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Origin of ferroan alabandite and manganoan

sphalerite from the Tisovec skarn, Slovakia

Article in Neues Jahrbuch für Mineralogie - Abhandlungen · April 2011

DOI: 10.1127/0077-7757/2011/0183

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 N. Jb. Miner. Abh. 188/2, 119–134 Article
Published online January 2011

Origin of ferroan alabandite and manganoan sphalerite from

the Tisovec skarn, Slovakia

Vratislav Hurai, Monika Huraiová

With 9 figures and 4 tables

Abstract: Sulphidic skarn in an exo-contact zone between diorite and Triassic carbonates contains the Mn-rich minerals ferroan
alabandite (Mn0.84-0.89Fe0.11–0.16S), manganoferroan sphalerite (Zn0.37–0.76Mn0.01–0..36Fe0.22–0.28S), hübnerite, manganoan magnesiohorn-
blende, and Mn-carbonates. The Mn-content in sphalerite (up to 21.4 wt. %) is the highest ever recorded in hydrothermal settings.
Magnetite and sulphides like galena, pyrite, pyrrhotite, arsenopyrite are also present. Anhydrite is ubiquitous as inclusions in
sulphide minerals and crystals in drusy cavities, postdating hydrothermal Ca-Mn-Fe carbonates. Primary aqueous inclusions with
variable salinity (2.9–44.8 wt. % NaCl eq.) occur in sphalerite and Mn-calcite. The fluid inclusions locally exhibit textural evidence
for heterogeneous entrapment of boiling fluids. Crystallization temperatures of 300–350 °C were obtained from various mineral
geothermometers, δ34S values in coexisting galena and sphalerite, and infrared fluid inclusion microthermometry. The observed
anhydrite-chalcopyrite-magnetite-pyrrhotite-arsenopyrite-alabandite assemblage constrains fO2 and fS2values to –34.5 ± 1.5 and
–12.5 ± 0.5 log units, respectively, at 300 °C and atmospheric pressure. Together with an assemblage of silicate minerals (chlorite,
sericite, K-feldspar, hyalophane) and high-salinity fluids, the calculated oxygen and sulphur fugacities are consistent with an inter-
mediate sulphidation hydrothermal system. The increased δ34S values of the ore-forming fluids, 2–2.5 ‰, result from the disequi-
librium isotopic exchange between mantle-derived H2S and marine sulphate.

Key words: alabandite, manganoan sphalerite, skarn, sulphur isotopes, infrared microthermometry, Western Carpathians

1. Introduction town (Fig. 1) revealed massive sulphide ores with hitherto

The ore deposits near Tisovec town in central Slovakia
are an example of ancient mining sites, from where mod-
ern analytical data are not available. In spite of preserved
remnants of mining activity (smelters, dumps, slag heaps,
adits), as well as local geographic names reminiscent of
the exploitation of iron and silver ores, only few descrip-
tions are available, the latest dated 38 years ago. The
oldest written record from the beginning of 17th century
mentions private lead mining works conveyed to estate
ownership. Other documents refer to iron ore exploitation
around 1752, and its decline in 1864 (EISELE 1907), subse-
quent resurgence and final breakup of the mining activity
in 19th century (PAPP 1919). Present knowledge is mainly
based on reconnaissance studies and geological mapping
in the middle of 20th century (ADAM et al. 1956, BACSÓ
1964).
Investigation of dump materials on the eastern slopes
of the Magnetový vrch hill, 5 km northwest of Tisovec
© 2011 E. Schweizerbart’sche Verlagsbuchhandlung, Stuttgart, Germany
DOI: 10.1127/0077-7757/2011/0183
eschweizerbart_xxx
unknown Mn-rich mineralization. The sulphide assem-
blage includes ferroan alabandite associated with manga-
noferroan sphalerite with extremely high Mn content, up
to 0.36 apfu. Apart from description of mineral paragene-
sis, the present study aims to characterize thermodynamic
parameters and origin of the ore-forming fluid, employing
mineral thermobarometers, fluid inclusion infrared mi-
crothermometry, thermodynamic modelling and sulphur
isotopes. The obtained data will be compared with other
skarn occurrences of the Western Carpathians.
2. Geological setting and previous works
The mining area near Tisovec exhibits complex and still
unresolved geological structure composed of: 1. Variscan
crystalline basement of the Veporic unit (granitoids, bio-
titic paragneiss with intercalations of acid metavolcanic
rocks), 2. weakly metamorphosed autochthonous sedi-
www.schweizerbart.de
0077-7757/2011/0183 $ 4.00
120 V. Hurai and M. Huraiová

Fig. 1. Map of old mining works northwest of Tisovec town (BACSÓ 1964) with simplified geological background: 1 – Neogene andesite,
2 – post-Triassic diorite, 3 – Variscan granite and granodiorite of the Veporic unit, 4 – Mesozoic sediments, mainly carbonates, of the Silica
unit and the Veporic cover sequences, 5 – thrusting planes. Asterisk denotes location of dumps with samples studied (GPS coordinates:
latitude 48° 43′ 8″ N, longitude 19° 53′ 48″ E, altitude 765 meters above sea level). Abbreviations in inset: T – Tatric, V – Veporic, G – Ge-
meric tectonic units.

mentary cover of the Veporic unit (arkose, quartzite), 3.
Carboniferous-Triassic sediments (phyllite, sandstone,
conglomerate, quartzite) of the Gemeric unit, 4. Middle-
Upper Triassic limestones and dolomites as a part of the
Silica nappe. All these elements are intruded by post-Tri-
assic diorites along E-W oriented faults, and by Badenian
volcanic rocks (PÉCSKAY et al. 2006), mainly andesites,
along younger NW-SE to N-S trending faults (BACSÓ
1964, VOJTKO 1999).
Iron-bearing accumulations near Tisovec were as-
signed to a group of contact-metasomatic skarn deposits
(ADAM et al. 1956). Magnetite- and garnet-bearing skarns
formed along contacts between diorite intrusion and Tri-
assic marly limestone (Fig. 1). Polymetallic Fe-Pb-Zn
ores precipitated during a hydrothermal sulphidic stage
at a greater distance from the intrusion contact. Evidence
of pneumatolytic-exhalative processes and contact meta-
somatism are found also at a greater distance from the
skarn deposits as macroscopic needles and aggregates of
schorl tourmaline along foliation planes of Carboniferous
quartzite and arkose.
Mineralogical studies carried out on magnetite and
garnet–bearing skarns focused on the optical proper-
ties and chemical composition of anisotropic garnets

eschweizerbart_xxx
 Origin of ferroan alabandite 121

(ŠAMAJOVÁ 1966, 1972). A total of three mineralization
stages have been distinguished: 1) rare high-temperature
anorthite-magnetite predating the main skarn formation
(ŠAMAJOVÁ 1968), 2) skarn-forming stage with pyroxene,
garnet, sporadic vesuvianite and wollastonite, postdated
by epidote and magnetite, 3) post-skarn carbonate-quartz-
sulphidic hydrothermal stage with pyrrhotite, sphalerite,
galena, pyrite, marcasite, chalcopyrite and Mn-Fe carbon-
ates. Gangue minerals of the latest stage are represented
by quartz, chlorite, and calcite, and in places also by zeo-
lites (ŠAMAJOVÁ 1965). Main sulphidic minerals (pyrite,
pyrrhotite, chalcopyrite) were characterised by means of
X-ray powder diffraction and quantitative optical emis-
sion spectrography (CAMBEL & JARKOVSKÝ 1967, 1969).
Structural state and sulphur isotope composition of pyr-
rhotite from the Leopold adit was studied by KANTOR &
ĎURKOVIČOVÁ (1977).
3. Analytical techniques
Mineral compositions were measured in polished carbon-
coated thin sections by WDS analysis using a CAMECA
SX-100 electron microprobe at the Geological Survey,
Bratislava, at the following analytical conditions: 15 kV
acceleration voltage for silicates, 20 kV for sulphides, 10–
15 nA sample current for silicates, 20 nA for sulphides,
10–15 s counting times and 5 μm beam diameter. The
following standards were used: albite (Na), wollastonite
(Si, Ca), orthoclase (K), fayalite (Fe), chalcopyrite (Fe,
Cu and S in sulphides), rhodonite (Mn in silicates), chro-
mite (Cr), barite (Ba), synthetic SrTiO3 (Sr), Al2O3 (Al),
MgO (Mg), TiO2 (Ti), Mn, Co, Ni, Ag, Bi, ZnS (Zn), Cd,
BaF2 (F), NaCl (Cl), Sb2S3 (Sb), InSb (In), FeAsS (As).
Conventional correction (ARMSTRONG 1988) was used for
conversion of raw data to wt. % of elements and oxides.
Fluid inclusions were studied in 90–100 μm thick,
doubly polished wafers using an OLYMPUS BX-51IR
microscope equipped with a 1.2 mm Hitachi KP-161 in-
frared CCD camera at Comenius University, Bratislava.
A LINKAM THMSG-600 freezing-heating stage enabled
microthermometric measurements of phase transitions.
The freezing-heating stage was calibrated using natural
and synthetic fluid inclusions. Accurracy of IR-microther-
mometric measurements was checked in sphalerite-host-
ed fluid inclusions from another locality, visible in both
VIS and NIR spectral ranges. The accuracy of tempera-
ture measurements was ±0.1 °C in the temperature range
between –100° and +100 °C, and ±0.2 °C at greater tem-
peratures.
Sulphide grains carefully selected under binocular
microscope were powdered in agate mortar, mixed with
CuO and annealed in vacuum at 320 °C for 30 minutes
to remove volatile impurities. The evacuated and purified
sample was then combusted at 770 °C for 30 minutes.
The liberated SO2 gas was purified in cryogenic traps and

Table 1. Overview of mineral phases identified in the samples studied.

Mineral Composition Intergrowths Mode of occurrence
Apatite Fluorapatite (0.44 apfu Mn, 1.1 wt. % F) Ttn inclusions in Gn
Alabandite Mn0.84-0.89Fe0.11-0.16S (Table 2) Mn-Sp, Po isolated grains, inclusions in Gn,
Amphibole Manganoan magnesiohornblende (LEAKE et al. 1997, Table 3) inclusions in Py
Anglesite PbSO4 product of Gn weathering
Anhydrite CaSO4 Dol, Chl, Ms inclusions in Py, drusy cavities in
carbonate veinlets
Arsenopyrite FeAsS (Table 2) Gn aggregates
Dolomite CaMg(CO3)2 Chl, Ms, Anh inclusions in Py
Galena PbS Po, Mn-Sp aggregates
Hübnerite (Mn0.9Fe0.1)WO4 Gn, Mn-Sp, Py inclusions in Rds
Hyalophane (K0.7Ba0.21Na0.08Fe0.03)Al1.18Si2.8O8 (Table 3) inclusions in Py
Chalcopyrite CuFeS2 Po, Sp aggregates, inclusions in Py and Sp
Chlorite Mg-chlorite (WIEWIÓRA & WEISS 1990, Table 3) Dol, Ms, Anh inclusions in Py
Mn-carbonates Mn-calcite, Mn-siderite, rhodochrosite veinlets
Pyrite FeS2 Fe-Sp, Po metacrystals in Sp-Po matrix
Pyrrhotite Fe0.88-0.91S (Table 2) Sp, Gn aggregates, inclusions in Gn
Sphalerite Zn0.37-0.76Mn0.01-0.36Fe0.22-0.28S (Table 2) Po, Gn, Alb aggregates, inclusions in Gn
Titanite CaTiSiO5 (0.13-0.14 apfu Al, 0.5-1.24 wt. % F) Ap inclusions in Gn
White mica Muscovite s.s. (TISCHENDORF et al. 2007, Table 3) Dol, Anh, Chl inclusions in Py

Abbreviations (WHITNEY & EVANS 2010): Alb – alabandite, Anh – anhydrite, Ap – apatite, Chl – chlorite, Dol – dolomite, Gn – galena, Ms
– muscovite, Po – pyrrhotite, Py – pyrite, Rds – rhodochrosite, Sp – sphalerite, Ttn – titanite.

eschweizerbart_xxx
122 V. Hurai and M. Huraiová

Table 2. Representative electron microprobe analyses (wt. %) of alabandite, arsenopyrite, pyrrhotite and sphalerite.

Anal. # 5/7 5/5 6b 6a 10/1 10/2 4/1 5/1-1 5/8 5/4 5/3 9a
Phase Alb Alb Alb Alb Asp Asp Po Po Po Mn-Sp Mn-Sp Fe-Sp
in Gn in Gn in Gn in Gn in Gn in Gn
Fe 9.02 8.60 10.33 9.44 34.88 34.98 60.37 61.30 60.82 16.33 16.85 13.09
Co 0.06 0.05 0.10 0.08
Mn 53.98 54.02 52.35 53.69 1.20 1.04 0.03 20.21 21.38 0.71
Ag 0.02 < mdl 0.02 0.04 0.04 < mdl
Zn 0.02 < mdl < mdl < mdl < mdl 27.35 26.12 51.67
Cd 0.04 0.03 0.02 0.08 0.02 0.31 0.32 0.30
Sb 0.03 < mdl nd nd 0.03 < mdl < mdl 0.06 < mdl 0.13 0.06
Cu < mdl 0.03 < mdl < mdl < mdl < mdl 0.02 0.02 < mdl < mdl < mdl 0.40
In 0.06 0.04 < mdl 0.02 < mdl 0.12 0.05 0.04
Bi 0.23 0.07
As 43.56 44.32 < mdl 0.08
S 36.72 36.48 36.87 36.81 20.74 20.86 39.26 38.78 38.98 34.79 34.94 33.57
Total 99.89 99.22 99.59 100.05 100.47 101.48 99.85 100.32 99.88 99.29 99.71 99.78
Formula proportions on the basis of 1S-
Fe 0.141 0.135 0.161 0.147 0.966 0.963 0.883 0.908 0.896 0.270 0.277 0.224
Co 0.002 0.001 0.001 0.001
Mn 0.858 0.864 0.829 0.851 0.034 0.029 0.000 0.339 0.357 0.012
Ag 0.000 0.000 0.000 0.000 0.000 0.000
Zn 0.000 0.000 0.000 0.000 0.000 0.386 0.367 0.755
Cd 0.000 0.000 0.000 0.001 0.000 0.003 0.003 0.003
Sb 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.001 0.000
Cu 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.006
In 0.000 0.000 0.000 0.000 0.001 0.000 0.000
Bi 0.002 0.000
As 0.899 0.909 0.000 0.001
Total 1.001 1.001 0.990 0.999 1.900 0.995 0.885 0.910 0.897 0.999 1.004 1.000

< mdl – less than minimum detection limit

Table 3. Representative electron microprobe analyses of chlorite, muscovite, amphibole and K-feldspar inclusions in pyrite.

Phase Chl Chl Ms Ms Am Am Kfs Kfs Kfs Kfs

dark pale
SiO2 30.66 27.17 51.12 52.25 51.42 50.08 57.10 56.75 63.95 64.48
TiO2 0.09 0.03 0.02 0.01 0.02 0.04
Al2O3 20.50 24.86 33.27 32.59 5.20 4.54 20.35 20.34 18.65 18.27
Cr2O3 0.02 < mdl 0.04 0.03 < mdl 0.01
NiO 0.02 0.05 < mdl < mdl 0.03 0.04
FeO 3.19 6.67 1.28 2.33 9.62 7.70 0.49 0.63 0.68 0.60
MnO 0.30 1.86 0.02 0.04 5.31 4.92
SrO 0.06 0.02 0.06 0.02
BaO 10.32 10.61 0.08 0.70
CaO 0.01 < mdl 0.27 0.47 12.52 14.30 0.05 0.02 0.47 0.08
MgO 32.30 26.57 0.93 1.07 13.70 14.43 0.10 < mdl 0.01 0.15
K2O 0.01 < mdl 8.58 7.82 0.21 0.15 10.89 11.12 14.70 15.01
Na2O < mdl 0.01 0.04 0.06 0.56 0.54 1.03 0.82 0.79 0.42
F < mdl 0.14 0.17
Cl < mdl < mdl
Total 87.10 87.22 95.58 96.66 98.58 96.92 100.39 100.31 100.11 99.74

< mdl – less than minimum detection limit

eschweizerbart_xxx

sealed in breakable glass vial. Measurement of sulfur iso-
tope ratios were performed using a FINNIGAN MAT 250
mass spectrometer at Geological Survey, Bratislava. The
isotopic ratios were expressed in δ-notation as ‰ differ-
ence from the international V-CDT standard. Standard er-
ror is within ±0.01 % of the obtained value.
4. Mineral compositions and assemblages
The sulphide mineralization studied occurs in white-to-
grey fine-grained marly limestones and marbles. Samples
collected from dumps are represented by massive ores
dominated by pyrrhotite, sphalerite, and pyrite. List of
identified mineral phases and their representative electron
microprobe analyses are in Tables 1–3.
Pyrrhotite creates coarse-grained aggregates inter-
grown with sphalerite and galena (Fig. 2a, b) or rounded
inclusions in galena in association with alabandite and
Mn-sphalerite (Fig. 2c). Weak iron deficiency and in-
creased Co (0.14 wt. %), As (0.18 wt. %) and Mn (0.17 wt.
%) contents are diagnostic for all pyrrhotite types. X-ray
powder diffraction of pyrrhotites from the Leopold adit
and their reflected light images in magnetite suspension
(KANTOR & ĎURKOVIČOVÁ 1977) revealed complex domain
texture of the hexagonal pyrrhotite with lamellae and
elongated blebs of monoclinic pyrrhotite. The hexagonal
pyrrhotite is often replaced by the monoclinic pyrrhotite
along grain boundaries. This type of replacement is dis-
cernible also in BSE images of our samples (Figs. 2a, b).
Massive sulphide ores often contain large pyrite hexa-
hedrons embedded within fine-grained pyrrhotite-sphal-
erite matrix (Fig. 2d). A large number of inclusions were
identified in the pyrite: manganoan magnesiohornblende
(7.1–7.4 apfu Si, 0.44–0.65 apfu Mn2+, Mg/Mg+Fe2+ =
0.7–0.8), galena, anhydrite, Mg-chlorite, dolomite, mus-
covite, hyalophane, potassium feldspar and titanite. Two
types of Mg-chlorites were distinguished in BSE images
of composite aggregates: brighter chlorite with 0.47–0.54
Fe2+, 1.38–1.45 AlIV, and 3.82–4.01 Mg apfu, darker chlo-
rite with 0.21–0.25 Fe2+, 1.16–1.26 AlIV, and 4.43–4.55
Mg apfu (Fig. 2e).
Sphalerite is abundant sulphide in massive ores. Black
isometric grains of sphalerite create coarse-grained aggre-
gates intergrown with pyrrhotite (Fig. 2b). Some grains
exhibit gradual increase in Mn content toward margins
(Fig. 2f). The Mn-rich sphalerite is obviously associ-
ated with galena (Fig. 2f), in which it is also enclosed as
rounded inclusions intergrown with alabandite (Fig. 2 g)
and closely spatially associated with pyrrhotite (Fig. 2c).
Mn-sphalerite from intergrowths with alabandite exhibits
extremely high Mn contents, up to 21.4 wt. %, while the
eschweizerbart_xxx
Origin of ferroan alabandite 123
Mn concentrations in the matrix sphalerite are lower, at-
taining 18.8 wt. %. Matrix and inclusion sphalerites show
uninterrupted transition from ferroan (Zn0.76Fe0.22Mn0.01S)
to manganoferroan (Zn0.37Mn0.36Fe0.28S) compositions.
Alabandite creates rounded inclusions in galena
(Fig. 2c) and isolated grains associated with galena and
Mn-sphalerite in massive sulphide ores. The galena-host-
ed inclusions are sometimes intergrown with Mn-sphal-
erite (Fig. 2 g). Iron contents vary between 6.9 and 10.4
wt. %, without any systematic compositional difference
between the matrix and the inclusion alabandites.
Other sulphide minerals, arsenopyrite (closely associ-
ated with galena) and chalcopyrite are present in minor
amounts. Iron oxides are represented by magnetite, which
creates isolated grains in the sulphide matrix. Hematite
was not observed.
Sulphate assemblage consists of anhydrite and an-
glesite. Anglesite replaces galena along grain boundaries
and it probably originated during supergene alteration
of primary ores. In contrast, anhydrite is primary hydro-
thermal mineral. Irregular anhydrite inclusions are ubiq-
uitous in pyrite metacrystals, where they are closely as-
sociated with chlorite and dolomite-muscovite aggregates
(Fig. 2d). Anhydrite was observed also as the latest min-
eral phase in drusy cavities in Mn-carbonates (Fig. 2h).
5. Fluid inclusion microthermometry
Primary fluid inclusions in sphalerite exhibit irregular
to negative crystal shapes. Most frequent are two-phase
inclusions composed of aqueous solution and a vapour
bubble. Multiphase aqueous inclusions with several trans-
parent and opaque daughter crystals are less abundant.
Essentially gas inclusions devoid of optically discernible
water also occur. Secondary inclusions arranged along
healed fractures are represented only by two-phase aque-
ous inclusions with consistent volume fraction of vapour
phase (5–15 vol. %).
Phase changes in multiphase inclusions are illustrated
in Fig. 3. Low temperature phase transitions in multiphase
inclusions are unknown, because they failed to freeze out
at any temperature down to –190 °C. Phase transition
sequence on heating above 25 °C is as follows: LVS1S2
→ LVS1 277–303 °C→ LS1 308–380 °C→ L, where LVS1S2
69 –190 °C
designates aqueous liquid, vapour bubble, solid phase 1
and solid phase 2, respectively. The isotropic transparent
soluble daughter phases probably correspond to sylvite
(S2) and halite (S1).
Unlike multiphase inclusions, two-phase aqueous in-
clusions froze out readily on cooling. Eutectic melting
was observed between –21 and –49 °C. Temperatures of
ice melting varied between –1.7 and –15 °C. Metastable
hydrohalite melting between 20–28.7 °C was observed in
124 V. Hurai and M. Huraiová

Fig. 2. Back-scattered elec-

tron images of ores in the
Tisovec skarn. a) Galena
(Gn) enclosed in massive
hexagonal pyrrhotite (Po-
hex.) aggregate replaced by
monoclinic pyrrhotite (Po-
mon.) along grain bounda-
ries. b) Equi-granular
pyrrhotite-sphalerite aggre-
gate, with galena inclusions in Fe-sphalerite (Sp) and hexagonal pyrrhotite replaced by monoclinic pyrrhotite along grain boundaries. c)
Rounded alabandite (Alb) and pyrrhotite (Po) inclusions in galena. d) Pyrite crystal in fine-grained sulphide matrix. Numerous solid inclu-
sions in the crystals are galena (bright), anhydrite (grey), and dolomite-muscovite aggregates (dark inhomogeneous specks). e) Anhydrite-
chlorite (Chl) aggregate enclosed in pyrite crystal. f) Zoned sphalerite grain showing gradual change from Mn-poor ferroan sphalerite in
centre to manganoferroan sphalerite at margin. Apparent inhomogeneities of the sphalerite grain are caused by scratched carbon coating.
g) Intergrowth of ferroan alabandite and manganoan sphalerite in galena. h) Drusy cavity in massive sulphidic ore filled with manganoan
calcite (Mn-Cal), manganoan siderite (Mn-Sd) and anhydrite (Anh). Inset shows brightness-contrast-enhanced image documenting oscil-
latory zoning of the Mn-calcite.

eschweizerbart_xxx
 Origin of ferroan alabandite 125

Fig. 3. Infrared images of primary fluid inclusions in Fe-sphalerite. a) Two-phase inclusion containing aqueous liquid (L) and vapour (V)
phases. b) Group of multiphase brine inclusions with consistent phase ratios. c-f) Sequence of phase transitions on heating. Abbreviations:
V – vapour bubble, L – aqueous liquid, S1- solid phase, probably halite, S2 – solid phase, probably sylvite.

eschweizerbart_xxx
126 V. Hurai and M. Huraiová

Fig. 4. Correlation of total homogenization temperature with salinity in aqueous inclusions. Halite saturation curve and densities of vapour-
saturated NaCl-H2O solutions are from BODNAR (1983).

some two-phase inclusions with high salt content. Total 6. Sulphur isotopes
homogenization to liquid occurred at 204–306 °C.
Eutectic melting between –21 and –30 °C corresponds A total of 19 sulphide samples have been selected for mass
to stable and metastable eutectic temperatures in the H2O- spectrometric determination of 34S/32S isotope ratios. The
NaCl-KCl system; lower temperatures indicate additional obtained δ34S values range between –1.3 and 0.5 ‰ for
Fe-, Mg- and Ca chlorides (BORISENKO 1977). Total salt galena, at 2.3–2.9 ‰ for sphalerite, 1.5–2.4 ‰ for chalco-
contents varied between 2.9 and 44.8 wt. % NaCl eq. pyrite, 2.4–2.8 ‰ for pyrite, and 2.1–2.7 ‰ for pyrrhotite
Fluid inclusions in carbonates from drusy cavities (Table 4). The sulphur isotope ratios in the investigated
in massive sulphidic ores show slightly different phase pyrrhotites significantly differ from the value of –1.5 ‰
transition temperatures. Eutectic temperatures between obtained for the pyrrhotite from the Leopold adit by KAN-
–44 and –56 °C are indicative of aqueous chloride so- TOR & ĎURKOVIČOVÁ (1977).
lutions with divalent cations, mainly CaCl2. The CaCl2
weight fractions estimated from dissolution temperatures
of ice and hydrohalite (VANKO et al. 1988) are 0.37–0.56
of total salt content, which varies between 3 and 43 wt. Table 4. Sulphur isotope composition of sulphides (‰ V-CDT).
% NaCl eq. Increased CO2 concentrations in some car-
bonate-hosted, halite-containing inclusions are indicated Sample Py Gn Sp Cp Po T (°C)*
by the nucleation of CO2-clathrate on cooling and sub- T1/10b –1.28 2.61 143–173
sequent dissolution at warming to around –5 °C. CO2- T1/1a 2.66 2.71 2.4 2.71
liquid phase was not observed. Total homogenization T1/2 2.41 2.09
temperatures, either by vapour bubble disappearance or T1/6 0.47 2.87 256–295
T1/18 2.72 2.86 1.5 2.31
halite dissolution, are comparable with those in sphaler-
T1/24 2.83 1.7 2.13
ite, but a number of Th values are shifted below 200 °C, T0H-1 0.11 2.27 285–326
thus indicating a lower trapping temperature (Fig. 4). No
correlation exists between salinity and total homogeniza- * temperatures calculated assuming equilibrium isotope fractiona-
tion temperature for the inclusions trapped in sphalerite tion between coexisting galena and sphalerite (OHMOTO & RYE
and calcite. 1979)

eschweizerbart_xxx
 Origin of ferroan alabandite 127

Fig. 5. Phase diagram of the Fe-S and Fe-As-S systems at atmospheric pressure compiled from TOULMIN & BARTON (1964), KRETSCHMAR &
SCOTT (1976), OSADCHII & CHAREEV (2006). Dashed lines are isopleths for atomic % of As in arsenopyrite (Asp), thin solid lines are isople-
ths of mol. % FeS in pyrrhotite in the Fe-S system (TOULMIN & BARTON 1964), thick solid lines are phase boundaries. Other abbreviations:
Po – pyrrhotite, Py – pyrite, Lö – löllingite, Fe – native iron, As – native arsenic, L – liquid.

7. Interpretations an episodic trapping of halite-oversaturated brines cannot

7.1. Homogenization temperatures of fluid
inclusions
Gas inclusions and variable water volume fractions in a
group of coeval inclusions yield evidence for episodic
boiling of sphalerite- precipitating fluid. In view of this
observation, minimum total homogenization tempera-
tures of liquid-rich inclusions are likely to approximate
the mineral crystallization temperature.
Polyphase inclusions often homogenize by halite dis-
solution, and this behaviour is diagnostic of either homo-
geneous trapping at a higher pressure, or heterogeneous
trapping of halite-oversaturated brine. In the first case, the
temperature of total homogenization represents the lower-
most temperature of crystallisation. In the second case, the
lowermost limit is defined by the homogenization temper-
ature of the bubble in the presence of halite. Due to wide
range of the halite dissolution temperatures (158–380 °C),
be ruled out, though a similar trend can be explained by
dilution of homogenous high-salinity brines. We did not
find evidence for the entrapment of halite-oversaturated
brines in the form of halite-dominated inclusions. Moreo-
ver, the polyphase inclusions normally exhibit rather con-
sistent homogenisation and dissolution temperatures, and
therewith not favouring the concept of heterogeneous L+H
trapping. Anyway, homogenization in polyphase brine in-
clusions homogenizing by halite dissolution, 277–303 °C,
provides the most reliable estimate of the minimum crys-
tallisation temperature. Except for an outlier at 209 °C,
total homogenization temperatures of two-phase primary
inclusions are also rather consistent (234–306 °C), and
these can also be considered with a great deal of certainty
as minimum possible, pressure-uncorrected trapping tem-
peratures. On the other hand, the maximum temperature
of halite dissolution (380 °C) can be considered as the up-
per temperature limit for the sphalerite crystallisation in
the case of episodic halite oversaturation of the ore fluids.

eschweizerbart_xxx
128 V. Hurai and M. Huraiová
Fig. 6. Sulphur isotope ratios in coexisting galena and sphalerite projected on temperatures and δ34S values of the equilibrium H2S gas
(OHMOTO & RYE 1979).
In case of homogeneous trapping, the maximum tempera-
ture may be higher. In conclusion, the microthermometric
data place the most probable crystallisation temperature
of sphalerite to the range of 234–306 °C.
7.2. Pyrrhotite-arsenopyrite ± pyrite equilibria
Pyrrhotite-pyrite equilibrium allows the estimation of
temperature and sulphur fugacity (TOULMIN & BARTON
1964, OSADCHII & CHAREEV 2006) in sub-volcanic envi-
ronments, where pressure plays an insignificant role. The
range of FeS contents in pyrrhotite (93.4–95 mol. %) from
the Tisovec skarn corresponds to a wide range of tempera-
tures, 250–467 °C, and sulphur fugacities, between –5 and
–13.5 log units (Fig. 5). Maximum FeS content in ferroan
sphalerite, 22.3 mol. %, is by 1 mol. % higher than that
in the sphalerite buffered by the pyrite-pyrrhotite assem-
eschweizerbart_xxx
blage at temperatures between 300–500 °C (BOORMAN
1967), but it is within the limit of 19–23 mol. % as sug-
gested by LEPETIT et al. (2003). Pyrite sometimes replaces
pyrrhotite along grain boundaries, and pyrite has not been
observed as inclusions in galena. Hence, we assume that
most ferroan sphalerite coexisted only with pyrrhotite at
low temperature and low sulphur fugacity.
Similarly arsenopyrite, which is closely associated
with galena, provides information about the crystallisa-
tion temperature of accompanied alabandite, Mn-sphaler-
ite and pyrrhotite. Arsenic contents between 31.0 and 31.3
at. % correspond to temperatures of 362–383 °C, and sul-
phur fugacities between –7.6 and –8.2 log units, assum-
ing equilibrium with pyrrhotite and pyrite (KRETSCHMAR
& SCOTT 1976). These temperatures must be considered
as uppermost limits as pyrite is absent in this mineral as-
semblage. On the other hand, the lowermost temperature
and sulphur fugacity, 282–307 °C and –12.3 to –13.5

Fig. 7. Summary of T-fS2 parameters constrained by fluid inclusions, mineral thermo-barometers and sulphur isotopes.
logfS2 units, are constrained by the absence of löllingite.
Assuming equilibrium conditions between arsenopyrite
and pyrrhotite, the isopleths for the minimum As content
in arsenopyrite (31 at. %) and the maximum FeS content
in pyrrhotite (95 mol. %) intersect at ~325 °C and –10.5
logfS2. However, about 30 % of the pyrrhotites, with less
than 94.2 mol. % FeS, is out of equilibrium with the ob-
served arsenopyrite composition.
7.3. Chlorite thermometer
The chlorite thermometer (CATHELINEAU 1988) applied to
zoned aggregates of chlorite associated with anhydrite
enclosed in pyrite crystals (Fig. 2d-e) yields temperatures
from 366 °C to 382 °C for Fe-rich chlorites and 297–
330 °C for Mg-rich chlorite. The inferred temperatures,
however, not necessarily represent the crystallisation con-
ditions of alabandite and sphalerite, because these miner-
als are not associated with chlorites in the assemblage of
the pyrite-hosted inclusions.
7.4. Sulphur isotopes
Galena is most depleted and sphalerite is most enriched in
34
S. This is in accord with equilibrium isotope fractiona-
tion in the sulphide-H2S system (OHMOTO & RYE 1979).
As both minerals must have crystallised simultaneously
(Fig. 2a, b) we may use their sulphur isotope compositions
for calculating the formation temperature and the δ34S
value of the parental fluid. The calculated temperatures
eschweizerbart_xxx
Origin of ferroan alabandite 129
and δ34SH2S values range at 143–326 °C and 2.0–2.5 ‰,
respectively (Fig. 6).
7.5. Thermodynamic model
T-fS2 parameters constrained by fluid inclusions and min-
eral equilibria are summarized in Fig. 7. Temperatures be-
tween 300 and 325 °C, representing the intersection of all
geothermometers, are considered to be the best estimate
for the alabandite-sphalerite-pyrrhotite assemblage.
The temperature of 300 °C was used as input for ther-
modynamic modelling with the aim to calculate oxygen
fugacity (Fig. 8). The latter parameter controls the ratio of
oxidised and reduced sulphur, and is therefore needed to
evaluate the reliability of δ34Sfluid values and temperatures
inferred from sulphur isotope ratios in coexisting galena
and sphalerite.
Thermodynamic modelling was made at a reference
pressure of 1 bar in order to allow correlation with ex-
perimental sulphide systems. Oxygen and sulphur chemi-
cal potentials were calculated by using the PERPLE_X
’06 computing package (CONNOLLY 1990) and database of
minerals, gases and gaseous species included in the SUP-
CRT92 program (JOHNSON et al. 1992). The hard sphere-
modified Redlich-Kwong equation of state involved in the
computing package was employed for the calculation of
the equilibrium H-O-S fluid composition.
Limits of oxygen and sulphur fugacities are con-
strained by the presence of chalcopyrite in the stability
field of anhydrite, and the absence of hematite. The up-
130 V. Hurai and M. Huraiová

Fig. 8. Schreinemaker’s phase diagram for the Fe-Cu-S-O system at 300 °C and 1 bar, with selected univariant curves from the Ca-S-O,
Mn-S-O and Pb-S-O systems calculated using PERPLE_X ’06 package. Contoured are stability fields of alabandite (Alb), anglesite (Ang),
anhydrite (Anh), bornite (Bn), covellite (Cv), chalcocite (Cc), chalcopyrite (Ccp), galena (Gn), hematite (Hem), lime - CaO, magnetite
(Mag), manganosite (Mng), pyrite (Py), pyrrhotite (Po), position of a quartz-fayalite-magnetite buffer (αQFM), and H2S/SO2 ratios in
the equilibrium gas, and invariant points: 1) Mag-Po-Bn-Ccp, 2) Mag-Po-Py-Ccp, 3) Mag-Hem-Bn-Cc, 4) Mag-Hem-Bn-Ccp, 5) Mag-
Hem-Py-Ccp, 6) Hem-Py-Bn-Ccp. The black trapezoid overlaps the most plausible range of fO2-fS2 parameters inferred from the mineral
assemblage of the Tisovec skarn.

permost log fS2 limit of –11.5 is defined by the pyrrhotite-
pyrite equilibrium. However, because pyrite replaces pyr-
rhotite along grain boundaries, it is reasonable to assume
that ferroan alabandite and manganoferroan sphalerite
crystallised within the stability field of pyrrhotite, and the
corresponding sulphur fugacities are more accurately re-
flected by the arsenopyrite composition. In summary, the
anhydrite-magnetite-chalcopyrite-pyrrhotite-arsenopy-
rite-alabandite assemblage and the absence of bournonite
brackets the fO2 values in the system to the range from
–33 to –36 log units, and those of fS2 to –12.5 ± 0.5 log
units. At 300 °C, these conditions must have been slightly
below the Mag-Po-Py-Ccp invariant point (2). At equilib-
rium conditions, the sulpho-carbonic gas is reduced, and
dominated by CH4 and H2S, with H2S contents exceeding
that of SO2 by at least ten orders of magnitude.
8. Discussion
Mn-enrichment, the presence of K-feldspar-sericite and
pyrite-chlorite assemblages, mixed low-to-high-salinity
aqueous fluids and relatively high formation temperatures
are similar to adularia-sericite-type base metal sub-vol-
canic deposits (HEALD et al. 1987). Such deposits form in
geothermal systems, where meteoric water may mix with

eschweizerbart_xxx

Fig. 9. Compositional variations of alabandite and
sphalerite in the Tisovec skarn
deep, hot, saline, and nearly neutral-pH magmatic waters
at depth. In contrast to high sulphidation, acidic-sulphate-
type deposits formed in root zones of volcanic domes, the
adularia-sericite-type is not directly associated with in-
trusive volcanism (ibid.). According to the assemblage of
sulphide minerals, high Fe-content in sphalerite, and the
calculated sulphur and oxygen fugacities, the sulphidic
carbonate-replacement skarn near Tisovec can be classi-
fied as a medium-sulphidation sub-volcanic system.
Thermodynamic parameters and sulphur isotopes at
Tisovec indicate strongly reduced parental fluid, which
was significantly enriched in 34S compared to the mantle-
derived reservoir with the δ34S value close to zero. The
inferred δ34S values in Tisovec sulphidic ores are higher
than those in typical magmatic hydrothermal deposits
(porphyry-copper deposits and skarns) with δ34S in sul-
phides between –3 and +1 ‰ (HOEFS 2009). Such enrich-
ment probably reflects an isotopic exchange with marine
sulphate probably originating from evaporites.
Examination of chemical reactions in seafloor hydro-
thermal systems has shown that adiabatic mixing at tem-
peratures around 350 °C can produce δ34S values between
1.5 and 4.5 ‰ during the precipitation of sulphides. The
δ34S of the solution increases only if the chemical equilib-
ria are coupled with sulphate-sulphide isotopic exchange
disequilibrium. In such case, the maximum increase cor-
responds to 2 ‰ above the initial δ34Sfluid value due to the
limited reducing capacity of the hydrothermal solution
(JANECKY & SHANKS 1988). In accord with this model,
eschweizerbart_xxx
Origin of ferroan alabandite 131
the initial δ34Sfluid value at Tisovec could be close to 0 ‰,
thus being diagnostic of a mantle-derived source. The ob-
served final 34S enrichment of the parental fluid, between
2 and 2.5 ‰, can be attributed to sulphate-sulphide iso-
topic exchange disequilibrium during simple adiabatic
mixing reactions.
High salinity fluids and essentially mantle isotopic sig-
nature of sulphur modified by marine sulphate document-
ed in the Tisovec skarn were for the first time recognized
in the Western Carpathian sub-volcanic settings. Retro-
grade calcite, quartz and sphalerite in genetically similar
skarn deposit at Vyhne-Klokoč in central volcanic zone
of the Neogene Štiavnica stratovolcano (~85 km SWW
of Tisovec) trapped only diluted (0–4 wt. % NaCl eq., Th
= 215–380 °C) aqueous solutions with signs of boiling,
while high-salinity aqueous inclusions (up to 22.8 wt.
%) attributed to magmatic fluid were found only in early
garnet (KODĚRA et al. 1998). Mixing of fluids of different
origins (magmatic vs. present-day meteoric water) was
indicated by oxygen and hydrogen isotope ratios in OH-
bearing skarn minerals and fluid inclusions (KODĚRA et al.
2004).
Occurrence of Mn-bearing minerals (ferroan alaban-
dite, manganoferroan sphalerite, hübnerite) in the Tis-
ovec skarn merits some special comment. Alabandite has
been described from a variety of geological settings of
the Western Carpathians: 1. metamorphosed stratiform
pre-Variscan volcanic-exhalative pyrite-pyrrhotite and
Mn-carbonate deposits, 2. Early-Cretaceous siderite-
132 V. Hurai and M. Huraiová
polymetallic and quartz-stibnite veins in low-grade Palae-
ozoic basement, 3. polymetallic veins and porphyry-type
disseminated mineralizations in central zones of Miocene
stratovolcanoes (KODĚRA et al. 1990). From genetic point
of view, the Western Carpathian occurrences of alaban-
dite are similar to those known worldwide (OLIVO & GIBBS
2003, TRACY & BEARD 2003, and references therein).
However, except for the alabandite from metamorphosed
pyrite-pyrrhotite ores (KANTOR & KRIŠTÍN 1973), other
Western Carpathian occurrences are poorly documented.
Descriptions of alabandite dating from 19th century have
not been confirmed recently. The only recent identifica-
tion of alabandite by means of electron microprobe comes
from an Au-bearing quartz-polymetallic vein genetically
linked with a Miocene quartz-porphyry intrusion in the
central horst structure of the Štiavnica stratovolcano of
Central Slovakia (FERENC et al. 2009).
Strong iron and manganese enrichment is typical of
sphalerites from the Tisovec skarn. FeS content in sphal-
erite is controlled by the activity of FeS in the coexist-
ing iron sulphides. The sphalerite solvus reaches the FeS
maximum of 19–23 mol. % in the presence of pyrite and
pyrrhotite and 51–53 mol. % along the iron-troillite buffer
(BOORMAN 1967, LEPETIT et al. 2003). Significant amounts
of ferric iron can be present if sphalerites contain more
than 6 mol. % FeS (LEPETIT et al. 2003). FeS contents in
ferroan sphalerite from Tisovec (19–22 mol. %) are close
to the maximum limit defined by the pyrite-pyrrhotite
buffer, but they increase up to 28 mol. % in the manga-
noferroan sphalerite (Fig. 9). Substantial Fe3+ contents are
unlikely to be present, as electron microprobe analyses
with total iron expressed as Fe2+ sum around 100 % (Ta-
ble 2). The sphalerite compositions, however, differ from
those in the adularia-sericite-type base metal deposits,
where FeS contents vary typically between 1 and 4 mol.
% (HEALD et al. 1987).
Increased manganese contents are common in natural
sphalerites associated with Mn-rich minerals (COOK et al.
2009). Manganese incorporation in sphalerite takes place
by simple cationic exchange: Zn2+ ↔ Mn2+. However, the
galena-type sphalerite structure can adopt only 7 mol.
% MnS as solid solution (SOMBUTHAWEE at al. 1978). In
contrast, the hexagonal wurtzite absorbs approximately
50 mol. % MnS. The extent of the Zn-Mn substitution
is temperature-independent (KANEKO et al. 1984). Larger
Mn concentrations in sphalerite should result in separa-
tion of sphalerite-wurtzite domains (COOK et al. 2009).
MnS concentrations in sphalerite from Tisovec skarn
vary between 2.4 and 52.6 mol. %. The maximum con-
centrations slightly extend the upper structural limit of the
hexagonal wurtzite lattice, but they are inconsistent with
the cubic galena-type sphalerite structure. Exsolutions
eschweizerbart_xxx
or domains with variable Mn contents have not been ob-
served. Alabandite-sphalerite intergrowths exhibit fuzzy
boundaries (Fig. 2 g). However, electron microprobe
analyses confirm distinct immiscibility gap in the hypo-
thetic (MnFe)S-(Zn,Fe)S solid solution, due to negligibly
low ZnS content, few thousandths of mole fractions, in
the coexistent alabandite (Fig. 9). The observed composi-
tional variation agrees with experimental studies, showing
~ 50 mole % MnS in wurtzite, and essentially no ZnS
substitution in MnS (KANEKO et al. 1984). It is likely that
the gradually increasing Mn contents in zoned sphalerite
from Tisovec (Fig. 2f) are accommodated by the change
of galena-type to wurtzite-type lattice.
The manganoferroan sphalerite from Tisovec contains
the highest Mn concentration recorded so far in hydro-
thermal settings. Available literature sources report on
Mn-rich sphalerite with 0.25 Mn apfu associated with
alabandite in epithermal Ag-bearing sub-volcanic deposit
at Santo Toribio, Peru (OLIVO & GIBBS 2003), alabandite-
hosted sphalerite inclusions with up to 13.4 wt. % Mn in
Neogene sub-volcanic epithermal Au-Te veins at Sac-
arîmb, Romania (CIOBANU et al. 2005), and an average
Mn content of 9.9 wt. % in Cu-Ag-In-Sn-rich sphalerite
from Cretaceous granite-related sulphide-manganese (al-
abandite-rich) veins in the Vysokogornye ore field, Russia
(KOKIN et al. 2010). Compositions of sphalerite and the as-
sociated alabandite from the Tisovec skarn overlap those
described from the Oldoinyo Lengai natrocarbonatites
(Tanzania), where both minerals crystallized as primary
magmatic phases at temperatures over 650 °C (MITCHELL
& BELTON 2004).
Acknowledgements
Financial support was provided by the Ministry of Envi-
ronment and the Geological Survey of Slovakia project
No. 0503, and the grant No. 2/0040/08 from the VEGA
agency. Thanks are due to V. HARČOVÁ and P. ČECH for
mass spectrometric and to P. KONEČNÝ for electron mi-
croprobe analyses. Early draft of the manuscript greatly
benefited from constructive comments of C. CIOBANU
(Adelaide) and an anonymous reviewer.
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Received: June 11, 2010; accepted: July 30, 2010.

Responsible editor: R. Klemd

Authors’ address:
VRATISLAV HURAI, Geological Institute of the Slovak Academy of Sciences, Dúbravská cesta 9, 840 05 Bratislava, Slovak Republic;
vratislav.hurai@savba.sk
MONIKA HURAIOVÁ, Department of Mineralogy and Petrology, Comenius University, Mlynská dolina, 842 15 Bratislava, Slovak Republic;
huraiova@fns.uniba.sk

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