503
The Canadian Mineralogist
Vol. 46, pp. 503-514 (2008)
DOI : 10.3749/canmin.46.2.503

CUPROMAKOVICKYITE, Cu8Pb4Ag2Bi18S36, A NEW MINERAL SPECIESOF THE PAVONITE HOMOLOGOUS SERIESDan TOPA§ and Werner H. PAAR
Department of Materials Research & Physics, University of Salzburg, Hellbrunnerstr. 34, A–5020 Salzburg, Austria

Abstract
Cupromakovickyite, ideally Cu8Pb4Ag2Bi18S36, is a new mineral species that occurs at the skarn deposit of Băiţa Bihor,
Romania, and at the scheelite deposit Felbertal, Salzburg Province, Austria. The associated minerals are makovickyite, bismuthinite derivatives (aikinite–friedrichite range), hodrušite, kupčikite, padĕraite, emplectite, wittichenite and tetradymite (Băiţa
Bihor), and makovickyite, bismuthinite derivatives (aikinite–krupkaite range), hodrušite, kupčikite, wittichenite and native
bismuth (Felbertal). The opaque mineral is grey, has a metallic luster and is brittle without any discernable cleavage. The mean
micro-indentation hardness is 295 kg/mm2, corresponding to a Mohs hardness of 4. In reflected light, it is grayish white; thebireflectance is weak, and the anisotropy is moderate in air and strong in oil. Internal reflections are absent. The reflectancedata (air) are: 42.1, 48.5 at 470 nm, 41.0, 46.9 at 546 nm, 40.2, 45.8 at 589 nm and 39.6, 45.0% at 650 nm. The average resultsof five electron-microprobe analyses are: Cu 7.66(1), Ag 4.01(3), Pb 9.45(3), Bi 60.02(9), Se 0.30(1), Te 0.76(3), S 17.55(2),total 99.75(7) wt.%, corresponding to Cu7.79Ag2.4Pb2.95Bi18.55(Se0.24Te0.39S35.37)S36, calculated on the basis of S(S + Se + Te)= 36 atoms per formula unit. The simplified formula, Cu8Pb4Ag2Bi18S36, is in accordance with the empirical formula and that
deduced from the crystal-structure analysis. The density, 6.78 g/cm3, was calculated using the ideal (structural) formula and Z =1. Cupromakovickyite has a monoclinic cell with a 13.405(8), b 4.016(3), c 29.949(19) Å, b 99.989(16)°, V 1587.8(17) Å3, spacegroup C2/m, and Z = 1. The strongest lines in the calculated powder-diffraction pattern [d in Å(I)(hkl)] are: 3.478(100)(114),
2.842(94)(312), 3.646(57)(206), 3.486(41)(208), 3.345(33)(402), 2.964(33)(310), 2.282(31)(1110). Its c dimension is double thelength of the c dimension of makovickyite, the N = 4 member of the pavonite homologous series. Cupromakovickyite is closely
structurally related to makovickyite. The name of the new mineral expresses this relationship. Both the mineral and its namewere approved by the Commission on New Minerals and Mineral Names (IMA 2002–58).
Keywords: cupromakovickyite, sulfosalt, new mineral species, single-crystal X-ray diffraction, electron-microprobe analyses,
pavonite homologous series, Felbertal deposit, Austria, Băiţa Bihor skarn, Romania.

Sommaire
Nous décrivons la cupromakovickyite, de formule idéale Cu8Pb4Ag2Bi18S36, nouvelle espèce minérale trouvée dans le gisement de type skarn de Băiţa Bihor, en Roumanie, et le gisement de scheelite de Felbertal, Province de Salzburg, en Autriche. Luisont associés makovickyite, dérivés de bismuthinite (intervalle aikinite–friedrichite), hodrušite, kupčikite, paděraïte, emplectite,
wittichenite et tetradymite (Băiţa Bihor), et makovickyite, dérivés de bismuthinite (intervalle aikinite–krupkaïte), hodrušite,kupčikite, wittichenite et bismuth natif (Felbertal). Le minéral est opaque, gris, avec un éclat métallique, cassant, et apparemment
sans clivage. La dureté déterminée par micro-indentations est 295 kg/mm2, ce qui correspond à une dureté de Mohs de 4. En
lumière réfléchie, la cupromackovickyite est blanc grisâtre, la biréflectance est faible, et l’anisotropie est modérée dans l’air etforte dans l’huile. Aucune réflexion interne n’est évidente. Les données de réflectance, déterminées dans l’air, sont: 42.1, 48.5 à
470 nm, 41.0, 46.9 à 546 nm, 40.2, 45.8 à 589 nm et 39.6, 45.0% à 650 nm. Les résultats moyens de cinq analyses effectuées avec
une microsonde électronique sont: Cu 7.66(1), Ag 4.01(3), Pb 9.45(3), Bi 60.02(9), Se 0.30(1), Te 0.76(3), S 17.55(2), pour un
total de 99.75(7)% (poids), ce qui correspond à la formule Cu7.79Ag2.4Pb2.95Bi18.55(Se0.24Te0.39S35.37)S36, calculée sur une base deS(S + Se + Te) = 36 atomes par formule unitaire. La formule simplifiée, Cu8Pb4Ag2Bi18S36, concorde avec la formule empiriqueet celle qui découle de l’analyse structurale. La densité, 6.78 g/cm3, a été calculée en utilisant la formule structurale idéale et
Z = 1. La cupromakovickyite possède une maille élémentaire monoclinique ayant a 13.405(8), b 4.016(3), c 29.949(19) Å, b
99.989(16)°, V 1587.8(17) Å3, groupe spatial C2/m, et Z = 1. Les sept raies les plus intenses du spectre de diffraction sur poudre
calculé [d en Å(I)(hkl)] sont: 3.478(100)(114), 2.842(94)(312), 3.646(57)(206), 3.486(41)(208), 3.345(33)(402), 2.964(33)(310),
et 2.282(31)(1110). La dimension c est le double de la dimension c de la makovickyite, le membre de la série d’homologues de§E-mail address: dan.topa@sbg.ac.at

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la pavonite ayant N = 4. Le nom exprime le lien structural étroit avec la makovickyite. Le nouveau minéral et son nom ont reçul’approbation de la Commission des Nouveaux Minéraux et des Noms de Minéraux (IMA 2002–58).
(Traduit par la Rédaction)
Mots-clés: cupromakovickyite, sulfosel, nouvelle espèce minérale, diffraction X sur monocristal, analyses par microsonde électronique, série d’homologues de la pavonite, gisement de Felbertal, Autriche, skarn de Băiţa Bihor, Romanie.

Introduction
Several natural members of the pavonite homologous series, defined by Makovicky et al. (1977), arecomposed of exsolved lamellae (or lamellar intergrowths) of compounds respectively rich and poor in
Cu (and Pb). A detailed X-ray-diffraction study of apavonite-like material, with such a lamellar structure,
revealed the presence of two phases, pavonite andcupropavonite, chemically and structurally different.
Both phases have almost identical a and b parameters (13.4 and 4 Å, respectively), whereas the c axis
is doubled for the Cu- (and Pb)-rich phase, named
cupropavonite to denote its Cu content (Karup-Møller
& Makovicky 1979, Nuffield 1980). Analogous exsolution phenomena, which are interpreted as the resultof decomposition of a homogeneous high-temperaturephase, were observed for homologue N = 4, makovickyite (Žák et al. 1994, Mumme 1990) and homologue
N = 8, mummeite (Karup-Møller & Makovicky 1992).
Such exsolution-related pairs represent two mineral
species, separated by a definite miscibility-gap; consequently, the Cu- (and Pb)-rich varieties (for N = 4 and8) received the modifier “cuproplumbian”. However, no
information about the expected doubling of the c axis
was provided for either species.
During a systematic study of mineral specimens from Băiţa Bihor and Felbertal deposits, wehave found Cu-free and Cu-bearing makovickyite,lamellar intergrowths of makovickyite and “cupro­plumbian” makovickyite, as well as homogeneous
grains of “cuproplumbian” makovickyite. This led
to an exhaustive study of their chemical composition
and an intensive search for good-quality material on
which a crystal-structure investigation could be done.
In the present contribution, we provide the formal
mineralogical description of the new mineral species,
cupromakovickyite, the Cu- (and Pb)-rich phase(“cuproplumbian” makovickyite), whereas the discussion on the crystal structure of cupromakovickyite andmakovickyite and the nature of their relation is the
subject of a companion paper (Topa et al. 2008).

Provenance of the Samples
Cupromakovickyite has been detected in two genetically different ore deposits. At Băiţa Bihor, Apuseni
Mountains, Romania, it occurs in a skarn that was
created by the reaction of granitic magma (Cioflica &Vlad 1973, Žák et al. 1994) with Triassic dolomites.
Samples kindly provided by Dr. P. Kolesar (Kempten,
Germany) and by Prof. G. Cioflica (University of
Bucharest, Romania) were analyzed. Cupromako­
vickyite occurs as rare homogeneous grains and inaggregates that consist of a lamellar intergrowth withmakovickyite (Figs. 1a to d). The associated minerals
are bismuthinite derivatives in the range aikinite (bd83)– friedrichite (bd80), hodrušite, padĕraite, traces of
kupčikite, emplectite, wittichenite, tetradymite, andabundant chalcopyrite in a matrix of dolomite. The
Cu–Bi association appeared during the late stages ofthe skarn formation.
In the scheelite deposit of Felbertal, Hohe Tauern,
Austria, pavonite homologues with N = 4 (cupromakovickyite and makovickyite) are known only in the
orebodies K7 and K8 (Figs. 1e and f), whereas Cu-freemakovickyite and pavonite (N = 5) occur in orebodies
K1, K3 and K5 (Topa 2001, Topa et al. 2003b). The
minerals associated with cupromakovickyite arebismuthinite derivatives in the range aikinite (bd92) –krupkaite (bd56), hodrušite, cuprobismutite, kupčikite,
traces of wittichenite, native bismuth, chalcopyrite
and pyrrhotite in a matrix of quartz. This mineralization formed by the recrystallization of quartz veins
containing sulfides and sulfosalts and hosted within
felsic gneisses and amphibolites. Recrystallization
occurred during the retrograde stage of Alpine metamorphism (Topa et al. 2002).

Fig. 1. The association of sulfosalts with cupromakovickyite
from Băiţa Bihor (a–d) and Felbertal (e–f). BSE photographs; the scale bars represent 100 mm. a) Homogeneous
aggregate of cupromakovickyite. b) Homogeneous grain of
cupromakovickyite with locally exsolved lamellae (bright)of makovickyite. c) Intergrowth of lamellar cupromako­
vickyite (dark lamellae) and makovickyite (bright lamellae) in a matrix of aikinite (bd83) that is locally rimmed bykrupkaite (bd50); frame 1 and 2 denote the surfaces used forquantitative image-analysis. d) Detail of the lamellar intergrowth shown in c); the lamellae of makovickyite containsmall and oriented fractures and a second generation of
exsolved cupromakovickyite. e) Lamellar intergrowth ofcupromakovickyite–makovickyite similar to that shownin b–d. A homogeneous grain of cupromakovickyite andanother one of hammarite (bd72) border the lamellar aggregate. f) A four-phase aggregate composed of krupkaite(bd54), Cu-bearing makovickyite (4P), kupčikite (ku) andnative bismuth (bi).

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Physical Properties

Chemical Data

Cupromakovickyite from Băiţa Bihor and Felbertal
occurs as independent composite grains and as aconstituent of exsolution-induced intergrowths withmakovickyite. At Băiţa Bihor, the grain aggregates do
not exceed 0.3 mm, whereas at Felbertal, such grainsattain a size of 0.1 mm. Cupromakovickyite is opaqueand metallic, has a grey color and a grey streak. The
mineral is brittle, the fracture is uneven, and no cleavage
or partings were observed. The Vickers hardness wasdetermined using a Leitz Miniload 2 hardness testerwith a load of 50 g. The Vickers hardness number ranges
between 257 and 321 kg/mm2, mean 295 kg/mm2 (eight
indentations). This corresponds to a Mohs hardness of
4, quite similar to that of makovickyite. The density
could not be measured because no suitable grains wereavailable. The calculated density is 6.78 g/cm3, and isbased on the ideal formula and Z = 1.

Quantitative chemical data for cupromakovickyite
and the associated sulfosalts minerals were obtainedwith an electron microprobe (JEOL Superprobe
JXA–8600, controlled by LINK–eXL system, operated
at 25 kV and 35 nA, beam diameter 5 mm), installed at
the Department of Geography and Geology, Universityof Salzburg. The following standards (all synthetic
except galena) and emission lines were selected: Bi2S3(BiLa, SKa ), galena (PbLa), chalcopyrite (CuKa,
FeKa), Ag metal (AgLa), CdTe (CdLb, TeLa), andBi2Se3 (SeLa). The raw data were corrected with theon-line Zaf–4 procedure. The results of the electronmicroprobe analyses for Cu-free makovickyite andCu-free pavonite are compiled in Tables 2 and 3,
whereas compositional data for Cu-bearing makovickyite and cupromakovickyite are presented in Tables
4 and 5. Most analyses show the absence of iron andantimony, minor amounts of tellurium (usually below
1 wt.%) and selenium (usually around 0.3 wt.%), andthe systematic presence of cadmium (up to 3.2 wt.% in
Cu-free makovickyite, 4.4 wt.% in Cu-free pavonite andaround 1 wt.% in Cu-bearing makovickyite and cupromakovickyite). We assume that Cd and Fe substitute for
Pb, Sb for Bi, and Se and Te for S. The trace amountsof Cu in Cu-free makovickyite and pavonite (Tables
2, 3) are considered to substitute for Ag and allow us
to calculate the empirical formulae on the basis of thetotal number of atoms per formula unit (i.e., 32 formakovickyite and 36 for pavonite).
The empirical formulae of Cu-bearing makovicky­ite
and cupromakovickyite (Tables 4, 5) were calculatedon the basis of S + Se + Te = 18 atoms per formula
unit for makovickyite and S + Se + Te = 36 apfu
for cupromakovickyite, and lead to Cu 7.79 Ag 2.40
Pb2.95 Bi18.55 (S35.37 Se0.25Te0.39)S36 for Băiţa Bihor
material (anal. 1, Table 5), and Cu 7.93Ag2.43(Pb2.73
Cd0.43)S3.16Bi18.45(S35.95Te0.05)S36 for Felbertal material(anal. 5, Table 5), respectively.
The results, obtained from five aggregates in two
polished sections of the holotype specimens (Băiţa
Bihor and Felbertal material), show only minor variation of the chemical composition of cupromakovickyite(Table 5). On the basis of S = 36 and Me = 32 (fromthe single-crystal study), the ideal formula of cupromakovickyite for both occurrences can be written as
Cu8Ag2Pb4Bi18S36 and requires Cu 7.86, Ag 3.34, Pb
12.81, Bi 58.15, S 17.84, total 100.00 wt.%.
The analyses of exsolved lamellae (Tables 4, 5) weredone with a slightly defocused beam of electrons (~2–3mm) to avoid damage of the surface of the samples
and thus, problems in sulfur determination. The results
deviate from above-mentioned values, indicating clearlya mixture of the two components.
A combination of electron-microprobe data on
Cu-bearing makovickyite and homogeneous cupromakovickyite with quantitative image-analysis on selected

Optical Data
In polarized light, cupromakovickyite is greyish
white, without internal reflections. Bireflectance isperceptible in air and moderate in oil; pleochroism
is absent. Anisotropy is moderate in air and strong inoil. The rotation tints between crossed polars are dark
bluish grey to yellowish brown for the most anisotropic
grains. Reflectance data were obtained in air, usinga Leitz MPV–SP microscope photometer and WTiC
as standard. The observed Rmin and Rmax values are
summarized in Table 1 and plotted in Figure 2. Both the
Rmin and the Rmax curve are flat, with a weak maximum
at 440–470 nm coincident with that of homogeneous
Cu-bearing makovickyite from Felbertal.

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Fig. 2. Reflectance data (in air) for Cu-bearing makovickyite (open circles) from Felbertal
and cupromakovickyite (diamonds) from Băiţa Bihor.

areas (Fig. 1c, frame 1 and 2) was used to evaluate therange of original, pre-exsolution chemical compositionsof the high-temperature phase from which both minerals
exsolved (anal. 9 and 10, Table 5).
Chemical data for the Cu-free, Cu-bearing mako­
vicky­ite and cupromakovickyite (presented in Tables 2,
4 and 5) are plotted in the triangular diagram Bi – (Ag)
– (Pb + Cu) in Figure 3.
The chemical composition of kupčikite, hodrušiteand cuprobismutite is presented in detail in Topa et al.
(2003a, b), whereas bismuthinite derivatives are treatedin Topa et al. (2002).

X-Ray-Diffraction Data
Owing to the very small amount of pure cupromakovickyite material found, only a few single-crystal
fragments (~ 0.06 3 0.05 3 0.04 mm) were obtainedby dissolving the carbonate matrix. These were investigated only by single-crystal method. The X-raydiffraction data were aquired with a CCD-equipped
single-crystal diffractrometer (four-circle Bruker AXS
diffractometer). Cupromakovickyite is monoclinic,
space group C2/m, with a 13.396(9), b 4.013(3), c
29.93(2) Å, b 100.07(2), V 1584(3) Å3, Z = 1, witha structural formula Cu8Ag2Pb4Bi18S36. The unit-cellvolume of cupromakovickyite is equal to double theunit-cell volume of Cu-bearing makovickyite, which
has space group C2/m, a 13.239(3), b 4.0547(7), c

14.667(3) Å, b 100.07(2)°, V 776.7(3) Å3, Z = 1, witha structural formula Cu2.12Ag1.36Bi11.20S18.
The crystal-structure determinations presented in
a companion article (Topa et al. 2008) reveal thatthe doubling of the c parameter results from: (1) theoriented replacement of pairs of Bi pyramids by pairsof Pb–Bi pyramids (combined with the appearance ofa new tetrahedrally coordinated Cu site), and (2) the
replacement of the octahedrally coordinated Ag site bya tetrahedrally coordinated Cu site in the thin layers of
the cupromakovickyite.
Theoretical powder-diffraction patterns for cupromakovickyite (Table 6) and makovickyite were calculatedusing PowderCell 2.3 software (Kraus & Nolze 1999)
for a Debye–Scherrer configuration. They are plottedfor comparison in Figure 4. We used CuKa radiation(l 1.540598 Å), a fixed slit, no anomalous dispersion
correction and unit-cell parameters, space group, atom
positions, site occupancy and anisotropic displacement
factors from both single-crystal determinations of thestructures (Topa et al. 2008).

Discussion
The experience gained from numerous studies ofthe pavonite homologous series suggests an important
structural role for silver and copper. The ideal formulaof makovickyite unsubstituted by Pb or Cu (or both)(Žák et al. 1994, Makovicky et al. 1977) is Ag3Bi11S18

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Fig. 3. Chemical composition of cupromakovickyite, Cu-bearing and Cu-free makovickyite in the diagram Bi – Ag – (Pb+ Cd + Cu). Red line: Pb substitution, blue line: Cu and Pb substitution. The results of the image analysis: point 1 and 2.
Analytical data affected by intimate mixture of makovickyite and cupromakovickyite are denoted by a and b. Color-coded
symbols: open red diamond: ideal makovickyite; open brown diamond: Cu-free makovickyite (Felbertal); red diamond: ideal
cupromakovickyite; open lavender diamond: homogeneous makovickyite, Felbertal, K8; open green diamond: homogeneous
makovickyite, Feblertal, K7; open yellow diamond: exsolved lamellae, bright, makovickyite, Felbertal, K7; open blue diamond: exsolved lamellae, bright Băiţa Bihor; yellow diamond: exsolved lamellae, dark, cupromakovickyite, Felbertal, K7;
open black diamond: homogeneous cupromakovickyite, Băiţa Bihor; blue diamond: exsolved lamellae, dark, Băiţa Bihor;
turquoise diamonds mark a gap at Băiţa Bihor.

for Z = 1, or thin layer(Ag2Bi4) thick layer(AgBi7)S18, withsilver present in the separate octahedra of the thin layer
and in a single octahedron of the thick layer. The wellknown mechanism of substitution Ag+ + Bi3+ ! 2Pb2+
will introduce substitutional Pb into the thick layer(Table 2), leading to the substitutional trend presented
as the red line in Figure 3.
Copper was found (Žák et al. 1994, Mumme 1990)
in planar trigonal and tetrahedral coordinations, both
replacing the flattened octahedrally coordinated Ag siteof the thin layer. The combined influence of Cu-for-Agand (Cu + Pb)-for-Bi mechanisms of substitution ispresented as the blue line in Figure 3.

The formulae for the recognition of Np (estimationof homologue number) from results of the chemical
analyses, given by Karup-Møller & Makovicky (1979),
are based on the following assumptions: (1) the total Cu
recorded in the chemical data is assumed to representinterstitial iCu (Np1), (2) the total Cu is assumed torepresent substitutional sCu (Np2), and (3) the total Cu
is equally distributed between iCu and sCu (Np3). Thus,
the empirical formula for Cu-free makovickyite can becalculated (from electron-microprobe data) on the basisof total number of atoms (32) per formula unit, whereas
the same principle will not function for Cu-bearing
makovickyite, owing to the unknown percentage ofinterstitial Cu.

cupromakovickyite, a new member of the pavonite series

Fig. 4.

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Calculated X-ray-diffractometer patterns (CuKa) of makovickyite and cupromakovickyite for a 2u range of 6–45°.

The only way to calculate the empirical formula is
to base it on S cations = 18, for analytical datasets withgood charge-balance (ch and ev). Several authors (e.g.,
Žák et al. 1994, Karup-Møller & Makovicky 1992)
have emphasized the fact that the sum of cations in theformula does not have to be an integral number. For N= 4, the “fundamental” sites give Me14S18. The electronmicroprobe data indicate for Cu-bearing makovickyite(Table 4) a range from 14.32 to14.86 and 14.56 to 14.78
cations pfu, for Băiţa Bihor and Felbertal material,
respectively. Thus, the possible interstitial Cu ranges
between 0.32 and 0.86 cations pfu.
Cupromakovickyite has N p2 � 5 (meaningless,because from the single-crystal study, Np = 4) andNp3 � 4 (Table 5), with a clear indication that Cu isequally distributed between iCu and sCu, and has asum of anions equal to 32, in good agreement withthe results of the single-crystal study. An attempt canbe made to construct a simplified formula by applying
a partial 2Pb-for-(Ag + Bi) substitution to the excess
Ag and Bi. This gives a simplified model formula
Cu8Ag2Pb4Bi18S36 for both occurrences. On the one
hand, this formula is richer in lead than the analytical
data indicate; on the other hand, it shows that the highcontents of Cu in cupromakovickyite are caused by
the distribution of copper over more sites than the514

the canadian mineralogist“fundamental” ones that are universal for the entire
series of pavonite homologues.
In no case is the cupromakovickyite analyzed a purephase. Rather, it contains a certain proportion of themakovickyite phase, finely distributed as lamellae down
to few unit cells in thickness. It is for this reason that
the Pb content reported is lower than expected.

Mineral Name and Type Material
Cupromakovickyite is related to makovickyite inexactly the same way as cupropavonite is related topavonite (Karup-Moller & Makovicky 1979). In order
to articulate this relationship (we expect more such pairs
in the pavonite homologous series), we proposed a nameanalogous to cupropavonite. The prefix “cupro” also
expresses the primary chemical difference between thetwo species and replaces “cuproplumbian” as a modifier. Both the mineral and its name were approved by
the Commission on New Minerals and Names (IMA
2002–58). The holotype material is deposited underNo. 14943 and 14944 (two polished sections) in thereference collection (museum) of the Division of Mineralogy, University of Salzburg, Austria.

Acknowledgements
We gratefully acknowledge the financial supportof the Austrian Science Fund (FWF) research project
P17349–N10, which made possible this study througha grant to the senior author. We are grateful to Dr. Peter
Kolesar (Kempten, Germany) and to Prof. G. Cioflica(University of Bucharest, Romania) for supplying uswith old and new material from Băiţa Bihor, Romania,
for study purposes, and to Dipl. Ing. Dr. Peter Walser,
superintendent of the tungsten mine at Felbertal, forgiving us permission to sample prospective sulfosalt
sites. The manuscript benefitted from comments of N.
Mozgova and A. Pring, as well as from the editorial
care of Robert F. Martin.

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Received January 16, 2006, revised manuscript accepted
February 15, 2008.