GEOLOGICA CARPATHICA
, JUNE 2018, 69, 3, 221–236
doi: 10.1515/geoca-2018-0013
www.geologicacarpathica.com
Garavellite and associated sulphosalts from the Strieborná
vein in the Rožňava ore field (Western Carpathians)
TOMÁŠ MIKUŠ
1,
, JULIAN KONDELA
2
, STANISLAV JACKO
2
and STANISLAVA MILOVSKÁ
1
1
Earth Science Institute, Slovak Academy of Sciences, Ďumbierska 1, 974 01 Banská Bystrica, Slovakia;
mikus@savbb.sk
2
Institute of Geosciences, Faculty of Mining, Ecology, Process Control and Geotechnologies, Technical University, Park Komenského 15,
042 00 Košice, Slovakia
(Manuscript received February 13, 2017; accepted in revised form March 15, 2018)
Abstract: The article presents the first description of a complete and continuous series from berthierite to garavellite
sulphosalts in the Western Carpathians. Berthierite is a common main or accessory phase of Sb mineralizations in
the Western Carpathians, and occurs at many localities and ore deposits as well. On the other side, garavellite or Bi-rich
berthierite is a relatively rare accessory phase. The highest Bi content in garavellite reaches up to 38.04 wt. %
which represents 0.90 apfu, and its crystallochemical formula can be written as Fe
0.97
Sb
1.07
Bi
0.90
S
3.98
. Raman band shifts
were observed in the isomorphic berthierite–garavellite series. Garavellite occurs in the younger stages of sulphidic
minera lization, and associates with tetrahedrite, berthierite, Bi-chalcostibite, Sb-bismuthinite, Bi-stibnite, ullmanite and
cinnabarite. It creates irregular grains and veinlets in pre-existing tetrahedrite, or forms myrmekite intergrowths with
chalcopyrite in tetrahedrite. Bi content in chalcostibite is up to 0.20 apfu. Besides the tetrahedrite, pre-existing sulphosalts
are the members of the tintinaite–kobellite series, Bi-jamesonite and bournonite. The Sb/(Sb+Bi) ratio of minerals of
the tintinaite–kobellite series varies from 0.37 to 0.80. The maximum content of Bi in jamesonite is up to 1.22 apfu.
A vertical zonation at the ore vein body (mining levels 6 / 180 a.s.l., 8 / 80 a.s.l., 10 / 20 b.s.l.) is represented by the Sb
decrease along with the Bi increase with increasing depth. Bi content continuously decreases during the older ore
mineralization stage and Sb increases at the younger mineralization stage. Both of the stages have been enriched by
Sb as well.
Keywords: garavellite, tintinaite–kobellite isoseries, Bi-sulphosalts, Micro-Raman spectroscopy, siderite–sulphidic
mineralization, Strieborná vein deposit, Gemeric Superunit.
Introduction
Garavellite (FeSbBiS
4
), in contrast to berthierite (FeSb
2
S
4
),
is one of the rare minerals occurring in the ore deposits of
the Western Carpathians. The rare mineral garavellite was first
identified by Gregorio et al. (1979) in the Cu–Fe deposit of
Valle del Frigido, Apuane Alps, Italy, in ore bodies composed
of siderite with disseminated chalcopyrite. From the world
occurrences, garavellite was also found in Pb–Zn deposits of
Shaanxi (Wei et al. 1985), and more recently in Sn-base metal
ore field of Dachang (Li et al. 1998) in China. Garavellite is
also known from the Au-bearing quartz veins of the Kasejovice
deposit in Czech Republic (Litochleb et al. 1990), and was
found in Au-bearing quartz veins related to the shear zone of
the Aprelkovskii deposit, Russia (Borovikov et al. 1990).
Garavellite is reported from a historic sample from the Cas pari
mine (Germany) where garavellite is associated with ber-
thierite, bismuthinite, chalcopyrite, and siderite (Bindi &
Menchetti 2005). In Slovakia (Western Carpathians), gara-
vellite is reported from the Sb–Au deposit in Pezinok (Andráš
et al. 1993) and from the Mlynná dolina–Hviezda occurrences
(Majzlan & Chovan 1997). Most recently, garavellite has been
found in the Western Carpathians at the Klenovec–Medené
locality within the quartz-sulphidic mineralization (Ferenc &
Dzúrová 2015). Garavellite or Bi-rich berthierite associated
with Bi sulphosalts occurs at the end of the sulphidic stage
of the various types of mineralizations in the Western Car-
pathians: siderite–sulphidic, quartz–stibnite, and stockwork/
disseminated.
Orthorhombic garavellite belongs to the berthierite isotype
series (Bindi & Menchetti 2005; Moëlo et al. 2008) which
includes also berthierite (FeSb
2
S
4
) and clerite (MnSb
2
S
4
).
The atomic arrangement in the garavellite structure is topo-
logically the same as in berthierite (Buerger & Hahn 1954;
Lemoine et al. 1991; Lukaszewicz et al. 2001; Bindi &
Menchetti 2005). The main building blocks of berthierite
crystal structure are [SbS5] orthorhombic pyramids and
[FeS6] octahedral; nevertheless, the non-ideal equality of
inter-atomic distances and angles suggests slight distortion.
One of two Sb positions (Sb2) of berthierite is increasingly
occupied by Bi
3+
up to 100 % in garavellite end-member
(Gregorio et al. 1979; Bindi & Menchetti 2005), causing
differences in the geometry, dimensions and constellation of
coordination polyhedra.
This contribution is focused on the mineralogical and spec-
troscopic characterization of the garavellite–berthierite solid
solution and associated Bi-sulphosalts from the Strieborná
vein deposit, as well as on some paragenetic aspect.
The Raman spectra of berthierite and garavellite were pre-
viously published by Kharbish & Andráš (2014), and in
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, 2018, 69, 3, 221–236
the public spectral database RRUFF (Lafuente et al. 2015).
Kharbish & Andráš (2014) studied how crystal structure
influences the number of the Raman bands, and discussed
frequency shifts by the Sb2–Bi substitution. Here we are pre-
senting the Raman spectra of these minerals along with a phase
with an intermediate chemical composition, with an intention
to identify equivalent Raman modes, and observe their wave-
number shift dependence on elemental substitutions.
Geological setting of the Strieborná vein
The Strieborná vein deposit of the Rožňava ore field (ROF)
is situated at the south-eastern margin of the Western Car-
pathian basement units, inside the Gelnica Group formation
of the Gemeric Superunit. The Early Paleozoic Gelnica
Group forms the oldest sequence of the metasedimetary/ meta-
volcanitic formations of the Gemeric Superunit. The ROF area
is penetrated by the subparallely arranged hydrothermal
siderite–sulphidic veins of SE–NW direction. The history of
mining in the ROF started in the 13
th
century, when the greatest
interest was focused mainly on gold (Eisele 1907), silver,
copper (Schifter 1938; Pavlík 1967), antimony (Papp 1915) and
mercury (Herčko 1971). In 1981, northwards from the Rožňava
mining city, a new Strieborná vein was discovered near the
Čučma village, and it became the most significant vein
structure in the ROF. The vein position was compared with
the historically known, parallely oriented Mária vein (Mesarčík
1994). The veins are situated in the NE–SW transpressive
Transgemeric shear zone (Maťo & Sasvári 1997) where
the Strie borná vein is divided into boudine structure, while
the Maria vein is relatively solid. The distance between
the Strieborná and Mária veins is 600 m (Fig. 1). The vein
filling and the structural position in the ore field suggest
a close link between the veins origin and structural evolution.
The Strieborná vein genesis is the product of multiple
Fig. 1. Geological cross-section through the NE part of Rožňava–Mária ore segment (Mesarčík et al. 1991— modified). 1 — recrystallized
metavolcanics (mafic pyroclastics); 2 — metasandstones interbedded by keratophyre metapyroclastics; 3 — altered grey metasandstones with
black phyllite intercalations; 4 — coarse laminated metasandstones intercalated by green-grey phyllites; 5 — ore veins; 6 — mining levels;
7 — prospecting hole; 8 — faults; 9 — sampling location. The age of volcano-sedimentary complex is Late Paleozoic. The inset shows
the location of the Rožňava ore field (ROF).
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GARAVELLITE AND ASSOCIATED SULPHOSALTS FROM THE STRIEBORNÁ VEIN (ROŽŇAVA ORE FIELD)
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, 2018, 69, 3, 221–236
epigenetic hydrothermal mineralization (Sasvári & Maťo
1998; Hurai et al. 2002), with a close relationship between
the vein filling and rheologically contrasting environment.
Consequently, the vein does not crop out on the surface.
The largest accumulation is known from the 10
th
mine horizon
(20 m b.s.l.) in the total length of 1300 m. On this horizon,
the veins have a NNE–SSW direction and general inclination
75–85° to the NNW, where the vein abruptly ends. The conti-
nuation of the vein gradually decays in the overlaying dark-
black metapelites and grey metasandstones. Metaclasts often
contain layers of quartz and lithic wackes. Below the 10
th
level
(below 0 m a.s.l.) the ore body is situated within metasedi-
ments and metavolcanic rocks.
Mineralogy of the Strieborná vein
Major vein minerals are medium to the coarse-grained
siderite of two generations and younger multi-generational
quartz–sulphide mineralization of two generations. The most
abundant ore minerals are tetrahedrite, chalcopyrite, pyrite
and arsenopyrite. Brittle, steel-grey coloured tetrahedrite,
which is the most important ore mineral, is spatially controlled
by the older siderite that is in the form of reticulated veins and
clusters. A more brittle tetrahedrite variety with steel blue
colour and high metallic lustre is usually enriched by Cu, Ag,
Bi, Sb and Hg. A darker low lustre variety contains more Zn
and Fe (Sasvári & Maťo 1998). The high content of silver in
tetrahedrite was the reason for the name of the Strieborná vein.
The concentration of tetrahedrite in the vein bodies has a zonal
distribution, and gradually decreases downwards to under-
lying rocks where it is substituted by pyrite (Mesarčík et al.
1991; Maťo & Sasvári 1997; Sasvári & Maťo 1998). Quartz is
the main gangue mineral and forms several generations
(Sasvári & Maťo 1998). The products of the youngest quartz–
sulphide phase are tetrahedrite, kobellite, bismuthinite,
bournonite, jamesonite and stibnite.
Methods
Samples for mineralogical study were collected in 1997 from
the 8
th
and 10
th
mine horizons, and in 2015 from the 6
th
horizon
(Fig. 1; Mária Mine — 48°40’35.3” N, 20°32’28.1” E). Polished
samples were prepared for mineralogical and spectroscopic
studies.
The chemical composition of sulphosalts was determined
by using a wavelength-dispersive spectrometry (WDS) on
an electron probe microanalyser (EPMA) JEOL JXA 8530FE
(at the Earth Sciences Institute of the Slovak Academy of
Sciences in Banská Bystrica) under the following conditions:
accelerating voltage 20 kV, probe current 15 and 20 nA, beam
diameter 2–3 µm, ZAF correction, counting time 20 s on peak,
10 s on background. For WDS analyses the following stan-
dards were used: X-ray lines and D.L. (in ppm): Ag(Lα, 45)
— pure Ag, S(Kα, 26) — pyrite, Cu(Kα, 39) and Fe(Kα, 26)
— chalcopyrite, As(Lβ, 208) — GaAs, Se(Lβ, 281) — Bi
2
Se
3
,
Cd(Lα, 55) — CdTe, Sb(Lα, 47) — stibnite, Hg(Mα, 101) —
cinnabar, Bi(Lα, 240) — Bi
2
S
3
, Pb(Mα, 93) — galena,
Ni(Kα, 32) — gersdorffite, Co(Kα, 32) — pure Co, Zn (Kα,
45) — sphalerite.
The non-polarized Raman spectra were measured from
berthierite and garavellite (polished sections) with the diffe-
rent content of Bi and Sb. We have used a LabRAM HR
(Horiba Jobin-Yvon) microspectrometer with an Olympus
BX41 microscope, and with confocally coupled Czerny-
Turner type monochromator (focal length 800 mm). A laser
emission at λ = 632.8 nm (He–Ne laser) was used for excitation.
The Raman scattered light was collected at 180° geometry
through 100×/0.80 objective lens, and dispersed by a diffrac-
tion grating with the density of 600 gr.mm
−1
onto a cooled
CCD detector. The system resolution was 2 cm
−1
, and the
wave number accuracy was ± 1 cm
−1
. The grating turret accu-
racy was calibrated between a zero-order line (180° reflection)
and laser line at 0 cm
−1
. The spectral accuracy was verified on
734 cm
−1
line of teflon. Measurement conditions were adjusted
to achieve the best signal/noise ratio, and to prevent photo-
chemical reactions (Makreski et al. 2013): laser power was
dimmed to 0.054 mW on the sample surface (a level that was
empirically found to be harmless to the sample), and this weak
excitation power was compensated by long collection times.
Each point was visually checked for thermal damage after
the measurement. The spectra with high backgrounds were
corrected by the subtraction of blank background record.
The spectra were acquired in the range of 50–500 cm
–1
,
the exposition time was 6×500 s, using 6-fold sub-pixel shift.
The positions of Raman lines were refined by peak fitting,
using the Gaussian–Lorentzian function in the program PeakFit
(SeaSolve Software Inc.). A factor group analysis was per-
formed, using the tools of the Bilbao Crystallographic Server
(www.cryst.ehu.es; Kroumova et al. 2003), using published
crystallographic parameters for the studied minerals.
Results of the mineralogical research
Geological documentation
The Strieborná vein was discovered after drilling prospec-
tion in the 6
th
mine level (Fig.1). The studied part of the
Strieborná vein mine gallery is localized in significantly
foliated dark grey, thin-bedded metasandstones and black
metapelites (Fig. 2). Surrounding rocks of the ore veins also
contain subordinate pyrite and arsenopyrite involved in quartz
veinlets. Idiomorphic pyrite grains are not jointed, and their
size is up to 0.5 cm. Fine-grained arsenopyrite forms dark grey
strips of up to 3 mm in thickness. Vein bodies are developed
along foliation planes, and they are — like the host rocks —
significantly tectonically affected. The Strieborná vein has
NE–SW direction and shows SE steep inclination angle.
The vein footwall is strictly cut by a fault, and the mine gallery
vein thickness attains approximately 4.6 m (Fig. 2). Siderite is
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MIKUŠ, KONDELA, JACKO and MILOVSKÁ
GEOLOGICA CARPATHICA
, 2018, 69, 3, 221–236
the major vein mineral, and it is intensively jointed and rarely
brecciated. The second most abundant mineral of the vein is
quartz. Along with tetrahedrite, it closes cracks in siderite, or
fills nests and irregular veinlets. The tetrahedrite is the third
most abundant mineral of the vein filling. It fills joints within
the siderite body, or creates both thin veins and rare massive
ore lenses (up to 0.5 m
2
). At the 6
th
mine level of the Strieborná
vein, tetrahedrite forms 3 textural types in siderite: stockworks,
massive and breccia textures (Fig. 3). Pyrite and arsenopyrite
are further macroscopically visible ore minerals of the vein
infill. Pyrite grains having up to 1 cm dimensions show either
irregular shapes or sizes, and they are also intensively jointed.
Fig. 2. Geological mine gallery cut through the Strieborná vein on
the 6
th
mine level and ore textures from the stockwork in the footwall
of the Strieborná vein. a — Transversal cross-section A–A´ in
the Transgemeric shear zone where the Strieborná vein and subsidiary
stockworks are ductile deformed to individual rigid boudine bodies
circumscribed by plastic phylites and metapsamites. b — Horizontal
cross-section parallel with Transgemeric shear zone and Strieborná
vein too. The vein is filled by massive tetrahedrite in the siderite
mineralization.
b
a
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Paragenetic associations
Based on the detailed mineralogical study, several mineral
associations of sulphosalts can be distinguished in the quartz–
sulphidic stage of the Strieborná vein. The first older phases
are represented by an association of tintinaite–kobellite series
— Bi-jamesonite–bournonite–tetrahedrite (from oldest to
youn gest). The second one, the younger association than tetra-
hedrite, is represented by chalcostibite – berthierite–garavellite
series — “horobetsuite” (Bi-stibnite, Sb-bismuthinite)–native
Bi-stibnite. Considering the succession scheme of sulphosalts
formation, the temporal decreases/increases of bismuth could
be assumed for a period of sulphosalts evolution, namely
the gradual decrease of Bi content in the fluids in the older
stage, and its increase during the younger sulphosalts stage.
The younger stage is also characteristic with Sb enrichment.
Beside temporal relationships, spatial diversity could also be
proposed in sulphosalts formation. In general, Sb content
shows an apparently inverse depth proportional relationship
(e.g., from the 6
th
to 10
th
mine level). Tetrahedrite content
shows the same relationships, while Bi content increases at
the same depth span. We have tried to outline and improve
the succession scheme for the Strieborná vein as the result of
our paragenetic study (Fig. 4). The proposed scheme also used
data from Sasvári & Maťo (1998) and Dianiška (2013).
Berthierite FeSb
2
S
4
– Garavellite FeSbBiS
4
solid solution
Minerals of this series are relatively abundant, mainly at
the 6
th
and 8
th
mine levels. They form several morphological
types at the 6
th
mine level. Berthierite often associates with
garavellite, forming a few mm. long veinlets or myrmekitic
intergrowths with chalcopyrite in tetrahedrite. Berthierite
creates intergrowths with chalcostibite and stibnite. Garavellite
comprises up to 50 µm isometric grains, and associates with
Bi-stibnite and Sb-bismuthinite in tetrahedrite. Hairline vein-
lets (Fig. 5c) formed by myrmekitic intergrowths of berthierite
and chalcopyrite in tetrahedrite rarely contain garavellite and
arsenopyrite (Fig. 5d). Occasional berthierite associates with
ullmannite and cinnabar (Fig. 5b). At the 8
th
mine level gara-
vellite often forms isometric grains up to 200 µm in tetra-
hedrite, where it is one of the most common sulphosalts
associated with Sb-bismuthinite (Fig. 6d). Berthierite of
the same mine level is fairly rare. The chemical heterogeneity
of garavellite is a quite common feature. It often forms zones,
which have an irregular shape, with diffuse interfaces in
berthierite (Figs. 5d, 6d). Berthierite and garavellite are younger
than tetrahedrite and chalcostibite but earlier than stibnite.
The chemical composition of this series is represented by
a continuous transition from a berthierite end member on
the one side, to a garavellite end member on the other one (Fig. 7)
through transition members — Bi-berthierite and Sb-gara-
vellite. An empirical formula for berthierite (Bi-free) can be
written as Fe
1.0
Sb
1.98
S
3.98
based on 7 apfu. Bi content and other
measured elements in this type are negligible. Bi
3+
→ Sb
3+
sub-
stitution in garavellite is intensive, showing a strong positive
correlation (Fig. 7). Bi content continuously increases from
1.16 wt. % up to 38.04 wt. % which represents 0.02–0.91 apfu.
Divalent cations are dominantly represented by Fe. Other
elements are present only in minor amounts, except for Cu,
which can reach up to 0.65 wt. %. An empirical formula for
garavellite with the highest Bi content can be expressed as
Fe
0.97
Sb
1.06
Bi
0.91
S
4.01
based on 7 apfu. Representative micro-
probe analyses are presented in Table 1. With increasing depth,
garavellite is more enriched in Bi and more abundant than
berthierite (from 6
th
to 8
th
level). However, garavellite and
berthierite were not found on the 10
th
mine level.
Based on the crystal symmetry and atomic coordinates of
orthorhombic berthierite (Lukaszewicz et al. 2001) and gara-
vellite (Bindi & Menchetti 2005), both of the spatial group
Pnam (#62 — standard Pnma), Z = 4, our factor group analysis
yielded a total of 42 Raman-active vibration modes (14Ag +
7B1g + 14B2g + 7B3g). Not all of them are equally pronounced
due to crystal orientation to the polarized laser beam.
Fig. 3. Tetrahedrite textures from the Strieborná vein filling (6
th
mine level) showing transition from breccia to massive ore.
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Berthierite with 0.00 and 0.20 apfu of Bi, and garavellite
with 0.89 apfu of Bi were chosen for the spectroscopic study
(Table 1, Fig. 6d).
All Raman spectral peaks of berthierite, garavellite and
the Bi-berthierite occur between 500–60 cm
−1
(Fig. 8), their
fitted values are listed in the Table 2. The dominant Raman
peak of berthierite is centred at 268 cm
−1
, other intense peaks
are at 353, 278 and 58 cm
−1
. Sharp bands occur in the region
110–58 cm
−1
. The deconvolution of the spectrum yielded 25
significant bands (Table 2). The feature at 269 cm
−1
dominates
for the garavellite spectrum, the fitting resulted in 30 bands.
The Bi-berthierite consists of 28 peaks and shows spectral
similarities to both minerals (berthierite and garavellite).
The strong berthierite band at 353 cm
−1
tends to energy
decrease towards garavellite (346 cm
−1
); it has an asymmetric
shape and is composed of three peaks (Table 2). With decrea-
sing Bi content, the weak garavellite peak at 310 cm
−1
progres-
sively splits and grows into two stronger peaks at 304, 315 and
302, 317 cm
−1
in Bi-berthierite and berthierite, respectively.
The dominant band centred at 268 cm
−1
has virtually no shift
towards garavellite; however, it broadens and splits into at
least to two peaks. The berthierite Raman band at 258 cm
−1
is probably incorporated into a broad peak at 269 cm
−1
in
the garavellite spectrum. Both, the evolution of the medium
and low intensity peaks in the spectral region between 250 and
110 cm
−1
are unclear. The wavenumber position of features at
104 and 95 cm
−1
is changing towards lower frequencies with
increasing Bi content, and bands at 80 and 74 cm
−1
seam to
transform to a broad weak band at 77 cm
−1
.
The broad shape of dominant peaks of expected internal
modes are typical for all spectra phases in the region. Despite
distinct shifts between some peaks in berthierite and gara-
vellite, their equivalence may be clearly traced through
the Bi-berthierite spectrum (Table 2).
Associated sulphosalts
Jamesonite FePb
4
Sb
6
S
14
It occurs rarely in studied samples and forms needle aggre-
gates up to 0.5 mm. On the 6
th
mine level, jamesonite is asso-
ciated with older tintinaite, and is corro ded by later tetrahedrite,
bournonite, bis muthinite and native Bi (Fig. 6 a, b).
Bi content is up to 7.98 wt. % that corresponds to 0.83 apfu.
Bi/(Bi+Sb) ratio (0.095) is less than in tintinaite (0.335), and
at the same time higher than in bournonite (0.017) and tetra-
hedrite (0.008). This could suggest the con-
sistent regress of Bi concentration in fluids
during the crystallization of sulphosalts in
the following succession: tintinaite–jame-
sonite–bournonite–tetrahedrite. This succes-
sion is also obvious from microscopic
observations. Other elements are present
only in minor amounts. Electron microana-
lyses are presented in the Table 3. An empi-
rical formula for jamesonite can be written
as Fe
0.95
Pb
4.02
(Sb
5.35
Bi
0.56
)
5.91
S
14.00
based on
25 apfu. Bi-rich jamesonite is associated
with tintinaite and bournonite. It occurs only
rarely at the 10
th
mine level, and contains up
to 11.78 wt. % of Bi (1.22 apfu) (Table 3).
Cu content is relatively high (0.29 apfu) and
probably partly substitutes Fe. This idea is
supported by a negative correlation trend
between Cu and Fe. Its empirical formula,
based on of 25 apfu, can be written as
Fe
0.85
Cu
0.29
Pb
3.95
(Sb
4.76
Bi
1.22
)
5.98
S
13.91
.
Bournonite CuPbSbS
3
It was found in all three studied mine
levels. It usually forms xenomorphous grains
up to 0.1 mm. At the 6
th
level, bournonite
intensively corroded tintinaite via cracks and
cleavage planes (Fig. 6b), and also corroded
jamesonite needles (Fig. 6a). The Bi content
is up to 3.24 wt. % (0.08 apfu) which is
characteristic for interstitial grains between
tintinaite and jamesonite. Locally, high Bi
Fig. 4. Succession scheme of the hydrothermal mineralization in the Strieborná vein.
The scheme is proposed based on this study and published data of Sasvári & Maťo (1998)
and Dianiška (2013).
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contents in bournonite could be the result of reaction between
fluids and older Bi-sulphosalts. Other measured elements are
present only in low concentrations (Table 4). At the 10
th
mine
level, bournonite intensively corroded kobellite, and rarely
associates with younger Sb-bismuthinite. It forms needle
crystals up to 0.5 mm.
Kobellite–tintinaite (Cu, Fe)
2
Pb
10
(Sb, Bi)
16
S
35
series N=2
Sulphosalts of this series represent the most common ones
in the deposit. They were found at the 6
th
and 10
th
mine levels.
At the 6
th
mine level, tintinaite forms needle crystals up to
seve ral cm in size. It occurs in association with jamesonite
(Fig. 6a), tetrahedrite, bournonite, bismuthinite and native
Bi (Fig. 6b). Tintinaite represents the oldest sulphosalt. Its
clea vage planes and cracks are rejuvenated by bournonite and
native Bi. At the10
th
mine level, the kobellite is associated and
intensively corroded with younger bournonite, Sb-bismuthinite
and Bi-jamesonite. In general, with increasing depth,
an increase of Bi and a decrease of Sb are observed. Sb-rich
members of the 6
th
mine level can be considered as tintinaite
and Bi-rich members at the 10
th
mine level as kobellite (Fig. 9).
Paradoxically, the highest Bi content occurs in kobellite which
forms isometric grains (up to 20 µm) in tintinaite found at
the 6
th
mine level. Antimony content in members of this series
ranges between 5.84 up to 12.96 apfu. Bismuth content varies
from 3.18 to 9.78 apfu. The Bi–Sb substitutional trend seems
to be ideal (Fig. 9). Sb/(Sb+Bi) ratio varies from 0.37 to 0.80
(Fig. 10). Silver content is only minor (in average 0.06 apfu).
Fe+Cu content in the studied phases is higher than that repor-
ted for the kobellite-tintinaite series (Fe+Cu=2 apfu, Zakrzewski
& Makovicky 1986). The maximum content of Cu+Fe is 3.12,
2.22 in average. Cu content in many studied samples exceeds
2 apfu (maximum 2.23). Among the minor elements, only Hg
is slightly increased (up to 0.86 wt. %). An empirical formula
for tintinaite with the highest Sb content (and assuming cation
substitutions) can be written as (Cu
1.92
Fe
0.08
)
2
(Cu
0.24
Ag
0.08
Hg
0.1
Pb
9.89
)(Sb
12.85
Bi
3.16
)S
34.67
with chemically calculated N=1.97.
An empirical formula for kobellite with the highest Bi content
can be written as (Cu
1.59
Fe
0.41
)
2
(Cu
0.11
Pb
10.31
Bi
9.78
Sb
5.84
)S
34.90
with calculated N=1.99 (Table 5).
Tetrahedrite (Cu, Ag)
10
(Fe, Zn...)
2
(Sb, As...)
4
(S, Se)
13
Tetrahedrite is one of the most abundant ore minerals of
the Strieborná vein. It forms xenomorphous aggregates up to
Fig. 5. a — BSE images of berthierite (Btt) and garavellite (Grv) associated with chalcostibite (Chs) and stibnite (Stb) replacing tetrahedrite
(Td) grain from the margin. Tetrahedrite is associated with siderite (Sd). b — Bi-berthierite associated with ulmanite (Ulm) and cinnabarite in
tetrahedrite with siderite (Sd). c — Veinlets of berthierite–chalcopyrite myrmekites in tetrahedrite. d — Myrmekitic intergrowth of berthierite
(Btt) with chalcopyrite (Ccp). Berthierite contains garavellite (Grv) grains with diffusional margins.
228
MIKUŠ, KONDELA, JACKO and MILOVSKÁ
GEOLOGICA CARPATHICA
, 2018, 69, 3, 221–236
Fig. 6. a — BSE images of tintinaite (Tnt) associated with jamesonite (Jms), bournonite (Brn), bismuthinite (Bis), kobellite (Kob) and native
Bi (Bi) are corroded by tetrahedrite (Td) and chalcopyrite (Ccp). b — Needle-shaped tintinaite crystal (Tnt) is replaced by bournonite (Brn)
and native bismuth (Bi). c — Exsoluted “horobetsuite” grain (Hbs) in tetrahedrite (Td) is associated with cinnabarite (Cnb). d — Garavellite
(Grv), Bi-berthierite (Bi-Btt) and berthierite (Btt) are associated with arsenopyrite (Asp) and replacing tetrahedrite (Td). Points from EPMA
measurements were used for micro-Raman study. WDS analyses are given in Table 1.
Fig. 7. Sb vs. Bi (apfu) graph for studied members of the berthierite–garavellite solid solution from the Strieborná vein, compared with some
other published data from their occurrences in the Western Carpathians and in the world.
229
GARAVELLITE AND ASSOCIATED SULPHOSALTS FROM THE STRIEBORNÁ VEIN (ROŽŇAVA ORE FIELD)
GEOLOGICA CARPATHICA
, 2018, 69, 3, 221–236
several cm in size. Tetrahedrite is corroded by an older sulpho-
salt association, represented by tintinaite, jamesonite and
bournonite on the 6
th
level. Tetrahedrite grains are intensively
corroded by chalcostibite, stibnite, berthierite–garavellite
(Fig. 5a) and myrmekites of Sb-bismuthinite (Fig. 6c). Cracks
or veinlets in tetrahedrite are often filled with myrmekites of
berthierite–garavellite, chalcopyrite and arsenopyrite (Fig. 5c, d)
as well as cinnabar. The crystallochemical formula of tetra-
hedrite was calculated according to Moëlo et al. (2008), as
[III]
A
6
[IV]
(B,C)
6
[III]
X
4
[IV]
Y
12
[VI]
Z
1
, where A= Cu, Ag; B = Cu, Ag
and C is a generally divalent metal (Fe, Zn, Hg, Cd etc.) in
the same coordination as B; X = Sb, As, Bi, Te; Y and Z = S and
Se. The analysed tetrahedrite has quite a simple composition.
The A site is dominantly occupied by Cu. Silver content
reaches up to 0.27 apfu (1.72 wt. %). The B site is fully occu-
pied by copper. The divalent C position is occupied mainly by
Fe (up to 1.8 apfu), Zn (up to 0.34 apfu), and minor Hg (up to
0.16 apfu) and Cd (up to 0.02 apfu). The X position is domi-
nantly occupied by Sb, and only minor contents of As (up to
0.63 apfu) and Bi (up to 0.03 apfu) are present. The overall
occupation of the X site (Sb + As + Bi) varies from 3.96 to 4.17
apfu with a mean of 4.05 apfu. The Y and Z sites are fully
occupied by sulphur. Se content is only minor and reaches up
to 0.02 apfu. The ave rage Se content from 90 analyses is zero.
The empirical average (90 analyses, Table 6) chemical formula
of the studied tetrahedrite can be written as: (Cu
5.86
Ag
0.14
)
Σ6.00
Cu
4.03
(Fe
1.66
Zn
0.22
Hg
0.1
Cd
0.01
)
Σ1.99
(Sb
3.91
As
0.14
Bi
0.01
)
Σ4.05
S
12.95
,
based on 29 apfu.
Chalcostibite CuSbS
2
Chalcostibite occurs mainly on the 6
th
mine level as
an accessory and phase associate with berthierite and stibnite
(Fig. 5a). It forms up to 10 µm xenomorphous aggregates and
rims on tetrahedrite grains. Chalcostibite is
corroded by stibnite (Fig. 5a). The chemi-
cal composition shows increased content
of Bi up to 0.03 apfu (2.36 wt. %). Higher
Bi contents are observed in chalcostibite,
associated with Bi-berthierite. Iron content
can be slightly increased (up to 0.04 apfu)
as well. The content of other elements is
only minor (Table 7). At the 8
th
mine level,
only sporadic Bi-chalcostibite was found,
likely as a product of breakdown of Bi-rich
sulphosalts. It forms myrmekitic over-
growth with Sb-bismuthinite in tetra hed-
rite. Sb is substituted by Bi in chalco stibite,
and Bi content reaches up to 0.20 apfu
(15.46 wt. %). The chemical formula
of Bi-chalcostibite can be written as
Cu
1.01
(Sb
0.80
Bi
0.20
)S
1.98
(Table 7). Chalco-
stibite was not found on the 10
th
mine
level.
Stibnite Sb
2
S
3
– bismuthinite Bi
2
S
3
solid
solution
Both end-members (stibnite and bis-
muthinite) were found at the Strieborná
vein as well as transition members
Bi-stibnite and Sb-bismuthinite, formerly
known as “horobetsuite”. Stibnite and
bismuthinite form isometric grains up to
50 µm in size. Bi-stibnite and Sb-bis-
muthinite are common minerals forming
myrmekitic intergrowths and exsolutions
in tetrahedrite up to 100 µm (Fig. 6c), or
isometric grains in tetrahedrite and stib-
nite. Stibnite is younger than chalcostibite
and berthierite (Fig. 5a). Bismuthinite
repla ces jamesonite and tetrahedrite
(Fig. 6a). Stibnite was found only on
Sample
h.no.
Fe
Sb
As
Bi
Cu
S
Zn
Pb
Total
J-2 (66)
8
12.69
56.71
0.06
0.00
0.20
29.95
0.01
0.04
99.68
RV 2750
6
13.02
56.20
0.05
0.11
0.06
30.60
0.06
0.03
100.13
1 RV-Z-2
6
13.19
54.17
0.01
1.16
0.37
29.62
0.03
0.02
98.56
RV 2750
6
12.61
52.70
0.07
4.10
0.27
29.07
0.03
0.07
98.92
1 RV-Z-2
6
12.74
48.96
0
8.32
0.19
28.88
0.02
0.02
99.13
J-2 (67)
8
12.15
48.23
0.07
9.14
0.18
28.68
0
0.07
98.51
1 RV-Z-2
6
12.37
45.62
0.03
12.83
0.40
28.33
0.04
0
99.61
RV 2750
6
12.31
43.89
0.04
14.02
0.39
28.30
0
0.05
99.00
5 RV-5 SOS
6
12.01
41.76
0.07
17.83
0.38
27.76
0.08
0.25
99.94
RV 2750
6
11.62
37.52
0.03
22.68
0.13
27.19
0.01
0.06
99.24
1 RV-Z-2
6
11.56
34.98
0.01
26.18
0.25
26.65
0.03
0.03
99.68
1 RV-Z-2
6
11.40
33.40
0.01
28.27
0.36
26.46
0.02
0.12
100.02
RV 2750
6
11.30
31.81
0
30.15
0.46
26.37
0
0
100.08
J-2
8
10.92
26.41
0.02
36.86
0.37
25.41
0.05
0.17
100.20
J-2 (65)
8
10.91
26.75
0.08
37.13
0.14
25.64
0.04
0.13
100.82
J-2
8
10.84
26.30
0
37.29
0.92
25.42
0.03
0.13
100.64
J-2
8
11.08
25.77
0.02
38.04
0.48
25.40
0.02
0.20
101.00
Formula calculated to sum Fe + Sb + Bi = 3
J-2 (66)
8
0.98
2.00
0.00
0.00
0.01
4.01
0.00
0.00
RV 2750
6
0.99
1.96
0.00
0.00
0.00
4.04
0.00
0.00
1 RV-Z-2
6
1.02
1.93
0.00
0.02
0.03
4.00
0.00
0.00
RV 2750
6
0.99
1.91
0.00
0.09
0.02
3.99
0.00
0.00
1 RV-Z-2
6
1.01
1.79
0.00
0.18
0.01
4.01
0.00
0.00
J-2 (67)
8
0.98
1.78
0.00
0.20
0.01
4.02
0.00
0.00
1 RV-Z-2
6
1.00
1.69
0.00
0.28
0.03
3.99
0.00
0.00
RV 2750
6
1.00
1.64
0.00
0.31
0.03
4.01
0.00
0.00
5 RV-5 SOS
6
0.99
1.58
0.00
0.39
0.03
3.99
0.01
0.00
RV 2750
6
0.99
1.46
0.00
0.51
0.01
4.02
0.00
0.00
1 RV-Z-2
6
1.00
1.38
0.00
0.60
0.02
4.00
0.00
0.00
1 RV-Z-2
6
0.99
1.33
0.00
0.66
0.03
4.00
0.00
0.00
RV 2750
6
0.98
1.27
0.00
0.70
0.04
4.00
0.00
0.00
J-2
8
0.98
1.09
0.00
0.89
0.03
3.99
0.00
0.00
J-2 (65)
8
0.98
1.10
0.01
0.89
0.01
4.01
0.00
0.00
J-2
8
0.97
1.07
0.00
0.90
0.07
3.98
0.00
0.00
J-2
8
1.00
1.06
0.00
0.91
0.04
3.98
0.00
0.00
Table 1: Electron microprobe analyses of berthierite–garavellite solid solution. Analyses
no. 66, 67 and 65 represent phases measured with micro-Raman spectroscopy (see Fig. 5d).
H.no. — horizon number.
230
MIKUŠ, KONDELA, JACKO and MILOVSKÁ
GEOLOGICA CARPATHICA
, 2018, 69, 3, 221–236
the 6
th
mine level. Sb-bismuthinite is
dominantly associated with garavellite in
tetrahedrite on the 8
th
mine level. Deeper,
on the 10
th
level, it occurs only rarely and
replaces earlier kobellite. The chemical
composition of stibnite is simple, with
slightly increased Fe (up to 0.59 wt. %)
and Cu (up to 1.13 wt. %) contents. Cu
excess can be caused by the contamina-
tion by chalcostibite intergrowths. Other
elements are present only in minor volu-
mes (Table 8). Sb content in Sb-bis-
muthinite (Fig. 11) ranges from 4.3 to
29.5 wt. % (0.17– 0.99 apfu). Bi content
in Bi-stibnite ranges between 8.17– 48.62
wt. % (0.14– 0.95 apfu). The Sb/Bi substi-
tution trend is shown in the Fig. 11. Some
Bi-stibnite and Sb-bismuthinite contain
increased amounts of Fe (up to 1.65 wt. %)
and Cu (up to 1.8 wt. %). Cu positively
correlates with Bi and Sb contents.
Ullmannite NiSbS
Ullmannite is only a rare minor phase.
On the 6
th
mine level, it associates with
tetrahedrite, Bi-berthierite and cinnabar.
Fig. 8. Raman spectra of berthierite (Btt) — Bi free, Bi-berthierite — Bi 0.2 apfu and garavellite (Grv) — 0.89 apfu from the Strieborná vein.
a. u. — arbitrary unit. Main Raman bands are labelled.
berthierite
Bi-berthierite
garavellite
Bi — 0.00 apfu
Bi — 0.20 apfu
Bi — 0.89 apfu
Band position FWHM
I
Band position FWHM
I
Band position FWHM
I
cm
−1
cm
−1
cm
−1
cm
−1
cm
−1
cm
−1
58
4
62
58
5
37
58
4
49
65
5
38
64
4
100
62
5
31
74
5
20
77
10
44
66
6
21
80
3
44
89
7
44
73
6
32
95
4
50
97
7
19
84
6
64
104
5
16
106
10
13
92
5
23
110
11
5
115
3
7
97
7
17
121
7
13
122
12
19
105
10
4
128
3
22
134
14
19
113
12
21
136
7
21
145
9
5
121
7
15
142
6
11
156
16
40
130
13
38
146
5
5
177
18
15
147
17
15
158
12
8
215
43
16
159
17
16
186
6
5
228
17
28
175
18
17
233
19
40
252
28
28
190
17
15
253
13
25
256
2
2
203
21
20
258
4
16
267
17
57
224
23
40
268
11
100
273
13
23
240
14
33
278
10
53
278
2
4
246
11
32
283
9
31
281
14
24
254
10
14
302
9
28
294
10
7
262
13
43
317
9
19
304
15
30
269
18
100
340
9
17
315
10
15
279
31
21
347
11
20
322
2
3
310
31
16
353
10
62
342
19
30
324
2
2
349
11
67
334
12
22
358
7
2
339
8
11
374
5
1
346
11
41
357
12
8
370
33
6
Table 2: Raman band positions of berthierite,
Bi-berthierite and garavellite. FWHM — Full
width at half maximum; I — normalized inten-
sity in %.
231
GARAVELLITE AND ASSOCIATED SULPHOSALTS FROM THE STRIEBORNÁ VEIN (ROŽŇAVA ORE FIELD)
GEOLOGICA CARPATHICA
, 2018, 69, 3, 221–236
It is more abundant on the 8
th
mine level where it associates
with chalcopyrite, chalcostibite and tetrahedrite. Ullmannite
forms isometric grains up to 200 µm. It often overgrowths
with tetrahedrite. Ullmannite was not found on the 10
th
mine
level. It shows small contents of Fe (up to 0.05 apfu) and As
(up to 0.04 apfu) (Table 9).
Discussion
The mineralogical research of the polystadial Strieborná
vein sulphosalts allows us to understand the berthierite to
garavellite transition mode in the vertical course of the
Strieborná ore vein. The vein’s evolution closely relates to
the Transgemeric shear zone (TGS) which has also partici-
pated in the incoherent structure of the Western Carpathians
during paleo-Alpine (Cretaceous) evolu-
tion (Lexa et al. 2003). The tectonometa-
morphic processes in the shear zone are
responsible for the formation of some
mine ralization stages (Mesarčík et al.
1991) and they are also responsible for
later boudinal destructions of the ore
veins.
The Strieborná vein ore bodies have
been observed on different mining levels
(6 / 180 a.s.l., 8 / 80 a.s.l., 10 / 20 b.s.l.).
The research results have confirmed
the vertical zonality of sulphosalts inclu-
ding berthierite to garavellite transition
(cf. Fig. 8) for first time in the Western
Carpathians. The chemical composition
of berthierite–garavellite solid-solution
from the Strieborná vein is the most com-
plex compared to published data world-
wide (Fig. 7).
We have tried to compare the spatial
zonation of the Strieborná vein sulpho-
salts with other world occurrences of
simi lar sulphosalts in shear zones, how-
ever this was not possible, as the pub-
lished data come from single spots in
each of the studied localities (e.g., Orlandi
et al. 2010; Ferenc & Dzúrová 2015).
Some other data come from mine waste
(Kharbis & Andráš 2014; Uher et al.
2000), others belong to a historical col-
lection (Bindi & Mencheti 2005), repre-
sent experimental analysis products (Liu
et al. 2008) or belong to a skarn occur-
rence (Ciobanu et al. 2014). The sulpho-
salts represent a genetically well-defined
group evolved in specific conditions of
hydrothermal processes. The tempera-
tures controlling the substitution of
extended solid solution of sulphosalts
vary from 300 to 400 °C (Moëlo et al. 2008).
Our Raman spectra are basically similar to those of Kharbish
& Andráš (2014) and results of the RRUFF database (Lafuente
et al. 2015), though they show significant differences in the
relative intensities of several bands. Since neither our nor their
spectra were excited by a depolarized beam, some modes may
be suppressed while others are enhanced, depending on a crys-
tal orientation. Our fitting yielded more peaks than were
recognized by Kharbish & Andráš (2014), who omitted seve-
ral shoulders that are clearly pronounced in our spectra as dis-
tinct peaks. Large discrepancies in the intensities of presumably
equivalent vibrations in their spectra are likely caused by
the different crystal orientation to the incident beam. In addi-
tion, our samples represent syntaxially grown zones (optical
observations), thus the spectra are similar, and corresponding
vibrational modes are believed to be equally pronounced.
Sample
h.no.
Fe
Sb
As
Bi
Cu
S
Zn
Pb
Total
4 RV-Z-1
6
2.49
30.89
0
4.94
0.29
21.11
0
39.32
99.04
4 RV-Z-1
6
2.53
31.41
0.04
4.47
0.29
21.02
0.04
38.97
98.79
4 RV-Z-1
6
2.49
29.13
0.08
7.45
0.19
20.87
0.01
38.82
99.02
4 RV-Z-1
6
2.40
28.86
0.05
7.98
0.25
20.61
0.02
38.22
98.40
4 RV-Z-1
6
2.54
31.44
0
3.30
0.24
21.10
0.04
39.44
98.10
4 RV-Z-1
6
2.50
31.46
0.04
3.95
0.51
21.13
0.03
39.04
98.65
4 RV-Z-1
6
2.40
29.89
0.04
6.25
0.32
21.12
0.05
39.22
99.29
108-4466
10
2.19
26.84
0.09
11.78
0.86
20.64
0
37.86
100.27
108-4466
10
2.10
25.90
0.02
12.71
1.90
20.69
0.05
36.82
100.19
Formula based on 11 cations
4 RV-Z-1
6
0.95
5.40
0.00
0.50
0.10
14.01
0.00
4.04
4 RV-Z-1
6
0.97
5.49
0.01
0.46
0.10
13.96
0.01
4.00
4 RV-Z-1
6
0.96
5.15
0.02
0.77
0.06
14.00
0.00
4.03
4 RV-Z-1
6
0.94
5.15
0.01
0.83
0.08
13.97
0.01
4.01
4 RV-Z-1
6
0.97
5.51
0.00
0.34
0.08
14.04
0.01
4.06
4 RV-Z-1
6
0.95
5.48
0.01
0.40
0.17
13.98
0.01
4.00
4 RV-Z-1
6
0.91
5.24
0.01
0.64
0.11
14.04
0.02
4.04
108-4466
10
0.85
4.76
0.03
1.22
0.29
13.91
0.00
3.95
108-4466
10
0.81
4.57
0.01
1.31
0.64
13.85
0.02
3.81
Table 3: Electron microprobe analyses of Bi bearing jamesonite. H.no. — horizon number.
Sample
h.no.
Sb
Hg
As
Bi
Cu
S
Cd
Pb
Total
RV 2753
6
23.97
0
0
0
13.29
19.77
0.11
43.48
100.61
RV 2753
6
22.32
0.24
0
3.24
12.29
19.56
0
42.32
99.96
RV 2753
6
23.19
0.01
0.08
0.80
12.95
19.37
0
42.93
99.32
RV 2753
6
24.77
0
0.02
0
13.46
19.70
0.15
42.09
100.19
4 RV-Z-1
6
25.11
0.15
0.04
0
13.60
19.98
0
41.14
99.47
n=28
23.93
0.03
0.07
0.43
13.38
19.63
0.06
42.50
100.05
Formula calculated to sum Sb + Cu + Bi + Pb = 3
RV 2753
6
0.96
0
0
0
1.02
3.00
0.00
1.02
RV 2753
6
0.91
0.01
0
0.08
0.96
3.03
0
1.01
RV 2753
6
0.94
0.00
0.01
0.02
1.01
2.99
0
1.03
RV 2753
6
0.99
0
0.00
0
1.03
2.98
0.01
0.99
4 RV-Z-1
6
1.00
0.00
0.00
0
1.00
3.02
0
0.96
n=28
0.96
0.00
0.00
0.01
1.03
2.99
0.00
1.00
Table 4: Electron microprobe analyses of bournonite (n is average of 28 analyses).
H.no. — horizon number.
232
MIKUŠ, KONDELA, JACKO and MILOVSKÁ
GEOLOGICA CARPATHICA
, 2018, 69, 3, 221–236
For instance, in our berthierite spectrum we recognized five
distinct bands in the region of 110–60 cm
−1
, while in the spec-
trum of Kharbish & Andráš (2014), five bands are visible, but
only three of them were fitted. In the region 355–330 cm
−1
, we
have found 3 bands instead of the two of the former authors.
Their relative peak intensities of garavellite also differ from
ours. The most striking is missing of their dominant band at
214 cm
−1
in our spectra, while others are amplified. The spectra
of garavellite and berthierite of this study show similar band
shapes, and accordance between equivalent peaks is even
more apparent if “linked” through the Bi-berthierite with its
intermediate band frequencies. According to Wang et al.
(1994), Kharbish & Andráš (2014), the stretching and ben-
ding vibrations of sulphides are expected at 500–200 cm
−1
.
The 160–60 cm
−1
features in the region could be assigned to
lattice modes. Kharbish & Andráš (2014) tentatively attributed
spectral band at 347 cm
−1
in berthierite to the symmetrical
stretching of Sb–S. The band at 347 cm
−1
in our spectra causes an asymmetry of
broad band centred at 353 cm
−1
. The shoul-
der at 340 cm
−1
could be then assigned to
the antisymmetrical stretching of Sb–S.
Bismuth substitution for Sb2 in gara-
vellite affects also the length of Sb–S
bands in polyhedra — Sb–S distances
shortened from 2.716 Å of (Sb1–S)
ber
to
2.678 Å of (Sb1–S)
gar
(Bindi & Menchetti
2005), resulting in the upshift of vibra-
tional frequencies (Kharbish & Andráš
2014). In our spectra, this effect may be
pronounced by the separation of weak
peaks at 358 and 374 cm
−1
in Bi-berthierite,
or 357 and 370 cm
−1
in garavellite, from
the large peak at 353 to 346 cm
−1
,
attributed to the symmetrical stretching.
On the other hand, Bi-S bonds should
vibrate at a much slower rate than Sb–S
and downshift their frequencies — such
a trend is obvious at 353, 349 and 346
cm
−1
for berthierite, Bi-berthierite and
garavellite, respectively, likely linked to
increasing Bi-substitution in this direc-
tion. The effect of the higher mass of bis-
muth probably combines with increasing
interatomic distances, which are 2.774 Å
and 2.818 Å for (Sb2–S)
ber
(Lukaszewicz
et al. 2001) and (Bi–S)
gar
(Bindi & Men-
chetti 2005), respectively. For this reason,
the peak at 346 cm
−1
, regarded by Khar-
bish & Andráš (2014) as the antisym-
metrical stretching, may still be attributed
to the v1 symmetric stretching mode.
Generally, this high-frequency domain is
marked by downshifts, possibly pointing
to the prevailing influence of the mass of
Bi atom over shortening of Sb1–S distan-
ces. For the more precise band assignment
and interpretation of the vibrational spectra of this type of
mineral with complex structure, polarized Raman measure-
ments would be necessary.
The complex evolution of the Strieborná vein contains
various mineralogical stages where the siderite stage is older
than the quartz–sulphidic stage. Proposals for the siderite for-
mation are fairly different. Žák et al. (1991) and Radvanec et
al. (2004) connect the veins with the hydrothermal circulation
of metamorphic fluids which were probably mixed with
meteoric waters leaching Permian evaporites. This model sup-
poses the Variscan mineralization phase to be dominant and
the Alpine one less important. A completely different view is
offered by Hurai et al. (1998, 2002), presuming the siderite
mineralization in the Gemeric area to be formed from basinal
brines expelled during compression, linked to a continental
collision of the Alpine Orogeny. Several (at least two)
Fig. 9. Sb vs. Bi (apfu) plot for tintinaite–kobellite series from the Strieborná vein. Dashed
line represents a formal border between kobellite and tintinaite.
Fig. 10. Comparison of Sb / (Sb + Bi) (in apfu) ratios of kobellite–tintinaite series minerals
from the Strieborná vein in the Rožňava ore field with other occurrences in the Western
Carpathians (hydrothermal Sb-Au mineralization, siderite–sulphidic and massive sulphide
deposits). Data from Kupčík et al. (1969), Chovan et al. (1998), Majzlan & Chovan (1997),
Pršek & Mikuš (2006) and Klimko et al. (2009).
233
GARAVELLITE AND ASSOCIATED SULPHOSALTS FROM THE STRIEBORNÁ VEIN (ROŽŇAVA ORE FIELD)
GEOLOGICA CARPATHICA
, 2018, 69, 3, 221–236
quartz–sulphidic mineralization
stages containing two tetrahedrite
generations appear to be markedly
younger compared to the siderite
mineralization (Mesarčík et al.
1991; Sasvári & Maťo 1998). In
our study, tetrahedrite fills tension
joints and tension irregular seg-
ments within deformed vein bou-
dine structures (Fig. 2). Typically,
tetrahedrite from the Gemeric
Superunit has a low Bi content
(e.g., Pršek & Biroň 2007; Števko
et al. 2015). In the Strieborná vein
the last two mineralogical stages
(older and younger sulphosalts
asso ciations) are documented from
all mine levels where sulphosalts
appear exclusively in apical parts
of the vein body. The garavellite
relation to tetrahedrite is marked
by the corrosion edges of mine-
rals of the berthierite–garavellite
series which most probably origi-
nated after the tetrahedrite mine-
ralization by a late hydrothermal
solution probably enriched in Bi
and Sb.
It was possible to determine
the vertical zonality of sulphosalts
(i.e. Sb, Ag decrease and vs. Bi
increase with depth) in the Strie-
borná vein. Sb-enriched phases of
the younger sulphosalt association
(chalcostibite–stibnite–berthierite)
were not found deeper than the 10
th
mine horizon. In contrast, the older
sulphosalt association (tintinaite–
kobellite–Bi-jameso nite–bourno-
nite) is more abundant on deeper
mining levels. The typical feature
of the berthierite– garavellite series
is its linkage to tetra hedrite nests
above the 10
th
mine level. The pre-
sence of Sb (the younger sulpho-
salts stage) in the vein body has
been observed only in apical vein
parts located in metasandstones
and metapelites between the 6
th
and 8
th
mining levels. Garavellite
–berthierite and other sulphosalts
are not present on the 10
th
mine
level hosted in metavolcanic
rocks. The multiple tectonometa-
morphic reprocessing of the vein
body in the shear zone also
Sample
h.n.
Ag
Fe
Sb
Hg
Bi
Cu
S
Pb
Total
RV 2753
6
0.05
0.04
20.64
0.67
19.90
2.44
19.39
36.41
99.52
4 RV-Z-1
6
0.17
0.03
22.53
0.59
18.61
2.26
19.76
36.28
100.24
4 RV-Z-1
6
0.00
0.06
19.19
0.29
22.11
2.22
19.11
36.87
99.92
4 RV-Z-1
6
0.04
0.22
18.74
0.86
21.74
2.11
18.82
36.35
99.00
4 RV-Z-1
6
0.19
0.06
21.30
0.42
20.29
2.44
19.12
35.43
99.26
4 RV-Z-1
6
0.18
0.05
22.62
0.73
18.18
2.24
19.48
35.44
98.91
4 RV-Z-1
6
0.22
0.06
25.24
0.63
14.95
2.22
19.73
35.88
98.92
4 RV-Z-1
6
0.25
0.05
24.51
0.56
16.18
2.32
19.49
34.98
98.33
103-446
10
0.17
0.09
14.42
0.55
30.19
2.18
18.63
33.84
100.08
103-446
10
0.09
0.11
14.58
0.63
29.79
2.20
18.62
34.54
100.56
103-446
10
0.07
0.39
15.06
0.87
28.57
2.00
18.63
34.32
99.91
4 RV-Z-1
6
0
0.38
11.63
0.26
32.73
1.87
18.21
34.87
99.95
4 RV-Z-1
6
0
0.44
11.58
0.18
32.42
1.78
18.27
35.07
99.73
4 RV-Z-1
6
0
0.37
11.55
0.11
33.21
1.76
18.18
34.70
99.88
Formula calculated to sum Pb + Sb + Bi + Ag = 26
Sb / Sb + Bi
N
RV 2753
6
0.03
0.04
9.81
0.19
5.51
2.22
35.01
10.17
0.64
2.08
4 RV-Z-1
6
0.09
0.03
10.53
0.17
5.07
2.02
35.07
9.96
0.68
2.03
4 RV-Z-1
6
0.00
0.06
9.23
0.08
6.20
2.05
34.90
10.42
0.60
2.11
4 RV-Z-1
6
0.02
0.23
9.12
0.25
6.16
1.97
34.76
10.39
0.60
2.08
4 RV-Z-1
6
0.10
0.06
10.18
0.12
5.65
2.23
34.68
9.94
0.64
1.99
4 RV-Z-1
6
0.09
0.05
10.71
0.21
5.02
2.03
35.02
9.86
0.68
1.99
4 RV-Z-1
6
0.11
0.06
11.78
0.18
4.07
1.98
34.97
9.84
0.74
1.98
4 RV-Z-1
6
0.13
0.05
11.55
0.16
4.44
2.10
34.87
9.69
0.72
1.94
103-446
10
0.09
0.10
7.12
0.16
8.69
2.06
34.93
9.82
0.45
1.97
103-446
10
0.05
0.12
7.18
0.19
8.55
2.08
34.84
10.00
0.46
2.00
103-446
10
0.04
0.42
7.42
0.26
8.20
1.89
34.84
9.93
0.48
1.94
4 RV-Z-1
6
0.00
0.42
5.87
0.08
9.62
1.80
34.87
10.33
0.38
2.01
4 RV-Z-1
6
0.00
0.48
5.84
0.05
9.53
1.72
34.98
10.40
0.38
2.01
4 RV-Z-1
6
0.00
0.41
5.84
0.03
9.78
1.70
34.90
10.31
0.37
1.99
Table 5: Electron microprobe analyses of tintinaite and kobellite with calculated N. N (homologue
number) was calculated from the microprobe analyses by the following equation (Zakrzewski &
Makovicky 1986): N = x (6M
2+
+ 3M
3+
) / (4M
3+
− M
2+
) + (1 − x)(5M
2+
+ 2M
3+
) / (4M
3+
− M
2+
), where
x = T
+
/(T
+
+ T
2+
), (1 − x) = T
2+
/(T
+
+ T
2+
) and T
+
is content of Cu, T
2+
is content of divalent cations
(Fe), M
2+
is sum of divalent “large” cations (Pb) and M
3+
is sum of trivalent “large” cations (Sb+Bi).
Ag content was divided to M
2+
and M
3+
through “lillianite substitution” Ag + Bi = 2Pb.
H.n. — horizon number.
Sample
h. no.
Ag
Fe
Sb
Hg
As
Bi
Cu
S
Zn
Cd
Total
RV 2750
6
0.88
5.55
28.63
1.42
0.39
0.32
36.98
24.86
0.82
0.03
99.91
RV 2753
6
1.31
5.38
28.63
1.87
0.17
0.40
37.19
24.87
0.77
0.16
100.75
5RV-5-SOS
6
1.00
5.92
29.59
1.10
0.04
0.20
37.49
24.75
0.57
0.08
100.74
5RV-5-SOS
6
0.84
5.56
28.43
1.51
0.48
0.03
37.81
24.71
0.59
0.11
100.06
1 RV-Z-2
6
0.91
5.91
28.88
1.15
0.41
0
37.30
24.64
0.66
0.10
99.96
1 RV-Z-2
6
0.87
5.78
28.94
0.99
0.37
0
37.21
24.31
0.66
0.06
99.18
n = 90
0.90
5.52
28.38
1.18
0.61
0.09
37.50
24.72
0.87
0.05
99.87
Formula based on 29 apfu
RV 2750
6
0.14
1.67
3.95
0.12
0.09
0.03
9.77
13.02
0.21
0.01
RV 2753
6
0.20
1.61
3.94
0.16
0.04
0.03
9.80
12.99
0.20
0.02
5RV-5-SOS
6
0.15
1.77
4.06
0.09
0.01
0.02
9.85
12.89
0.15
0.01
5RV-5-SOS
6
0.13
1.67
3.91
0.13
0.11
0.00
9.97
12.91
0.15
0.02
1 RV-Z-2
6
0.14
1.77
3.98
0.10
0.09
0.00
9.84
12.88
0.17
0.02
1 RV-Z-2
6
0.14
1.75
4.02
0.08
0.08
0.00
9.91
12.83
0.17
0.01
n = 90
0.14
1.66
3.91
0.10
0.14
0.01
9.89
12.92
0.22
0.01
Table 6: Electron microprobe analyses of tetrahedrite (n is average of 90 analyses). H.no. — horizon
number).
234
MIKUŠ, KONDELA, JACKO and MILOVSKÁ
GEOLOGICA CARPATHICA
, 2018, 69, 3, 221–236
facilitates ascent of hydrothermal fluids to rheologically
contrasting environments. The association of the tintinaite–
kobellite series (with Bi > Sb) — Bi-jamesonite belongs to the
end of the first sulphidic mineralization stage which is typical
for the entire Gemeric Superunit. Later on, the older sulpho-
salt stage was overprinted by a younger one with the increased
Sb content. Berthierite–garavellite series
and stibnite–bismuthinite series were
formed together. This stage corresponds to
the younger quartz–stibnite stage (Varček
1985; Hurai et al. 2008) which is well
documented in nearby Sb deposits of
the so called “stibnite belt” in the Gemeric
unit, ranging from Betliar to Zlatá Idka
(e.g., Klimko et al. 2009; Pršek & Lauko
2009).
The source of increased Sb content in
the fluids responsible for the formation
of the younger sulphosalt association
could be related to the remobilization or
deve lopment of the nearby Sb deposit
in Čučma. Beside the sulphosalt asso-
ciations, the vein filling of the Strie-
borná also contains at least two
gene rations of arsenopyrite, pyrite and
quartz. The outlined succession scheme
in Figure 4 reflects the multi-stage evo-
lution of the quartz-sulphidic minera li-
zation. We assume that different
para geneses could reflect structural
events in the shear zone, which are also
responsible for the complicated morpho-
logy of the Strieborná vein and other veins
in the Rožňava ore field.
Conclusions
The hydrothermal siderite and younger
quartz–sulphide mineralization in the
Strieborná vein was related to hydro-
thermal activity along the Transgemeric
shear zone during Cretaceous. The sul-
phide mineralization is dominated by
sulphosalts, the berthierite–garavellite
series. This study has determined compo-
sitional changes of this series with depth
and has confirmed the first complete con ti -
nuous series from berthierite (Fe
1.0
Sb
1.98
S
3.98
)
to garavellite (Fe
0.97
Sb
1.06
Bi
0.91
S
4.01
) through
the Bi-berthierite in the Western Car-
pathians and worldwide. The two sulpho-
salt stages include early association of
tintinaite–kobellite series — Bi-jamesonite
–bournonite–tetrahedrite and the later
association formed by chalcostibite–
berthierite–garavellite series — “horobet-
suite” (Bi-stibnite, Sb-bismuthinite) – native
Bi - stibnite.
Sample
h.no.
Ag
Fe
Sb
Hg
As
Bi
Cu
S
Total
RV 2750
6
0.02
0.87
49.19
0
0.02
0
24.84
25.10
100.04
RV 2750
6
0
0.90
49.02
0.02
0.13
0.10
24.99
25.15
100.32
RV 2750
6
0.02
0.39
47.28
0.07
0.01
1.78
25.34
24.93
99.90
RV 2750
6
0.01
0.60
45.52
0.07
0.10
2.36
25.15
25.64
99.46
RV 2750
6
0.03
0.36
47.68
0
0
0.34
25.58
24.87
98.87
n=10
0.02
0.78
48.15
0.03
0.06
1.04
24.72
25.33
100.17
PJ-5B
8
0.01
0.11
36.15
0
0.15
14.3
24.20
24.8
99.00
PJ-5B
8
0
0.09
36.72
0
0.02
15.9
24.41
24.21
100.53
PJ-5B
8
0
0.16
36.37
0
0.02
15.46
24.17
23.89
100.01
Formula calculated to sum Sb + Cu + Bi = 2
RV 2750
6
0.00
0.04
1.01
0.00
0.00
0.00
0.98
1.96
RV 2750
6
0.00
0.04
1.01
0.00
0.00
0.00
0.98
1.96
RV 2750
6
0.00
0.02
0.98
0.00
0.00
0.02
1.01
1.97
RV 2750
6
0.00
0.03
0.94
0.00
0.00
0.03
0.99
2.01
RV 2750
6
0.00
0.02
0.99
0.00
0.00
0.00
1.02
1.97
n=10
0.00
0.04
0.99
0.00
0.00
0.01
0.98
1.98
PJ-5B
8
0.00
0.01
0.79
0.00
0.01
0.18
1.01
2.00
PJ-5B
8
0.00
0.00
0.80
0.00
0.00
0.19
1.01
1.99
PJ-5B
8
0.00
0.01
0.80
0.00
0.00
0.20
1.01
1.98
Table 7: Electron microprobe analyses of chalcostibite and Bi-chalcostibite (sample PJ-5B,
no. 26, 27, 28). N is average of 10 analyses. H.no. — horizon number.
Sample
h.no.
Fe
Sb
Bi
Cu
S
Pb
Total
RV 2750
6
0.46
70.51
0
1.13
28.13
0
100.21
RV 2750
6
0.59
70.34
0.07
0.33
27.62
0.10
99.09
5 RV-5
6
0.84
62.70
8.17
0.06
27.12
0.64
99.65
RV 2750
6
0.71
38.84
35.82
1.31
23.78
0.07
100.52
RV 2754
6
1.45
37.82
36.07
1.31
23.55
0.30
100.54
RV 2754
6
1.65
37.29
35.53
1.73
23.11
0.18
99.54
RV 2750
6
0.72
32.70
43.25
1.12
22.48
0.14
100.43
RV 2754
6
0.19
16.48
59.21
1.80
20.38
0.11
98.26
RV 2754
6
0.18
15.27
63.94
1.14
20.87
0.16
101.56
5 RV-5
6
0.34
11.64
67.76
0.18
21.80
0
101.00
S-3B
8
0.17
6.58
74.86
0.15
19.83
0
101.58
4 RV-Z-1
6
0.06
0.29
81.03
0.49
18.57
0.35
100.76
Formula calculated to sum Sb + Cu + Bi = 2
RV 2750
6
0.03
1.95
0.00
0.06
2.96
0.00
RV 2750
6
0.04
1.98
0.00
0.02
2.96
0.00
5 RV-5
6
0.05
1.81
0.14
0.00
2.97
0.01
RV 2750
6
0.05
1.26
0.68
0.08
2.93
0.00
RV 2754
6
0.10
1.23
0.68
0.08
2.90
0.01
RV 2754
6
0.12
1.22
0.68
0.11
2.87
0.00
RV 2750
6
0.05
1.11
0.86
0.07
2.90
0.00
RV 2754
6
0.02
0.62
1.30
0.13
2.92
0.00
RV 2754
6
0.01
0.57
1.39
0.08
2.95
0.00
5 RV-5
6
0.03
0.44
1.49
0.01
3.02
0.00
S-3B
8
0.01
0.26
1.73
0.01
2.98
0.00
4 RV-Z-1
6
0.01
0.01
1.98
0.04
2.95
0.01
Table 8: Electron microprobe analyses of antimonite, antimonite–bizmuthinite solid
solution (“horobetsuite”) and bizmuthinite. H.no. — horizon number.
235
GARAVELLITE AND ASSOCIATED SULPHOSALTS FROM THE STRIEBORNÁ VEIN (ROŽŇAVA ORE FIELD)
GEOLOGICA CARPATHICA
, 2018, 69, 3, 221–236
The chemistry of sulphosalts changes with depth: the anti-
mony content decreases while Bi content increases.
The Raman spectra were obtained and interpreted for
representative phases (berthierite, Bi-berthierite and gara-
vellite). The Raman spectroscopy revealed the peak shifts
that depend on an elemental substitution and helped link
the equivalent peaks of garavellite and berthierite through
Bi-berthierite.
Acknowledgements: We are thankful to the handling editor
Dr. Peter Koděra and anonymous reviewers for constructive
critical comments which helped to improve the MS. This work
was financially supported by the VEGA project (2/0023/17)
and by the Operational Programme Research and Develop-
ment through the projects ITMS: 26220120064 and ITMS:
26210120013, which have been co-financed through the Euro-
pean Regional Development Fund.
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