944
no
o.272
4.392
1.034
32.000
24.252
1.959
nd
nd
nd
5122
nd
32.000
nd
ncl
no
12.3
nd
Nofe.' column head numbers are defined as follows: 1. and 2. Mongolia, Kafan deposit (Mikheev, 1941); 3. Bor deposit, Serbia (Kachalovskayaet
al., 1975); 4. Bor deposit, Serbia (Cvetkovi6 and Karanovi6, 1993); 5. South Yakutia, Russia (Novikov et al., 1974); 6. Hayakawa deposit, Japan
(lshiyama et al., 1990); 7. Osarizawa deposit, Japan (Taguchiand Kizawa, 1973).The abbreviationnd : not determined.
756
SPRY ET AL.: COLUSITE CRYSTAL CHEMISTRY
Fig. 3. SAED patterns of Sn-freecolusite along (a) [l00], (b)
I I l], and (c) [2] l].
mineralsby the Commissionon New Minerals and Mineral Names of the International Mineralogical Association (Mandarino, 1992\.
Two other sulfosalts, germanite (CuruFenGeoSrr)
and
renierite [Curo(Zn, ,Cu,)(Geo ,As")FerS' where x : 02], are isostructuralwith colusite,and their structureswere
determined on the basis of the preliminary structural results presentedby Orlandi et al. (1981).Germanite,like
colusite, is cubic and has the same spacegroup P43n and
a : 1.0586nm. The structuraldifferencebetweencolusite
and germanite is that Cu atoms in the interstitial tetrahedral site 2a occur at 0,0,0 in germanite (Tettenhorst
and Corbat6, 1984).In renierite, the ordering of the metal
atoms in a colusite-type structure results in a reduction
of symmetry from cubic to tetragonal, with spacegroup
P42c and cell parametersa : 1.0623and c : 1.0551nm
(Bernsteinet al., 1989).The crystalchemistryand various
occurrences of renierite were discussed by Bernstein
(1986), and the chemical variability was explainedby him
as resulting from continuous solid solution between the
and CurrGerAsrFerS.r,
end-membersCuroZnrGeoFerS.,
through the coupled substitution of Zn2* + Ge5+ : Cu+
+ As5+.The end-memberCu,GerAsrFerS' was simply
referred to as arsenian renierite by Bernstein (1986).
It is likely that the mineral described by Matsukuma
and Yui (1979)as Ge- and Sn-bearingcolusiteis actually
arsenianrenierite.
Vinciennite,first found by Cesbronet al. (1985)in the
pyrite deposits of Chizeuil, Sadne-et-Loire(France),and
Huaron (Peru), and subsequentlyby Jambor and Owens
(1987) in the Maggie porphyry Cu deposit, British Columbia, appearsto be the stannian counterpart of arsenian renierite. This suggeststhe formula CurrSnrAsrFerS.,
as profor vinciennite, rather than CuroSnrAsrFerSrr,
posed by Cesbron et al. (1985). This new formulation
gives a better agreementwith the analytical data of Cesbron et al. (1985). The agreementbecomesperfectwith
the data presentedby Jambor and Owens (1987) for the
specimensfrom British Columbia. Moreover, the heterovalency of Fe, claimed by these authors to reconcile the
theoreticaland actualcompositions,is no longer necessary.
The mineral speciesdescribedabove are characterized
by the ratio M/S : l/16, whereM: number of interstitial atoms and S : number of S atoms. The same M/S
ratio is found also in talnakite (Hall and Gabe, 1972),for
spacegroup I43m witlr.a : 1.0593nm, that is isostructural with colusite. The structural arrangementof stuffing
a metal atom into a tetrahedral interstice is not confined
to the minerals of the colusite, germanite, or renierite
group becausemetal atoms are located in this position
for a variety ofsulfides, including sulvanite (Pauling and
Hultgren, 1933; Trojer, 1966), mooihoekite (Hall and
Rowland, 1973),talnakite (Hall and Gabe, 1972),rnawsonite(Szymanski,1976),stannoidite(Kudoh and Tak6uchi, 1976),and haycockite(Rowland and Hall, 1975).
Compositional and structural data for these minerals are
summarizedin Table 7.
Crrnursrnv
AND srRUcruRE oF
ARSENOSULVANITE
Arsenosulvanite is a rare copper, arsenic, vanadium
sulfosalt that was identified by Betekhtin (1941) and
Mikheev (1941) in quartz-calciteveins cutting bituminous limestone in Mongolia. Betekhtin suggesteda formula of Cur(As,V)So(Table 8, analysesI and 2), whereas
X-ray data of Mikheev suggestedthat it has a cubic cell
with a : 0.5257 nm, a P43m spacegroup, and a sphalerite-type structure. Arsenosulvanite was subsequently
described from the Bor porphyry copper deposit, Serbia
(Sclarand Drovenik, 1960; Ifuchalovskayaet al., 1975;
Cvetkovi6 and Karanovie, 1993), the Kafan Cu deposit,
SPRY ET AL.: COLUSITE CRYSTAL CHEMISTRY
Fig. 4. The I I I 1] HRTEM image of Sn-free colusite, showing domains correspondingto two sublattice reflections (cf. Fig. 3).
(a) An optical diffraction pattern ofan ordered domain (solid arrows); (b) an optical diffraction pattern from a disordered domain
(dashedarrows). The three dashedarrows point to disordered regionsthat appear to have reversedcontrast, which is presumably
the result ofa differencein thickness.
Armenia (Afanas'yeva et al., 1972), the Lebdynov Au
deposit in South Yakutia (Novikov et a1., 1974; Khoroshilova et al., 1984),the OsarizawaCu deposit,Japan
(Taguchiand Kizawa, 1973),and the HayakawaCu-PbZn deposit, Japan (Ishiyama et al., 1990). Despite the
descriptionsof arsenosulvanitefrom theselocalities,there
is still confusion concerning its chemistry and structure,
as well as its relationshipwith colusite.For example,the
available compositional data (Table 8) show striking similarities with those given in Table 5 for Sn-free colusite
from Lorano and Calagio(Italy) and Gies (Montana),with
a common ideal chemicalformula CurnVrAsuS.r.
The similarities between arsenosulvaniteand colusite
are strengthenedwhen one considersthat the large variety
ofproposalsfor spacegroups,cell dimensions,and structures for arsenosulvaniteclosely follows that already presentedfor colusite.Cell dimensionsof 0.5257 (spacegroup
P43m) and 0.5260nm weregivenby Mikheev(1941)for
arsenosulvanite from Mongolia and Osarizawa, respectively. However, a doubled parameterwas found by Khoroshilovaet al. ( I 984) (a : | .0527 nm, I43m) for arsenosulvanite from South Yakutia, as well as by
Kachalovskaya
et al. (1975)(a: 1.052nm, P43m) and
Cvetkovi6and Karanovi6 ( I 993) (a : 1.0552 nm, P43m)
for arsenosulvanitefrom Bor.
There is considerable evidence to suggestthe space
grotp P43n and a colusite-like structure for arsenosulvanite. The X-ray powder diffraction pattern obtained by
Cvetkovi6 and Karanovi6 (1993) is representativeofarsenosulvanitefrom Bor. (The powder pattern of Kachalovskayaet al., 1975,has weak reflections,0.313,0.243,
0. 1906, and 0.1627nm, which do not appearin the powder pattern ofCvetkovi6 and Karanovi6; thesereflections
correspond to strong reflections of sulvanite, which is
at Bor.) The powcommonly mixed with arsenosulvanite
der pattern of Cvetkovi6 and Karanovi6 (1993) matches
that of colusite I (Sn-freecolusite) presentedby Orlandi
et al. (1981), and no reflectionviolates the n-glide rule
(hhl presentonly for I : 2n). Moreover, we recalculated
the intensities assuming a colusite-type structure and
found good agreementwith the visually estimated intensities.In contrast,the intensitiescalculatedon the basis
of the sphalerite-type structure proposed by Cvetkovi6
and Karanovib (1993) show marked discrepancieswith
758
SPRY ET AL.: COLUSITE CRYSTAL CHEMISTRY
estimated intensities. For example, reflections 210,
200, and 420 should be unobserved,yet these peaks
are evident.
The evidence for a colusite-type structure for arsenosulvanite is supportedby the resultsof the structural study
of Khoroshilova et al. (1984). Their refinement,carried
out in spacegroup I43m (a -- 1.0527 nm), utilized reflections collectedwith an automatic diffractometer from
a single crystal of arsenosulvanite from South Yakutia
and assumedatoms are stuffed into tetrahedral interstices, as in colusite-typestructures.Khoroshilova et al. refined the structure to R : 0.07 I and obtained the crystal
The relatively low R value indiformula CuroVrAsuSrr.
catesthat the solution is closeto correct, notwithstanding
the following problems: (l) As atoms occupy the tetrahedral intersticesat 0,0,0; this appearsunusual for As (no
other exampleis known); (2) the occupancyfactor is 1.2
(higher than the theoretical 1.0) for As at 0,0,0; and (3)
As-S and (As,V)-Sdistancesare 0.230 nm, considerably
larger than the value of 0.220 nm for Sn-poor colusite.
In our opinion, these inconsistenciesderive from the assumption of I centering assumed,when weak reflections
+ I are disregarded.If data had
with h + k + l:2n
been collected assuming spacegroup P43n and a structural model ofcolusite had been used for the corresponding refinement, a lower R value would be obtained and
would be removed.
the inconsistencies
Optical studiesof colusiteand most examplesof arsenosulvanite suggestisotropic behavior in polarized light, which
is consistentwith colusiteand arsenosulvanitehaving isometric slnnmetry. Exceptionsinclude samplesof arsenosulvanite from the kbdynov (Novikov et al., 1974)and Bor
deposits(Kachalovskayaet al., 19751'Cvetkovi6 and Karanovi6, 1993),which exhibit distinct anisotropy.
Cn.c,RAc'rERrsrrcs oF colusrrE
Gms onposrr
Fig. 5. (a) A I00l SAED pattern of Sn-free colusite. (b) A
I I 00] SAED pattern of Sn-freecolusite tilted around the a* axis,
and (c) tilted around the b* axis.
FRoM THE
The epithermalGies depositconsistsof gold-silvertelluride veins that occur along the contact between Late
Cretaceousto Paleocenealkaline intrusive rocks (quartz
monzonite, syenite, and tinguaite porphyries) and sedimentary rocks (shale, sandstone, conglomerate, limestone. and dolomite) of Middle Cambrian to Late Paleoceneagein the Judith Mountains, Montana. Thirty-eight
minerals occur over four stagesof mineralization. Colusite occurs in stage III, which is dominated by qluartz,
gold-silver tellurides, and roscoelite.Fluid inclusion studies by Zhangand Spry 0991,1994) suggestthat stageIII
mineralizationformed between185 and 237 "C (average
: 220 "C) from a fluid containing between 6.6 and 7.9
equivalent wto/oNaCl. Colusite had previously been reported from the Judith Mountainsby Forrest(1971),who
identified it in the small Collar Gulch silver deposit, 4
km southwest of the Gies deposit. Unfortunately, no
compositional or optical data were given.
Anhedral colusite up to 1.5 mm in size is intergrown
with chalcopyrite, tetrahedrite, pyrite, hessite, enargite,
and chalcocite. It is intimately associatedwith tetrahe-
SPRY ET AL.: COLUSITE CRYSTAL CHEMISTRY
759
Defocus(nm)
55
60
Fig.6. A [211]HRTEM imageof Sn-free
colusite,showing
a modulation
in the[110]direction.
Thewavelength
of themodulationis 3.57nm.
drite, chalcopyrite, or pyrite. In reflected light, colusite
exhibits weak pleochroism (cream yellow to pale brownish yellow) and anomalous, moderate to strong anisotropy (dark blue to dark brown). These optical properties
are unusual becauseprevious publications suggestedthat
colusite showsisotropic behavior. Somegrains of colusite
from the Gies deposit appear to display twin lamellae.
Reflectancemeasurementsin air at a wavelength of 546
nm are 3l-33o/o,comparableto those for colusitefrom
Lorano (Orlandi et al., 198l), Gay (Pshenichnyyet al.,
1974), Medet (Strashimirov, 1982), and Kounrad (Gazizova and Yarenskaya, 1966).The rangeof microindentation hardness(Vickers hardness)is 183-207 kglmmr,
which is considerably lower than values reported for colusite from Lorano (342-350k9/mm2), Kayragach (260320 kglmm'z),and Gay (258-357 kglmmr) (Pshenichnyy
etal.,1974;Orlandiet al., 1981;Spiridonovet al., 1984).
Colusite from the Gies deposit is Sn-poor (up to 0.2 wto/o)
and contains l2.l-14.9 wtoloAs, 0.5-4.3 wto/oSb, and
3.1-3.3 wtoloV, and it compositionallyresemblescolusite
from the Lorano marble quarry Gable 5).
Snvrpln AND TEM
EXpERTMENTALDETArrs
Sample 89-G5 from the Gies deposit was polished to
a thicknessof 0.03 mm and then thinned using a Gatan
6008 ion mill. A cooling stagewas used to minimize
damage during milling. HRTEM experiments were conductedwith JEOL 2000F and 4000EX transmissionelectron microscopesusing an acceleratingpotential of 400
kV ficr high-resolutionimaging.
HRTEM AND SAED oBsERvATroNs
SAED patterns obtained along the [00], I l l], and
[2ll] axes of sample 89-G5 show a set of weak superstructure reflections in addition to strong sublattice reflections (Fig. 3). The correspondingHRTEM imagesindicate two types of domains (Fig. a). Optical diffraction
(a)
50
55
60
15
19
23
Thickness(nm)
(b)
Fig.7. SimulatedHRTEM imagesat differentvaluesof defocus
andthicknessfor the (a) orderedand (b) disorderedstructures.
patterns of these domains (insets in Fig. a) indicate that
only one of the domains displays the superstructurereflections. Therefore, the two setsofreflections are caused
by structural differences.Upon visual inspection, the energy-dispersivespectra show no obvious compositional
differences.The crystal system indicated by the superstructure reflections is isometric, with systematic absenceshhl with / : 2n + l, as observed by tilting the
specimen around the a* and b* axes (Fig. 5), which is
consistent with space gronp P43n or Pm3n. The lattice
parameter determined from electron diffraction is a :
760
SPRY ET AL.: COLUSITE CRYSTAL CHEMISTRY
a
Fig. 8. Comparison between the observed and simulated HRTEM images. (a) A tllll HRTEM image of Sn-free colusite,
togetherwith an image simulated at a thicknessof 35 nm and a defocusof 20 nm (inset). (b) A [1 I l] HRTEM image of a disordered
domain, simulated at a thickness of 20 nm and a defocus of 60 nm. (c) A tl00l HRTEM image of Sn-freecolusite, simulated at a
thicknessof 2l nm and a defocusof 20 nm.
1.068 nm. Theseobservationsare consistentwith those
obtainedby Orlandi et al. (1981:a: 1.053nm for Snpoor colusite). From the systematicabsencesof the main
reflections,hkl with h + k : 2n -r l, h + I : 2n + l,
and k + I : 2n + l, it follows that the spacegroup of
the disordereddomain is F432, F43m, or Fm3m, wtth
a : 0.534 nm. No known mineral correspondsto the
composition,latticeparameter,and possiblespacegroups
of the domain indicated by the main reflections.
One-dimensionalstructure modulations along [1 l0],
with a wavelengthof 3.57 nm, occur in [2ll] HRTEM
images(Fig. 6). The causeof the modulation is uncertain.
Equally uncertain is the cause for the anisotropism of
colusite in sample 89-G5. Although speculative,the
modulation might be responsiblefor its anisotropism (see
Jannerand Janssen,1977).
DrscussroN
HRTEM images for Sn-poor colusite from the Gies
deposit show that ordered and disordered domains are
coherently intergrown. The space group P43n is appropriate for the superstructure(colusite) domains, whereas
-F432 seemsconsistentwith the disordereddomains.
The EMS program of Stadelmann(1987)was usedfor
image simulations and showed ordered and disordered
structuresat different values offocus and specimenthickness(Fig. 7). Although both ordered and disordered domains have the same distribution of bright spots for
HRTEM imagesobservedalong I I l] (Fig. 5), they show
different contrast details. The contrast ofthe ordered domains varies strongly as a function of specimenthickness,
whereaschangesfor the disordereddomain are more sub-
tle. Simulated images clearly display contrast differences
betweenthe two types of domain (Figs. 7, 8a, and 8b).
The consistency between the observed and simulated
HRTEM images supports the supposition that two types
of domain occur in colusitefrom the Gies deposit (Fig.
8a and 8b). Both ordered and disordered structural models are idealized to be free of modulations.
The structures derived from the single-crystal X-ray
diffraction studies are consistent with the structure derived from HRTEM and SAED studies for the ordered
domain of the Gies colusite. A sphalerite-like arrangement, with a random distribution of Cu, As, V, Sb, and
Fe on the Zn sites of the sphalerite structure, was assumed by us as a model for the disordereddomains (facecenteredcubic cell, a : 0.534 nm). However, V in sulfides and sulfosalts shows a strong preference for the
arrangement presented in Figure 2, as in sulvanite
(Cu.VSo) and also around the V site in all members of
the colusite group.
Experimental studies on the system Cu.VSo-CurAsSo
(sulvanite-enargite)
by Riedel and Paterno (1976) identified an intermediatecompound,with a CurVSo:CurAsSo
molar ratio of l:3. The compound, Cu,rVAsrS,u,displayed a diffraction pattern similar to that of Sn-freecolusite (and arsenosulvanite).The powder pattern lines are
consistentwith a cubic cell (a: 1.0528 nm) and space
group P43n. Furthermore, the intensities of the powder
pattern lines agreewith those calculated from the coordinates in Table 2 for our Sn-poor colusite. The infrared
spectra presented by Riedel and Paterno (1976) for
Cu,rVAsrS,u,sulvanite, and enargite support that V is
incorporatedin Cu,rVAsrS,uin the way that it is in sul-
SPRY ET AL.: COLUSITE CRYSTAL CHEMISTRY
vanite. This supports our inferencethat the intermediate
compound is Sn-freecolusite.
For different molar ratios of CurVSoand CurAsSo,two
phaseswere obtainedby Riedel and Paterno(1976),one
correspondingto colusite and the other correspondingto
sulvanite or enargite,dependingon whether CurVSoor
CurAsSo exceeded the amount necessaryto form
Cu,rVAsrS,r. In our view, the resultsof Riedel and paterno's study not only point to the same structure for
Cu,rVAsrS,.as for the ordereddomain in sample89-G5
from the Gies deposit but also indicate, as stressedby the
authors, that no solid solution exists betweenthe endmembers.Solid solution is preventedby the tendencyof
the V atoms to occupyinterstitial positions.Therefore,it
seemsprobable that V is also located in interstitial sites
of the disordered domain observed in sample 89-G5.
WhereasV atoms are regularlydistributed on sitesat 0,0,0
(and equivalentsitesat Vz,Vz,Vz)
in the ordereddomain of
sample 89-G5, V atoms are randomly distributed over
all interstitial sites in the disordered domain, with a coordinated distribution of As and Cu over the normal tetrahedral positions so as to avoid adjacent VSo and AsSo
tetrahedra.With sucha random distribution of V atoms,
a structurewith a cubic unit cell of a : 0.534 nm and
spacegroup F43m is obtained.The resultsofRiedel and
Paterno's(1976) study are also pertinent to understanding the presenceof ordered and disordereddomains in
sample 89-G5. Although a speculativesuggestion,it is
likely that the disordered domain is the stable form at
high temperature. As temperature decreases,interstitial
V atoms distribute in a regular manner according to the
orderedcolusilestructure(P43n,a : 1.06nm)
76r
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Mx 24, 1993
M,q.NuscnrrrRECEIVED
Feorunv 18, 1994
M,o,u-rscrrrr ACCESTED