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The Canadian Mineralogist
Vol. 40, pp. 849-869 (2002)

COMPOSITION RANGES AND EXSOLUTION PAIRS FOR THE MEMBERS
OF THE BISMUTHINITE–AIKINITE SERIES FROM FELBERTAL, AUSTRIADAN TOPA§
Mineralogical Institute, University of Salzburg, Hellbrunnerstrasse 34/III, A–5020 Salzburg, Austria

EMIL MAKOVICKY
Geological Institute, University of Copenhagen, Østervoldgade 10, DK–1350 Copenhagen K, Denmark

WERNER H. PAAR
Mineralogical Institute, University of Salzburg, Hellbrunnerstrasse 34/III, A–5020 Salzburg, Austria

ABSTRACT
A combination of electron-microprobe data, single-crystal X-ray diffractometry and BSE-based image analysis of polishedsections was used to evaluate the composition of single-phase grains, replacement aggregates and exsolution intergrowths of themembers of the bismuthinite–aikinite series from the scheelite deposit at Felbertal, Austria. Composition ranges of the classicalproducts and new members of the series have been established, and the mineral associations in products of replacement andexsolution defined. The deposit contains a nearly complete range of bismuthinite–aikinite derivatives, the proportion of theaikinite component in them ranging from 3 to 95%. Three independent events of sulfosalt replacement were recognized at
Felbertal, respectively yielding krupkaite, gladite and Cu-bearing bismuthinite as replacement products of the older bismuthinite–aikinite derivatives. Exsolution in the bismuthinite–aikinite series proceeds at each stage toward a pair of phases that arecompositionally closest to the parent phase, building up to three-stage exsolution-induced sequences not described before. Ample
documentation on these, as well as on all the measured compositions and crystallography of bismuthinite–aikinite derivatives,
form part of this paper. We attempt a geological interpretation of the observed spatial distribution of the observed phenomena
over the scale of the deposit.
Keywords: bismuthinite–aikinite derivatives, composition ranges, exsolution, replacement, miscibility gaps, scheelite deposit,
Felbertal, Austria.

SOMMAIRE
Nous utilisons une combinaison de données sur la composition, obtenues avec une microsonde électronique, de données
diffractométriques obtenues sur cristaux uniques, et une analyse d’images de sections polies obtenues par électrons rétrodiffusés,
pour évaluer la composition de grains homogènes, d’aggrégats dus au remplacement, et de domaines en intercroissance dus àl’exsolution de membres de la série bismuthinite–aikinite dans le gisement de scheelite à Felbertal, en Autriche. Les compositions
comprennent les produits classiques et de nouveaux membres des séries, et les associations de minéraux dans les produits deremplacement et d’exsolution sont définis. Le gisement contient une gamme presque complète de dérivés de la série bismuthinite–aikinite, la proportion du pôle aikinite allant de 3 à 95%. Trois événements indépendants de remplacement des sulfosels ont eu
lieu à Felbertal, menant à la formation de krupkaïte, gladite et bismuthinite cuprifère, respectivement, comme produits deremplacement des dérivés de la série bismuthinite–aikinite antérieurs. L’exsolution dans la série bismuthinite–aikinite a procédé
à chaque étape vers une paire de phases qui se rapprochent le plus possible du précurseur, menant à jusqu’à trois séquences duesà l’exsolution non identifiées auparavant. Nous fournissons une riche documentation sur ces produits, de même que sur toutes lescompositions mesurées et sur les aspects cristallographiques des dérivés de la série bismuthinite–aikinite. Nous proposons unereconstruction géologique de la distribution des assemblages dans l’espace à l’échelle du gisement.
(Traduit par la Rédaction)
Mots-clés: dérivés de bismuthinite–aikinite, intervalles de composition, exsolution, remplacement, lacunes de miscibilité, gisement
de scheelite, Felbertal, Autriche.

§

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THE CANADIAN MINERALOGISTINTRODUCTION
The treatment of the ordered derivatives of thebismuthinite–aikinite solid-solution series, CuxPbxBi2–x
S3 (0 ≤ x ≤ 1), seemed to be complete following the classical works of Ohmasa & Nowacki (1970a, b), Kohatsu& Wuensch (1971, 1976), Syneček & Hybler (1974),
Mumme (1975), Horiuchi & Wuensch (1976, 1977),
Mumme & Watts (1976), Mumme et al. (1976), and Žák
(1980). Makovicky & Makovicky (1978) proposed tocharacterize these structures as members of the solidsolution series aikinite (x) – bismuthinite (100–x) or, ina short form, by naik, corresponding to the percentage of
the CuPbBiS3 end-member in the Bi2S3–CuPbBiS3
series. The generally accepted scheme has involved
three compositions, Bi 2S 3 (naik = 0, bismuthinite),
Cu0.5Pb0.5Bi1.5S3 (naik = 50, krupkaite), and CuPbBiS3(naik = 100, aikinite), which have simple orthorhombic
structures with “11  11  4 Å unit cells” (i.e., 1b cell)and only one type of structural ribbons (Bi 4 S 6 ,CuPbBi3S6 and Cu2Pb2Bi2S 6, respectively) in eachstructure. These three compositions are interleaved withadditional ordered structures in which ribbons of two
different types combine (idealized formulae given):
CuPbBi11S18 (pekoite, naik = 16.67), CuPbBi5S9 (gladite,naik = 33.33), Cu2Pb2Bi4S9 (hammarite, naik = 66.67),
Cu5Pb5Bi7S18 (friedrichite, naik = 83.33), all these being
3b supercells, and Cu3Pb3Bi7S15 (lindströmite, naik =60.0), the only phase with a 5b supercell.
In recent years, attention shifted to the compositional
ranges of these ordered structures (e.g., Harris & Chen
1976, Makovicky & Makovicky 1978, Pring 1989,
Mozgova et al. 1990), syntheses of disordered intermediate compositions (Springer 1971, Mumme & Watts
1976), and the first annealing experiments to achieveorder (Pring 1989, 1995).
New material from the metamorphosed scheelite
deposit of Felbertal, Austria (Thalhammer et al. 1989),
has substantially altered this well-established scheme.
Besides yielding rich information on the compositional
ranges of the established phases, it yielded, in the formof independent grains and as lamellae in exsolution
pairs, three new members of the bismuthinite–aikinite
series; two of these (salzburgite, Cu6.4Pb6.4Bi25.6S48, naik
= 40, and emilite, Cu10.7Pb10.7Bi21.3S48, naik = 67.5) havenovel, 4b supercells structures, and the other (paarite,
Cu8.5Pb8.5Bi31.5S60, naik = 42.5) is a 5b supercell structure. The crystal-structure determinations and mineralogical descriptions of these phases are being publishedelsewhere (Topa et al. 2000, Balić- Žunić et al. 2002,
Makovicky et al. 2001).
In the present contribution, concise background information about the Felbertal deposit is given, followed
by a review of single, unexsolved phases and their associations. Exsolution phenomena are then treated in theorder of increasing complexity: simple exsolution pairs,
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discussion, an interpretation of the observed phenomena in terms of stability and compositions of individual
derivatives of bismuthinite (abbreviated as bd below)
and their bearing on the conditions of formation andhistory of the Felbertal deposit is outlined. Only a partof extensive chemical data that form the basis of thisstudy is published in Tables 1 and 2. Tables 3 (complete single-phase compositions), 4 (complete replacement associations), and 5 (complete exsolution
assemblages) were deposited and may be obtained fromthe Depository of Unpublished Data, CISTI, National
Research Council, Ottawa, Ontario K1A 0S2, Canada.

EXPERIMENTAL
Chemical composition
Chemical analyses were performed at the Mineralogical Institute, University of Salzburg, using a JEOL
JXA–8600 electron microprobe, controlled by a LINK–eXL system, operated at 25 kV, and 30 nA, 20 s counting time for peaks and 7 s for background. Under these
conditions, the expected diameter of the beam, ~0.5 m,
was slightly defocused (to ~2 m) to prevent damage tothe sample. The expected spatial resolution for the matrix of bismuthinite derivatives ( ~7 g cm–3 ) is ~3 m.
The following natural (n) and synthetic (s) standards and
X-ray lines were used: n-CuFeS 2 (CuK, FeK),s-Bi2S3 (BiL, SK), n-PbS (PbL), s-CdTe (CdL,TeL), n-Sb2S3 (SbL) and pure metal for AgL. The
raw data were corrected with the on-line ZAF–4 procedure. Standard deviations (error in wt.%) of elementssought for the matrix of bismuthinite derivatives (in thegladite–krupkaite range) are: Bi 0.17, Pb 0.1, Cu andSb 0.03, Fe 0.01 and S 0.06%. The other elements are
below 3 detection limit: Ag 0.07, Te 0.08 and Cd 0.17
wt.%. Results of three to five point-analyses obtained
from a homogeneous grain or individual exsolved phasewere averaged. These mean compositions are compiledin Tables 1 and 2 and used in Figures 2 to 13. Somegrains contain traces of Sb (less than 0.3 wt.%), andothers, traces of Fe (less than 0.12 wt.%). Empiricalformulae CuxPbyBi8–½(x + y)S12 (x = y for ideal compositions) were calculated for all grains and exsolution
lamellae on the basis (Cu + Pb)/2 + Bi = 8 atoms per
formula unit, apfu, after Makovicky & Makovicky(1978). The position of these phases in the bismuthinite–aikinite series is described by the hypothetical percentage of the aikinite end-member naik =25(x + y)/2. The
value of naik = ±12.5(y – x) is used to express the accuracy of the analytical data.
BSE imaging and image analysis
Valuable information was obtained on compositional
differences of bismuthinite derivatives and associatedphases by using back-scattered electron (BSE) signals.
The contrast in BSE images is related to the mean

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atomic number zm of a compound, defined as ( cizi)/
100, where ci and zi are concentrations in wt.% andatomic numbers for Cu, Pb, Bi and S, in case of abismuthinite derivatives. The resolution of a modern
BSE detector with respect to atomic numbers is less thanzm = 0.1. Bismuthinite derivatives, in the bismuthinite–aikinite range, have mean atomic numbers ranging from 70.47 for Bi2S3 to 65.49 for CuPbBiS3. Any
two phases in that range, separated by a 2% differencein the naik value, will have slightly different mean atomic
numbers [zm > 0.1], and consequently can be imaged.
BSE images with 200- to 1000-fold magnifications
were acquired digitally in Slow Kalman mode (about
15 frames for each image in order to obtain noise reduction) at 25 kV accelerating voltage and 10 nA beam
current under control of the LINK–eXL software. A typical BSE image of exsolution lamellae of bismuthinite
derivatives shows two or more phases (with differentzm) with different levels of grey (the brighter phase contains less Cu and Pb than the darker phase).
A LINK Image Phase Analysis package was used to
calculate the relative area of phases present in each image based on the distribution of pixel intensities (1024 1024 pixels). The area percentage and compositionof each phase are used to estimate the initial composition of exsolved grains.
Single-crystal X-ray diffraction
The chemical analyses were supplemented bysingle-crystal X-ray diffraction of all suitable singlephase grains extracted from the quartz matrix using HF
and mechanical means. Only the grains exactly characterized by electron-microprobe analyses were used.
The crystal fragments, with irregular shapes and <0.1
mm in diameter, were measured on a Bruker AXS fourcircle diffractometer equipped with CCD 1000K area
detector (6.25  6.25 cm active detection area, 512 
512 pixels) and a flat graphite monochromator using
MoK radiation from a fine-focus sealed X-ray tube.
The sample–detector distance was generally 6 cm, but agreater distance was used for the cases with large
superperiods. For some fragments, complete determination of the crystal structure was performed (to be reported elsewhere), resulting in data on the unit cell andspace group; in cases of less suitable material, only thesuperstructure periodicity was determined. These data,
supplemented by a small amount of data on bd fromother localities (Zirknitzstollen and Sedl, Tauern Window, Austria; Báiţ a Bihor, Romania; Outlaw mine,
Nevada, U.S.A.) are summarized in Table 1 and givethe most complete picture of bd mineralogy to date. The
SMART system of programs was used for unit-cell determination and data collection, SAINT+ for the calculation of integrated intensities, and SHELXTL for the
structure solution and refinement (all Bruker AXS products).

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GEOLOGY AND MINERALOGY OF FELBERTALThe Felbertal scheelite deposit is one of the largest
tungsten mines in operation. The deposit has produced
more than 7  106 t of ore. Its current production is 4 
105 t/yr at an ore grade of 0.5% WO3. The scheelite ore
is hosted by a Cambro-Ordovician volcanic arc sequence (metabasalts, metagabbros and orthogneisses)
and Variscan granites (Fig. 1). The latter belong to an
early episode (340 Ma) of a multi-stage cycle ofVariscan magmatic activity (Eichhorn et al. 2000). Economically significant scheelite orebodies are assumed
to be genetically associated with the Variscan K1–K3
granitic plutons (Raith et al. 2001).
The deposit consists of two parts, denoted locally as
ore fields; it is situated within a sequence up to 400 m
thick that is considered to represent stacked nappes(Ebner et al. 2000). The Western Ore Field comprises
two ore-bearing wedges separated by barren paragneiss
and micaschist (Fig. 1). Several distinct orebodies (K1–
K8) of this field are mined underground. The orebodies
dip steeply (on average at 45° in the SSE–NNW profile), each of them spanning a range of absolute heights
above the sea level. The Westfeld profile (Fig. 1b) isperpendicular to this dip. The Eastern Ore Field wasmined by open-pit methods and is abandoned now.
Three different generations of scheelite are distinguished (Höll 1975). The first two represent yellowishfluorescent Mo-bearing scheelite, whereas the third is aremobilized bluish-fluorescent scheelite. Scheelite may
be associated with beryl, phenakite and chrysoberyl,fluorite, as well as with a variety of sulfides andsulfosalts. The dominant sulfides are pyrrhotite, pyrite,
chalcopyrite (± stannite, sphalerite), and intermediate
members of the molybdenite–tungstenite solid solution(from WS2 to W0.9Mo0.1S2). These occur as finely dispersed flakes in the generations of greyish scheelite andas local concentrations within the orebodies. Traceamounts of arsenopyrite, pentlandite, marcasite, cobaltite, enargite, tennantite–tetrahedrite, stibnite, galena,cassiterite, columbite and ferberite are present as well
(Höll 1975).
The sulfosalt accumulations occur as (1) lens-shaped
massive accumulations in bodies of quartz, (2) fine layers in laminated and discordant quartz veins in amphibolites, and (3) irregular distributions in quartz stringers
and veinlets of the scheelite ore. There is an abundanceof galenobismutite, cosalite, bismuthinite derivatives,
members of the lillianite, pavonite, junoite andcuprobismutite homologous series, cannizzarite,
eclarite, as well as tetradymite, joséite-B, hessite andnative bismuth. Small amounts of microscopic native
gold may accompany the sulfosalts.
Both syngenetic and epigenetic models have been
proposed for the genesis of this deposit. The concepts
range from sedimentary-exhalative processes for thetungsten enrichment (Eichhorn et al. 1999) to epigenetic

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granite-related models (Briegleb 1991). Recent Re–Os
dating of molybdenite associated with scheelite andsulfosalts from the K1 and K2 orebodies revealed a mainore-forming event at 340–345 Ma (Raith et al. 2001),
suggesting its genetic link with the early Carboniferous
magmatic activity. On the basis of textural relationships,
the sulfosalt mineralization postdates the crystallizationof molybdenite and is also considered a result of thepolyphase Variscan magmatic events. Subsequently, theentire mass of rock and ore was subjected to the Alpine
prograde metamorphism of the upper greenschist tolower amphibolite facies (500–590°C and 4.5–7 kbar;
Eichhorn 1995), followed by retrograde recrystallization.

SINGLE PHASES
In most cases, bismuthinite derivatives (bd) in theFelbertal deposit form sulfosalt grains in a quartz
gangue; usually these are intergrowths of two or more
sulfosalts. Besides one or two distinct bd (homogeneousor exsolved), the aggregates may contain a member of853

the lillianite homologous series (lillianite–gustavite
solid solution, vikingite, heyrovskyite), a member of thepavonite homologous series (makovickyite, pavonite),junoite, felbertalite (Topa et al. 2001), cannizzarite or amember of the cuprobismutite homologous series[cuprobismutite, hodrushite, kupčíkite Cu3.4Fe0.6Bi5S10(Topa et al. in prep.)], in addition to some later products of decomposition (especially native Bi).
The total amount of empirical data on single-phasebd from Felbertal (Table 3, deposited) yields a quasicontinuous series of compositions with only two obvious compositional gaps, between pekoite (bd18) andgladite (bd33) and between krupkaite (bd47) and themembers with naik < 43, respectively (Fig. 2). Neither
the ideal aikinite, CuPbBiS3, nor the ideal bismuthinite,
Bi2S3, are reached, the respective limits found being naik
= 95 and naik = 3.
As indicated in Table 1, bismuthinite (1-fold structure), gladite (3-fold superstructure), krupkaite (1-foldstructure), hammarite (3-fold superstructure) andaikinite (1-fold structure) show appreciable compositional ranges. Salzburgite (4-fold superstructure),

FIG. 1. a) Schematic geological map of the central part of the Tauern Window (the Eastern Alps), with the position of theFelbertal ore fields indicated. b) Simplified geological profiles of the western and eastern parts of the Felbertal ore fields.

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FIG. 2. Empirical compositions of bismuthinite derivatives from Felbertal, with the ideal compositions of known minerals andnew, crystallographically characterized phases (salzburgite, paarite and emilite). Molar percentages as indicated.
Abbreviations used throughout the text: bs: bismuthinite, pe: pekoite, gl: gladite, sa: salzburgite, pa: paarite, kr: krupkaite, li:lindströmite, em: emilite, ha: hammarite, fr: friedrichite, ai: aikinite, and bdnaik: bismuthinite derivatives with the percentageof aikinite end-member equal to naik.

friedrichite (3-fold superstructure) as well as the newphases paarite (5-fold superstructure) and emilite (4-foldsuperstructure) have narrow compositions and also narrow compositional gaps with respect to the adjacent,crystallographically distinct phases. The width of thelindströmite and pekoite fields is less certain because
both appear to be analytically inseparable components
of nearly submicroscopic exsolution-induced intergrowths, respectively, with krupkaite and bismuthinite.

REPLACEMENT PAIRS
Ore textures of a number of small aggregates of
sulfosalts enclosed in quartz (or sulfides) indicate that
not all bd (and not all sulfosalts) crystallized at the sametime, in one pulse of ore formation. Where possible, wenote that the late phase is poorer in Cu–Pb, i.e., with alower naik value, than the earlier one. What is typical inthese intergrowths is partial replacement, either alongwell-defined boundaries or with a broad transitionalzone, implying a partial alteration of the former phase.
In these cases, exsolution textures probably develop in
the transition zone between the cores or last remnantsof the original phase and the rims or fingers of the newphase. The replacement textures (Fig. 3) and the coex-

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isting pairs (Fig. 4) suggest non-equilibrium associations, with the difference in respective naik values ranging from less pronounced (e.g., for the association
Cu-bearing bismuthinite – gladite) via intermediate values (e.g., bismuthinite–krupkaite) to the extreme cases,
such as at the contact of Cu-bearing bismuthinite withaikinite. Only in rare instances, typified by the pairs
krupkaite–gladite, krupkaite–salzburgite and lindströmite–krupkaite, might the coexistence of two bd phases
represent an equilibrium assemblage. The first of thesepairs, krupkaite–gladite, seems to be especially common.

FIG. 3. Typical examples of replacement associations of twoto-three bismuthinite derivatives. a–c: Replacement alongcleavage planes. b,d,f: Replacement from the margins.
Two-step replacements are in (c) and (e); post-replacement
exsolution took place in the reaction zone in (f). EMP data
are provided in Table 2. Associated phases: bd: bismuthinite derivatives, gb: galenobismutite, 4L: lillianite, 4P:
makovickyite, 5P: pavonite, ca: cannizzarite, co: cosalite,
ku: kupčíkite, bi: native bismuth.

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THE CANADIAN MINERALOGISTTABLE 2. ANALYTICAL DATA FOR SELECTED REPLACEMENT ASSOCIATIONS AND EXSOLUTION PAIRSIN THE FELBERTAL DEPOSIT, AS ILLUSTRATED IN FIGURES 3-13

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FIG. 4. Pairs of coexisting homogeneous bismuthinite derivatives typifying the disequilibrium and replacement associations
from Felbertal. For abreviations, see Figure 2. Boundaries between the fields assigned to distinct derivatives are of orientational
value only; for exact data, see Table 1.

Perusal of a large number of observed cases [Tables
2 and 4 (deposited), and Fig. 4] allows definition of three
replacement trends in the Felbertal deposit: 1) those withthe end-product being krupkaite, the starting material
varying from naik = 93 to naik = 62, 2) those with theend-product being gladite, starting generally from stoichiometric to oversubstituted krupkaite (Cu- and Pbbearing krupkaite), and 3) those with the end-productbeing bismuthinite, rarely also bd13. In this case, thestarting derivatives span practically the entire range ofbismuthinite–aikinite series, from aikinite to bd13.
Other replacement pairs are rare, e.g., the association bd54 → bd40.4 in Figure 3b. In several instances,
two-step replacement is observed, e.g., bd50 → bd37 →bd5 (Fig. 3e). In this and other one-step instances, thecompact late bismuthinite derivative with naik in the
bismuthinite range is in some cases associated with chalcopyrite–bismuthinite symplectite, which roughly replace decomposed grains of, presumably, an original
Cu–(?)Fe–Bi sulfosalt.

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EXSOLUTION PAIRS
Exsolution pairs that formed from original single bd
grains represent the majority of bd aggregates at
Felbertal. Elongate drops to wavy lamellae of one component are quasi-regularly distributed in the matrix ofthe major phase (Fig. 5), in some cases showing a predilection for the ancient planes of weakness. With few
exceptions, the BSE images show that both exsolved
phases are chemically homogeneous.
Careful analyses of exsolution products by means of
the electron microprobe gave the first indication of thechemical complexity of the exsolved phases and theexistence of new, hitherto undescribed phases. Wellorganized exsolution lamellae in which the two exsolved
phases differ by naik of 2–3% were later found to correspond fully to two crystallographically distinct although chemically very similar phases (Table 1).
The best developed and most common examples are
the exsolved phases in the gladite–krupkaite range

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FIG. 5. Exsolution pairs in the bismuthinite–aikinite derivatives (the gladite–krupkaite range) from the Felbertal deposit. Distinct
associations are illustrated, originating from bulk compositions (capital letters) clustered around naik intervals of 40.2–40.5,

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859

41.5–41.8, 43.2–43.8, and 45.9–46.5. Where not indicated, bar length is 100 m. Figure 5l shows a sequence of pairs, bd37.3– bd39.7, bd37.3 – bd42.1, and, finally, bd37.3–bd48.2 developed from the original composition bd39.1.

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THE CANADIAN MINERALOGIST[Table 2 and 5 (deposited), Figs. 5, 6], for which theexsolved phases can be identified as classical or new
mineral species. A combination of electron-microprobe
data on exsolved species with image analysis allowed
us to estimate the original, pre-exsolution compositionof the bd phase (given as BD below). Table 2 and Figure 6 show that the krupkaite (bd48.5) – paarite (bd42.5)
aggregate formed from BD46–47, the krupkaite (bd48.5) –salzburgite (bd40.5) aggregate, from BD45–47, and the
krupkaite (bd48.5) – gladite (bd38.5) aggregate, from
BD45–46 (Table 2, Fig. 6), i.e., all three cases haveroughly the same starting composition. The exsolutionof the original BD~46 phase situated in the paarite–
krupkaite gap into the association of krupkaite (in which
we observe gradual enrichment in Cu–Pb, indicatedby different shades of grey in Figs. 5j, k), with bd42.9,
bd40.1–40.4, and bd38.5, respectively, is illustrated in
Figures 5h–k.
Pre-exsolution compositions with lower naik values
abound as well: the pair gladite (bd37) – krupkaite(bd48.5) exsolved from BD38.5, the same pair containing
more Cu-rich gladite (bd≤38.7) exsolved from BD40 and

BD43, respectively. The pair gladite (bd37) – salzburgite(bd41) formed from BD40, whereas high-Cu gladite(bd38.5) – paarite (bd42–43) formed from a range of
salzburgite-like compositions. The principal exsolutionrelated pairs plotted in Figure 6 are illustrated in Figures 5a–c, d–e, f–g for the starting bulk-compositions
clustered on BD40.2–40.5, BD41.5–41.8, and BD43.2–43.8, respectively. The compositions shown in Figure 6 wereordered according to the composition of the phasepoorer in Cu–Pb in order to establish possible related
compositional trends in the high-Cu phases; however,
only weak and partly contradictory trends were found.
Chemical compositions of very fine lamellae were notincluded. A crystallographic confirmation of exsolution
trends was found in the single-crystal X-ray-diffraction
study of a grain of bd42.6 in which the original 5-foldsuperstructure decomposed partly into a mixture of
3-fold and, presumably, 1-fold structure (Table 1).
Exsolution pairs in the bismuthinite–gladite region[Tables 2 and 4 (the latter deposited) and Figs. 7, 8] areless common in the Felbertal deposit and not so well
documented. Gladite (bd≥33) is the most common com-

FIG. 6. Exsolution pairs of bismuthinite derivatives in the gladite–krupkaite range with pre-exsolution bulk-compositions (p.e.b.c.) of selected exsolution-induced aggregates indicated by black bars. Symbols indicate types of association. Boundaries
between the fields assigned to distinct derivatives are of orientational value only.

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FIG. 7. Exsolution pairs in the bismuthinite–aikinite derivatives (the bismuthinite–gladite range) from the Felbertal deposit.
Distinct associations originating from bulk compositions (capital letters) having naik = 24, 28, 31 and 33, are illustrated.

ponent. It associates with bismuthinite (bd10), pekoite(bd16), but also with the rather frequent lamellae bd13.
Less frequent are lamellae bd21–22 and bd25–27, whichassociate with bd13, pekoite and, in a single case, withgladite (Fig. 8). None of these bd phases was found as asingle, unexsolved grain.

COMPLEX EXSOLUTION AGGREGATES
Some exsolution aggregates contains more than two
distinct bismuthinite derivatives, the number of such

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components increasing up to five. For three-component
grains, microscopic observations always indicate lamellar aggregates in which the “third” phase either is developed as residual areas (slabs) of the originalbulk-composition or it is a phase exsolved in the earlier
stage of exsolution and is clearly being replaced by anew, compositionally more extreme bismuthinite derivative (Figs. 9a–c). The latter type either occurs as thecontinuation of the older exsolved lamella (Figs. 9a–c)
or, less commonly, it coats a lamella of the older phaseat its contacts with the other, persisting exsolved com-

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THE CANADIAN MINERALOGIST

FIG. 8. Exsolution pairs of bismuthinite–aikinite derivatives in the bismuthinite–gladite range. Symbols indicate types ofassociation.

ponent (Figs. 9b, e). This persisting component is common to the early and the late exsolution association; only
exceptionally was a slight change in its composition
observed (the krupkaite component in Fig. 9e). In cases
where the compositional difference increased in thetransition from the earlier to the later association, therelative amount (lamella thickness) of the unchanged,
persisting exsolved component increases and thelamellae of the newest component are thinner than thoseof the component being consumed (Figs. 9a, c).
Polished grains in which four distinct bd components
were observed combine these two principles: both theareas of original, single composition exist, and an alteration sequence for one of the two primarily exsolved
phases is observed. In the most dramatic example (Fig.
10), the original bd39.2 phase (Cu–Pb-rich gladite) decomposes into gladite, bd36.7, and salzburgite, bd41.1.
The latter locally alters into krupkaite (bd47.5) with adramatic decrease in lamella thickness and a corresponding increase in the volume of gladite (bd36.7).
A sequence of laterally proceeding modifications,bd40.1 → bd41.9 → bd47.2 (all in association with bd38.5)
is illustrated in Figure 9d, in which no primary phase ispresent. Among the rare instances of five-component bd

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intergrowths, Figure 9f shows a sequence from an
exsolution pair that is not quite well defined, bd38.3–
bd39.8, to the final pair bd37.2–bd48.6. Figure 5l presents
an exsolution sequence starting with bd39.1 that on the
one hand produced lamellae of persisting gladite (bd37.3)
and, on the other, a sequence bd39.7 → bd42.1 → bd48.2,
all within a span of 150 m.
Estimates of compositions of the precursor in thecase of the exsolution pairs from the grains withthree to four components are infrequent, owing to the

FIG. 9. Evidence of multistage exsolution for the bismuthinite–aikinite derivatives in the Felbertal deposit. a) Modificationof bd42 lamellae into bd49 lamellae (plus additional bd39)
advancing from grain boundary; b) similar process for
bd40.2 → bd47.8 on a diagonal plane of weakness and fromgrain margin (bd47.8 overgrowing bd40.2, associated with
bd37.4); c) a virtually completed second stage of exsolution;d) evidence of three-stage exsolution, with exsolved
lamellae creating a sequence bd40.1 → bd41.9 → bd47.2; e)
the exsolution pair bd41.2–bd47.7 being replaced by bd37.4–
bd47.9; f) lobed remnants of bd~39 with indistinct lamellaeof bd39.8 being replaced by the matrix bd37.2 and a sequenceof exsolution lamellae bd39.8 → bd42.3 → bd48.6.

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863

864

THE CANADIAN MINERALOGIST

difficulty in separating sufficiently large, representative
areas for each of the pairs present in the process of image analysis. Image analysis of a well-developed
exsolution-induced intergrowth with a large originalcore of BD40.3 and two areas of lamellar intergrowths(the first-stage association bd38.8 – bd41.9 and the subsequent association bd38.8 – bd48.0) gave BD40 as a bulk
composition for both associations.

DISCUSSION AND CONCLUSIONS
The results of our studies complicate substantiallythe solvus of the pseudobinary system Bi2S3 – CuPbBiS3
in the gladite–krupkaite region. Suggestions for similarcomplications were also found in the bismuthinite–
gladite region, whereas no exsolution textures were located for the derivatives with naik over 50. Our initial
simple working model for the gladite–krupkaite region
was based on the assumption of a stable final association gladite–krupkaite. The first (i.e., highest-temperature) association would be paarite–krupkaite as the firstprecursor, invariably followed by the association
salzburgite–krupkaite at a somewhat lower temperature,
which would finally yield the stable pair gladite (bd33)– krupkaite (bd50). This model implies that salzburgite
invariably decomposes into gladite and krupkaite, andthat sequences of consecutive exsolution-lamellae suchas bd39.7 → bd42.1 → bd48.2 from the original bd39, occurring in every case in association with bd37.3 lamellae(Fig.5l), are impossible.

None of these assumptions was fulfilled, however;the bd~38–40 compositions yield equally well two-phaseintergrowths with the “allowed” or the “forbidden” combinations of phases (Fig. 5), even the salzburgite–paarite
exsolution aggregates were observed, and the above“forbidden” temporal sequence of lamellae, salzburgite→ paarite → krupkaite in association with gladite, iscommon (Figs. 5l, 9d and f). The other possibility,
paarite being stable to lower temperatures thansalzburgite, would preclude the associations of the typeobserved in Figure 5i, in which the original BD46.5
exsolves into krupkaite, bd48.6, and salzburgite, bd40.1.
Therefore, an alternative explanation was sought which
would explain all the observed facts.
Being structural combinations (i.e., mixtures) of just
two types of tightly bonded ribbons (or of two types ofstructure modules), the individual derivatives ofbismuthinite in the gladite–krupkaite range do not differ substantially in their Gibbs free energy. Because ofthis, the activation energy of ordering assumes a dominant role in the exsolution process, in which not only
the easy redistribution of copper atoms and vacancies
but also the much more difficult redistribution of leadand bismuth atoms take place. Therefore, the disorderedor ordered parent phase exsolves into two compositionally adjacent ordered derivatives, involving a minimumof diffusion and compositional separation, and not intoa more widely separated pair, which might be thermodynamically more stable. In all observed cases, further
development toward more stable, and more distinct,
separate compositions proceeds via an analogous pro-

FIG. 10. Large-scale development of exsolution patterns in a crystal of bd39.2 from Felbertal. Flat-grey area: original phase; lightand medium grey lamellae: bd36.7–bd 41.1 intergrowth. Light and dark lamellae: second-stage exsolution producing krupkaite–
gladite intergrowth in selected zones.

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MEMBERS OF THE BISMUTHINITE–AIKINITE SERIES FROM FELBERTAL, AUSTRIA

cess in one (presumably metastable) member of the pair,again yielding a pair of structures compositionally closest to the decomposing derivative. This process again
involves minimal changes in the previous pattern of Cu
and Pb–Bi distribution. The difficult ordering process
might be facilitated by a local development of structural
faults or, more probably, by the influence of intergranular fluids as suppliers of itinerant protons able to catalyze local interchange of cations by temporarily
attaching themselves to the sulfur atoms involved. Bothof these factors would cause the zonal and patchy development of the younger exsolution-induced associations, observed in our material.
The highest portion of the solvus for the two observed compositional gaps in Figure 2 might well reach
into the disordered regions of the bismuthinite–aikinite
solid solution, but the fine aggregates of exsolution
products just described, with small compositional
differences between the exsolved components, and withthe observed sequential development, are connectedwith the existence of ordered, compositionally clearly
defined phases.

Owing to its predominantly kinetic nature, theexsolution process in the gladite–krupkaite range of thebismuthinite–aikinite series does not allow us to recognize and define the thermodynamically determinedshape of the solvus and the relative stability of individual derivatives, with the exception of the apparently
most stable, terminal gladite–krupkaite association. Ourstudies show that factors related to thermodynamic stability are overshadowed by the kinetic ones in the ordering processes in Nature.
The exsolution aggregates in the bismuthinite–
gladite region resemble texturally those from thegladite–krupkaite interval, in sharp contrast to the aggregates with n aik over 50. In the latter, no clear
exsolution textures were recognized, even where the
X-ray data confirmed a mixture of two derivatives (e.g.,lindströmite and oversubstituted krupkaite). A possible
explanation is contained in Figure 11, in which datafrom Table 1 were used. The linear change in the subcell
volume throughout the series is accompanied by a similarly linear change in the length of the 4 Å parameter (adimension) but by an opposite, two-step change in the

FIG. 11. Change in subcell dimensions with increasing molar percentage of the aikinite component.

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865

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866

THE CANADIAN MINERALOGISTb and c parameters (Fig. 11). In the case of two coexisting phases, excessive strain or incoherency will develop
along contact planes containing the lattice vector withthe steep trend in Figure 11.
Although the ordering process proceeds by building(010) modules of various types, the exsolution lamellaeof two phases in the bismuthinite–aikinite series should
form most easily on the planes of least elastic strain.
Thus, the two trends in the development of b and c parameters, below and above naik = 50, should have a profound influence on the exsolution forms and kinetics.
They might cause the submicroscopic character of nearly
all observed exsolution-lamellae in the krupkaite–
aikinite range (i.e., naik > 50) range. Final confirmationof these ideas can only be obtained by a combination of
microscopic and diffraction studies on the exsolution
intergrowths in this range.
The temperatures of exsolution and ordering are
unknown. The synthetic materials produced by Springer(1971) at 300°C and by Mumme & Watts (1976) at
500°C are disordered, with an 11Å cell only, and norecognized superstructure (the latter authors also usedsingle-crystal X-ray diffraction). Pring (1995) observed
cation ordering and superstructure formation in synthetic Cu2Pb2Bi4S9 (hammarite) at 175° and 225°C after extended annealing. First, after 32 months at 175°C,
a non-periodic sequence of krupkaite and aikinite strips(010) of finite length appeared. It is replaced by fairly
regular 3a sequences (with occasional 4a intervals) after the total of 56 months at 225°C. Development of strip
sequences was very unequal in different fragments ofthe same charge.
The applicability of these observations to the principal body of our data is somewhat limited; they concern
the compositions above 50 mol.% of the aikinite component, not available in our exsolution aggregates. Thus
we can only tentatively accept the above temperatures
for our conditions. The catalysis of diffusion processesby the influence of tectonics and fluids, suggested here,
still awaits experimental verification.
Very good insight into the shape and orientation of
exsolution lamellae in the naik < 50 range was obtained
from a combination of BSE images of the exsolution
textures with the observed (001) cleavage of low-Cu
bismuthinite derivatives. In the sections of crystals approximately parallel to (100), the exsolution takes theform of straight lamellae → wavy lamellae → shorteror longer zig-zag lamellae → skeletal rhomb-like arrangements of lamellae → rhomb-shaped rods and theirstrings (Figs. 5, 7). In the best-oriented sections, theangle comprised by the lamellae (or surfaces of rhomblike rods) varies between about 110° and 135°. Itscomplement, 70°–45°, is bisected by the (001) cleavage
planes.
Examination of the crystal structures of bismuthinite
derivatives reveals that for the range bd0–bd50, in which
the smallest increments (i.e., differences) occur on theb axis, the planes of minimum elastic strain will be those849 40#3-juin-02-2368-06

866

filled by lone pairs of electrons of the Bi and Pb atoms
and the long cation–sulfur interactions. These are (a) theslightly wavy (100) planes, (b) planes (012)subcell withoccasional, periodic cross-chains protruding slightly
from the smooth surface, (c) planes (011)subcell with a
stepped surface, and (d) planes (013)subcell, which combine properties of both previous planes.
The (012) planes comprise an angle of ~126°, the(011) planes, of ~90°, whereas the (013) planes show
an angle of ~140°, depending on the derivative. The
most exact values observed in polished sections fit best
the exsolution on (012)subcell planes, although the local
twists and turns of the lamellae (Figs. 5, 7) suggest thatthey might follow alternatively any of these three lowstrain planes. Very locally, clear cases of (011) planes
appear, as in Figure 7.
The spatial distribution of bismuthinite–aikinite derivatives and of their replacement and exsolution pairs
in the deposit gives qualitative clues about the conditions of formation and development of the individual
orebodies K1–K8. The sampling of the orebody is afunction of its accessibility in the past ~15 years. Nevertheless, the overall picture is rather consistent andsuggests certain general trends.
There are two pronounced compositional gaps that,with few exceptions, persist throughout the deposit, indicating that the temperatures of formation only rarely
were high enough for their potential closure. The first
gap, between bd~16 and bd~32 (pekoite–gladite) is fairly
stable; it gets narrower or contains intermediate exsolved
phases only in the bodies K1, K3, eventually also K6
and K8 (Fig. 12). The second gap, at its broadest between bd37 and bd50 (gladite–krupkaite), narrows to
bd38–bd47 in K8 and K1 and, to a lesser degree, in K7,
whereas it is constricted to a narrow gap bd~44–bd~47 orcompletely bridged by the pre-exsolution compositions
on levels 4–6 of the K3 orebody. So far, the fourth levelof the K3 orebody is the only locality for the homogeneous salzburgite and paarite crystals. A similar bridging is largely absent for the previous gap on these levels,
although both gaps are outlined by exsolved compositions (Fig. 12).
Summarizing these observations, the K3 orebody
apparently formed at the highest temperatures, at which
point the bd38–bd50 region formed; the same can be assumed for the bd16–bd33 region in the K1 body. The
associations of the replacement type, with two to threebd phases coexisting, appear most commonly in thesmaller orebodies K6–K8 (Fig. 12) . The compositionof the phases involved, together with the near-absenceof exsolution textures in the bodies K7 and K8, suggestthat ore formation was taking place at temperatures atwhich both large miscibility-gaps were already welldelineated, although still narrow in the case of the K8
body.
The interesting question whether the sulfide orematerial was molten at the peak temperatures of metamorphism can on the one hand be addressed by review-

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MEMBERS OF THE BISMUTHINITE–AIKINITE SERIES FROM FELBERTAL, AUSTRIA

867

FIG. 12. Electron-microprobe data on bismuthinite–aikinite derivatives in the deposit of Felbertal, distributed over individual
studied levels of K1–K8 orebodies. Individual compositions, coexisting compositions, and exsolution grains are distinguished.
The observed miscibility-gaps for distinct orebodies are schematically indicated.

ing the known sulfide phase systems and on the otherby textural studies. According to Springer (1971), only
the aikinite–lindströmite region of the bismuthinite–aikinite solid solution should be molten in the range
550–600°C. No melt was observed in the system PbS–
Bi2S3–Sb2S3 (Chang et al. 1980) and Ag2S–PbS–Bi2S3(Hoda & Chang 1975) at 500°C. The binary eutectic
wittichenite–Cu3Bi5S9 occurs at about 515°C (Buhlmann
1971, Sugaki et al. 1974), and incongruent melting of“CuBi 3S 5”, i.e., synthetic makovickyite, occurs at
649°C. There is no liquid in the system PbS–Cu2S–
Bi2S3 at 400°C (Hoda & Chang 1975) or 450°C (Bente1980), or in the system Ag2S–Cu2S–Bi2S3 at 454°C(Chen & Chang 1974) or 500°C (Chang et al. 1988).
Liquid was observed in the Cu2S–wittichenite region,at up to 30 mol.% PbS in the system Cu2S–PbS–Bi2S3
at 500°C (Chang et al. 1988), and at up to 40 mol.%PbS if Ag2S is added to the system. Antimony lowers
the melting temperature substantially. These observations suggest that the peak-metamorphic melting of thesulfosalt component ought to be restricted to the ore
portions richest in copper. The textural observations
indicate that any possible textures from this stage were
obliterated by later segregation of mineral phases andgrowth of crystals in the long-duration retrograde stage,

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867

and by the competing growth of sulfide and quartz crystals along the ore-inclusion boundaries at this stage offormation.
Processes of reduction, in which bismuthinite–aikinite derivatives, together with other sulfosalts, arereduced to native bismuth plus other products of decomposition, are late and have no connection to the extensive replacement processes in which one sulfosalt(assemblage) replaces another (Fig. 13b).

ACKNOWLEDGEMENTS
This research was supported by a grant to D.T. fromthe University of Salzburg, Austria and by project No.
9901772 of the Danish Natural Science Council. The
diffraction equipment used was financed by the Danish
Natural Science Research Council. Support from both
institutions and the University of Copenhagen is gratefully acknowledged. The kind interest of Dr. Peter
Walser, Superintendent of the Wolfram Bergbau GmbH
Nachfolger CG, and logistical assistance of Mr. H.J.
Zoller, are greatly appreciated. We thank Dr. Allan
Pring, an anonymous reviewer, and Robert F. Martin
for their critical comments, which helped to improve thepaper.

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THE CANADIAN MINERALOGIST

FIG. 13. a) A subparallel aggregate of (presumably) gladite, replaced from margins by Cu-bearing bismuthinite. The transitionzone developed in the grain cores subsequently exsolved into a bd34–bd3 intergrowth. Associated phases: galenobismutite(gb) and lillianite (4L50). b) A grain of gladite (naik = 35) partly replaced by bd5, as well as a large complicated intergrowth of
bd5–7 with lillianite (4L53–59); both are corroded and replaced by a mixture of native bismuth (bi) with fine-grained secondary
products.

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Received August 27, 2001, revised manuscript accepted
May 18, 2002.

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