Acta Geologica Hungarica, Vol. 45/1, pp.

101–118 (2002)

Mineralogy and genesis of primary alunites from

epithermal systems of Hungary
Bernadett Bajnóczi Ferenc Molnár
Laboratory for Geochemical Research Department of Mineralogy,
Hungarian Academy of Sciences, Budapest, Hungary, Eötvös Loránd University, Budapest, Hungary
and Department of Mineralogy, Eötvös Loránd
University, Budapest, Hungary

Katsuhiko Maeda Géza Nagy

Department of Earth Resources Engineering, Laboratory for Geochemical Research
Kyushu University, Fukuoka, Japan Hungarian Academy of Sciences, Budapest, Hungary

Torsten Vennemann
Institute of Mineralogy, Petrology and Geochemistry,
University of Tübingen, Germany

Alunites from the low sulfidation-type epithermal systems of the Tokaj and the high sulfidation-
type epithermal systems of the Velence Mountains were compared in terms of mineralogical and
genetic aspects
Na-enriched (1.14 to 2.35% Na2O) tabular alunites from the advanced argillic alteration zones of
the Velence Mountains appear in the cavities formed from leached phenocrysts of andesitic rocks.
These magmatic-hydrothermal alunites display compositional zoning due to variation in Na and K
content and contain Ca-rich phosphate-sulfates with REE elements in their cores (i.e., woodhouseite
series). The source of P is probably magmatic apatite that dissolved during intensive leaching of the
host rock by acidic magmatic-hydrothermal fluids.
Alunites in the steam-heated alteration zones of the Tokaj Mountains appear in the cavities formed
from leached pumice fragments of rhyolite tuff units or in fractures in altered rhyolite domes.
Rhombohedral and platy alunites have minor Na content (0.02 to 0.61%Na2O) and display
compositional zoning due to the variation in Ba content. However, comb alunites contain more Na
(1.55 to 1.82% Na2O) and compositional zoning can be attributed to variation of Na and K content.
Alunites from the Velence Mountains have much higher δ34S values (24.2 to 25.3‰) compared to
alunites from the Tokaj Mountains (4.7 to 8.6‰). The δ18O values for the sulfate site in the alunite
structure are between 10.6 and 13.6‰ in both areas. High δ34S values can be attributed to S isotope
fractionation during the high temperature magmatic-hydrothermal formation of alunite from the
Velence Mountains, which did not occur during formation of low-temperature steam-heated alunites
from the Tokaj Mountains.

Key words: epithermal, low-sulfidation, high-sulfidation, alunite, stable isotope,

Al-sulfate-phosphate minerals

Addresses: B. Bajnóczi: H-1112 Budapest, Budaörsi út 45, Hungary, E-mail: bajnoczi@sparc.core.hu

F. Molnár: H-1117 Budapest, Pázmány Péter sétány 1/c, E-mail: molnar@abyss.elte.hu
K. Maeda: 6-10-1 Hakozaki, Higashi-ku, Fukuoka 812-8581, Japan,
E-mail: karl1818@mb.i-chubu.net.jp
G. Nagy: H-1112 Budapest, Budaörsi út 45, Hungary, E-mail: gnagy@sparc.core.hu
T. Vennemann: D-72074 Tübingen, Wilhelmstraße, Germany 56.
E-mail: torsten.vennemann@uni-tuebingen.de
Received: 4 October, 2001

0236–5278/2002/$ 5.00 © 2002 Akadémiai Kiadó, Budapest

102 B. Bajnóczi et al.

Introduction
There are two main regions where occurrence of hydrothermal alunite is
common in Hungary. In the Tokaj Mountains, alunite appears in shallow
alteration zones of low sulfidation-type epithermal mineralization (Molnár et al.
1999). Alunite is also a typical mineral in the advanced argillic alteration zones of
the high sulfidation-type epithermal systems of the Velence Mountains (Vendl
1931; Molnár 1996).
Studies on zoning of hydrothermal alteration and fluid inclusion
measurements helped to establish a conceptual model for the formation
mechanism of alunite in the Tokaj Mountains (Molnár et al. 1999; Molnár and
Pécskay 2000). This framework provided a comparative basis for the study of
alunites from the Velence Mountains. In this paper we document the principal
mineralogical, chemical and isotopic features of epithermal alunites from these
two areas, and provide a discussion of their genetic environment.

Types of alunites in epithermal environments

Alunite is a typical mineral in the acid-sulfate alteration zones of epithermal
systems. The acid-sulfate alteration, which is mainly composed of alunite,
kaolinite, quartz and pyrite (Meyer and Hemley 1967), forms from alteration by
acidic, sulfate-bearing hydrothermal fluids (Hemley et al. 1969). These fluids can
be generated in several ways in an epithermal environment and the differences
are reflected by mineralogical and especially stable isotope characteristics of
alunite (Rye et al. 1992).
In the magmatic-hydrothermal environment of active volcanoes and in
alteration zones of their fossil analogues, high sulfidation-type epithermal
deposits, primary (hypogene) alunite precipitates from fluids with significant
amounts of magmatic vapor. In this environment, HCl, SO2, HF and H2S gas-rich
vapor released by a cooling subvolcanic magma ascends to the surface along
volcanic conduits. As these magmatic gases reach levels closer to the surface, they
mix and condense into groundwater. The resulting high temperature (300 to
350°C) fluids are very acidic (pH=1–2) because of the dissociation of HCl and
H2SO4, the latter produced at slightly deeper levels by the disproportionate
amounts of magmatic SO2 (Hedenquist and Arribas 1999):

4SO2 + 4H2O = 3H2SO4 + H2S

H2SO4 = H+ + HSO4–
HCl = H+ + Cl–

This acidic fluid is capable of dissolving rock-forming minerals, even Al2O3,

completely, leaving a porous silica residuum (vuggy silica). The vuggy silica is
surrounded by an alunite-kaolinite-pyrophyllite-bearing advanced argillic
alteration zone, where sulfate precipitates with Al as alunite and co-existing H2S

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 Mineralogy and genesis of primary alunites from epithermal systems of Hungary 103

precipitates as pyrite. In this magmatic-hydrothermal environment tabular

alunite crystals may typically be found in the voids produced by leaching of
phenocrysts or lithic or pumice fragments of the host rock. The advanced argillic
zone is fringed by intermediate argillic (illite, smectite) and propylitic alteration
envelopes.
In geothermal fields and their fossil analogues, low sulfidation-type systems,
the alteration zoning is developed mostly by neutral to weakly alkaline pH fluids
with lesser amounts of acidic magmatic components. The key factor leading to
the development of a local acidic fluid regime within these systems is the boiling
of fluids at shallow levels (most typically only few hundred meters from the
paleosurface). Boiling results in separation of a steam phase enriched in gases
such as CO2 and H2S. During ascent of this gas-rich vapor to the surface
condensation into groundwater occurs and H2S becomes oxidized in the vadose
zone above the groundwater table:

H2S + 2O2 = H2SO4

The vapor heats the groundwater up and the result is the so-called "steam-
heated fluid". This type of fluid has lower temperatures (100 to 160°C) and
slightly higher pH (2–3) than magmatic-hydrothermal acidic fluids because of the
lack of HCl and smaller amount of sulfate (Hedenquist and Arribas 1999).
Because the pH is not low enough to mobilize Al2O3 from the rocks in the steam-
heated environment, residual silica is not formed and Al is locked in minerals
such as alunite and kaolinite formed during the hydrothermal alteration of the
rock. Typical steam-heated alunite occurs in forms of aggregates consisting of
very fine-grained crystals.
In both the low and the high-sulfidation epithermal systems, a rare and poorly
understood type of alunite also occurs. This type of alunite appears to precipitate
directly from magmatic vapor in which all sulfur is present as SO 2. This SO2
derives from a near-surface magmatic body at high temperatures and low
pressures and is not reduced during its ascent. Alternatively an SO 2-dominated
fluid system may also be formed if all the sulfur in the fluid was oxidized by
atmospheric oxygen during its ascent (Rye et al. 1992). This "magmatic steam"
alunite appears in veins and fractures as coarse-grained, plumose crystals.
Acidic fluids may also be formed during secondary oxidation or weathering of
primary sulfides in both epithermal environments: sulfide + O2 = oxide +
H2SO4. This process occurs in the vadose zone at temperatures of 30–40°C and
results in secondary (supergene) alunite with Fe-oxides and jarosite.

Acta Geologica Hungarica 45, 2002

104 B. Bajnóczi et al.

Characteristics of primary alunite occurrences

in Hungarian epithermal environments
In the low sulfidation-type systems of the Tokaj Mountains alunite occurs in
alteration zones developed mostly in Miocene rhyolite or mixed tuff and sub-
ordinately in andesitic lava flows and rhyolite domes (Fig. 1, Table 1).
In the Telkibánya epithermal Au–Ag deposit, alunite appears in the cavities
formed by leaching of pumice fragments from a silicified rhyolite tuff of Lower
Sarmatian age. The euhedral crystals of 0.5 to 2 mm size show two habits (Molnár
1993). Rhombohedral alunite has a pseudocubic appearance with a pre-
dominance of rhombohedron faces. Platy alunite is dominated by large basal
planes and has minor rhombohedron faces.
At the Király Hill of Mád alunite appears in alteration zoning developed in the
rhyolite tuffs of the Sarmatian volcanic sequence. There are intensively silicified,
mushroom-shaped bodies in the central, fault-controlled part of hydrothermal
alteration. Horizontally the intensity of the silicification decreases, that of the
kaolinite alteration increases and alunite also appears in addition to kaolinite.
Aggregates of fine-grained (0.1 to 0.5 mm) rhombohedral alunite crystals occur in
the cavities formed by leaching of the pumice fragments of the tuff. This alunite-
kaolinite zone is surrounded by kaolinite, then kaolinite-hydrohematite
alteration zones, which are fringed by intermediate argillic (illite-mont-
morillonite and montmorillonite) alteration zones.

Table 1
Characteristics of studied alunite samples from the Tokaj and the Velence
Mountains
Locality Crystal habit Size (mm) Host rock Occurrence

rhombohedral in cavities leached after

Telkibánya 0.5–2 silicified rhyolite tuff
pumice fragments
platy
rhyolite tuff with
Tokaj Mountains

Mád in cavities leached after

rhombohedral 0.1–0.5 quartz-kaolinite
Király Hill pumice fragments
alteration

rhombohedral 1–2 in cavities and fractures

Mád
silicified rhyolite
Mogyorós Hill
comb 4–8 in fractures

Regéc comb 1–10 silicified rhyolite tuff in cavities and fractures

andesite with quartz-
alunite-hematite- in cavities leached after
Templom Hill tabular 0.5–1
Velence Mountains

pyrite-kaolinite phenocrysts
alteration
andesite with quartz-
in cavities leached after
Nyíri Hill tabular 0.2–0.5 alunite hematite-pyrite
phenocrysts
alteration
andesite with quartz-
in cavities leached after
Csúcsos Hill tabular 0.5–1 alunite-hematite-pyrite
phenocrysts
alteration

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Mineralogy and genesis of primary alunites from epithermal systems of Hungary 105

Geologic map of the Tokaj and the Velence Mountains with indication of the sample localities
Fig. 1

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106 B. Bajnóczi et al.

At the Mogyorós Hill of Mád alunite occurs in a hydrothermally altered

rhyolite dome of Lower Sarmatian age. Alunite is restricted to fractures where it
forms comb aggregates with up to 8 mm crystal size. In the cavities and fractures
of the brecciated host rock aggregates of fine-grained (1 to 2 mm) rhombohedral
alunite with minor basal planes also occur. The host rock shows silicic alteration.
In various parts of the Regéc caldera, very fine-grained (<0.1 mm) alunite was
formed together with kaolinite and silica (quartz or opal) during the
hydrothermal alteration of felsic and mixed tuff of Sarmatian age. However,
comb aggregates of alunite crystals of 0.1 to 1 cm size were formed in the cavities
and fractures of the brecciated-silicified tuff horizon at the southern margin of
the caldera (Bajnóczi et al. 2000).
According to K–Ar age dating alunite was formed between 12.49±0.51 and
10.85±0.26 Ma in the various occurrences of the Tokaj Mountains (Molnár and
Pécskay 2000). These ages are indistinguishable from the K–Ar ages for the
volcanic rocks at the localities. Determination of the formation temperature of
alunite in the steam-heated alteration zones is difficult, because samples suitable
for fluid inclusion studies rarely occur. Homogenization experiments of fluid
inclusions from the quartz-barite cement of the brecciated-silicified bodies in the
core of an alunite-bearing alteration zone at Sárospatak indicate temperatures of
100 to 180°C (Molnár 1988).
In the high sulfidation-type systems of the Velence Mountains alunite appears
in hydrothermal alteration zones developed in an andesitic stratovolcanic
sequence of Eocene–Lower Oligocene age (Fig. 1, Table 1). The stratovolcanic
series is located above a diorite intrusion. Vuggy silica bodies surrounded by
alunite-quartz-pyrite-kaolinite alteration assemblage appear in the near-surface
portion of the alteration zone, 300–500 m above the subvolcanic intrusive body.
Occurrence of pyrophyllite, diaspore and topaz in the deeper zones (closer to the
subvolcanic intrusion) is also typical for these systems. Alunite samples for this
study are from the alunite-quartz-hematite-pyrite (-kaolinite) alteration zones of
the Templom, Nyíri and Csúcsos Hills (Fig. 1). These samples contain tabular
alunite crystals of up to 1 mm size occurring in the cavities formed after leached
phenocrysts of the porphyritic andesite. Fluid inclusion data from quartz veinlets
in alunite-quartz alteration zones indicate boiling of fluids at 220 to 380°C
temperatures (Molnár 1996).

Methods
Alunite was separated for the various analytical studies by handpicking and/or
HF leaching of accessory minerals (Itaya et al. 1996). Fe-oxide and hydroxide
encrustings on the surfaces of the crystals were removed by chemical treatment
with trisodium-citrate, sodium bicarbonate and sodium hydrosulfite (A. Arribas,
written communications).

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 Mineralogy and genesis of primary alunites from epithermal systems of Hungary 107

XRD profiles of alunites were measured by a Phillips PW1730-type instrument

at the Laboratory for Geochemical Research using Cu Kα radiation, graphite
monochromator, 45 kV and 35 mA. Samples were analyzed in the range 3 to 70°
2Θ using 1° divergence and 0.2° receiving splits, 0.01° 2Θ step and a counting time
of 1 s/step.
IR spectroscopy measurements between 400 and 4000 cm-1 were carried out by
a Bruker IFS-55-type, Fourier-transform IR spectrometer with 2 cm-1 resolution at
the Institute of Chemistry of the Eötvös L. University. The KBr pastille method
was used with about 2 mg of samples and 200 mg KBr. The contribution of quartz
was subtracted from the spectra in those samples where the presence of quartz
was detected. The spectra are baseline corrected and normalized to the highest
intensity peak.
Backscattered electron images and energy-dispersive X-ray spectrometry
measurements were made with an AMRAY I 1830-type scanning electron
microscope attached to an EDS system at the Department of Petrology and
Geochemistry of the Eötvös L. University. The applied accelerating voltage was
20 kV and counting time was 50 and 100 s, respectively. Quantitative elemental
analyses of alunite were made using a JEOL electron microprobe at the
Department of Earth Sciences of the Carleton University in Ottawa (Canada) and
a JEOL JXCA-733 electron microprobe at the Laboratory for Geochemical
Research in Budapest. At the Laboratory for Geochemical Research an
accelerating voltage of 15 kV was used with sample current of 30 nA and beam
size of 30 µm in diameter. Counting time was 24 s. Standards used were
orthoclase (K), albite (Na), apatite (Ca, P), barite (Ba, S), SrBaNb 4O10 (Sr), corun-
dum (Al) and chalcopyrite (Fe).
For the determination of the stable isotope composition, alunite was
transformed to Ba-sulfate according to the method described in Wasserman et al.
(1992). Ba-sulfate is suitable for determining the oxygen and sulfate isotope
composition of the SO4 site in the alunite structure. Determination of the stable
isotope composition of alunites from the Tokaj Mountains was carried out at the
Institute for Study of the Earth's Interior of the Okayama University and alunites
from the Velence Mountains were measured at the Department of Geochemistry
of the University of Tübingen. Oxygen was extracted by the conventional BrF5
technique of Clayton and Mayeda (1963). Fusion Prism and Finnigan Mat 252
mass spectrometers were used for measurement of the respective isotope ratios.
Sulfur was extracted according to the conventional method of Ueda and Sakai
(1983) and by an elemental analyzer coupled to a Finnigan Delta plus XL mass
spectrometer as described in Giesemann et al. (1994). The uncertainty of
measurement is ±0.2 ‰ for oxygen and ±0.3 ‰ for sulfur.

Acta Geologica Hungarica 45, 2002

108 B. Bajnóczi et al.

Results
XRD study on alunites
The c-parameter of the alunite structure is mostly a function of element
replacement for K. The position of the peak of (006) spacing of alunite varies with
Na-content (Aoki et al. 1993). Endmember K-alunite has (006) reflection at 30.9°,
while natroalunite has a peak at 32.1°. However, the linear correlation between
the Na-content and the position of the peak (006) is not well constrained (A.
Arribas, written communications).
Positions of the (006) reflections in the XRD profiles of alunites from the Tokaj
Mountains are slightly shifted from 30.9°to 31.0 and 31.1°, except for alunite from
Király Hill of Mád (Fig. 2). This shift indicates detectable Na replacement in the
alunite structure. Alunites from the Velence Mountains have peaks at 31.1°, 31.2°
and 31.4° (Fig. 2), which may imply higher Na content than alunites from the
Tokaj Mountains. The position of the (006) peak has some correlation with the
Na2O-content of alunite determined by microprobe analyses (Fig. 2), but not in
every sample (e.g. alunite from Regéc).

Fig. 2
Position of the (006) reflection in the
XRD patterns of alunites from the
Tokaj and the Velence Mountains
with indication of the average Na2O
content of samples (determined by
microprobe analyses)

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 Mineralogy and genesis of primary alunites from epithermal systems of Hungary 109

Infrared spectroscopy study on alunites

IR spectra of alunite samples from different occurrences are nearly similar to
each other and to the spectra of alunite from Marysvale (Utah, USA) from Van
der Marel and Beutelspacher (1976). However, their νOH bands at about 3500 cm-
1 have different patterns. Alunite from Mád and Telkibánya has two bands, while
in case of alunite from Regéc and the Velence Mountains the higher frequency
band is reduced to a shoulder (Fig. 3). Usually bands between 1300 and 400 cm-1
have lower intensity in the case of alunite from the Velence Mountains.

Fig. 3
Transmission infrared spectra between 4000 and 2600 cm-1-for alunites from the Tokaj and the Velence
Mountains with indication of the average Na2O content of samples (determined by microprobe
analyses)

Chemical composition of alunites

Backscattered electron images of alunites both from the Tokaj and the Velence
Mountains (Fig. 4A–D) display compositional zoning due to replacement of K in
the alunite structure. In alunites from the Tokaj Mountains zoning can be
attributed to presence of Ba (platy and rhombohedral alunites from Telkibánya)
(Fig. 4A) or to variation of Na vs. K content (comb alunite aggregates from Regéc
and Mogyorós Hill of Mád) (Fig. 4B). In alunite crystals from the Király Hill of
Mád the cause of zoning cannot be determined by SEM. Alunites with
rhombohedral and platy habit have an average Na2O content between 0.02 and
0.61% (Table 2), whereas comb alunite aggregates of Regéc and Mogyorós Hill of
Mád have 1.55 to 1.82 % Na2O content. Earlier studies on alunites from other

Acta Geologica Hungarica 45, 2002

110 B. Bajnóczi et al.

Fig. 4A, B
Backscattered electron images and energy dispersive spectra of hydrothermal alunites from the Tokaj
and the Velence Mountains. A. Ba zoning in platy alunite from Telkibánya; B. Na–K zoning in comb
alunite from Regéc

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 Mineralogy and genesis of primary alunites from epithermal systems of Hungary 111

Fig. 4C, D
C. Alunite from Nyíri Hill with Na–K zoning and phosphate-sulfate-bearing, bright mineral in the
core; D. Phosphate-sulfate mineral with REE-bearing rim in alunite from the Templom Hill

Acta Geologica Hungarica 45, 2002

 Table 2

112
Acta Geologica Hungarica 45, 2002
Average chemical composition of alunites from the Tokaj and the Velence Mountains

B. Bajnóczi et al.
Tokaj Mountains Velence Mountains
Wt% oxide
Mád
Telkibánya Mád
Király Hill Telkibánya Regéc Templom Hill Csúcsos Hill Nyíri Hill
rhombohedral Mogyorós Hill
rhombohedral platy alunite* comb alunite+ tabular alunite+ tabular alunite+ tabular alunite+
alunite* comb alunite*
alunite*
K 2O 10.76 10.25 10.04 8.06 7.48 8.12 7.22 6.52
Na 2O 0.02 0.56 0.61 1.55 1.82 1.14 2.25 2.35
CaO 0.00 0.01 0.01 0.08 0.08 0.04 0.07 0.08
BaO n. a. n. a. n. a. n. a. 0.15 0.15 0.48 0.33
SrO n. a. n. a. n. a. n. a. 0.05 0.01 0.04 0.18
Ag 2O 0.00 0.00 0.01 0.00 n. a. n. a. n. a. n. a.
PbO 0.00 0.00 0.00 0.00 n. a. n. a. n. a. n. a.
Al2O3 36.03 35.99 35.36 35.68 37.04 34.32 36.24 37.04
Fe2O3 0.00 0.01 0.00 0.29 0.02 0.01 0.01 0.00
CuO 0.01 0.00 0.00 0.00 n. a. n. a. n. a. n. a.
SO 3 37.66 37.62 37.22 37.33 37.81 34.80 36.84 37.61
P 2O 5 n. a. n. a. n. a. n. a. 0.07 0.07 0.30 0.03
Total 84.47 84.44 83.25 82.99 84.52 78.66 83.45 84.14
Ion structural positions (based on 11 oxygens)
K 0.972 0.925 0.919 0.733 0.668 0.783 0.655 0.582
Na 0.003 0.077 0.085 0.215 0.244 0.166 0.310 0.320
Ca 0.000 0.001 0.001 0.006 0.006 0.003 0.005 0.006
Ba n. a. n. a. n. a. n. a. 0.004 0.004 0.013 0.009
Sr n. a. n. a. n. a. n. a. 0.002 0.001 0.002 0.007
Ag 0.000 0.000 0.000 0.000 n. a. n. a. n. a. n. a.
Pb 0.000 0.000 0.000 0.000 n. a. n. a. n. a. n. a.
Al 3.006 3.002 2.990 3.000 3.050 3.057 3.037 3.059
Fe 0.000 0.001 0.000 0.015 0.001 0.001 0.001 0.000
Cu 0.001 0.000 0.000 0.000 n. a. n. a. n. a. n. a.
S 2.001 1.998 2.004 1.999 1.973 1.973 1.966 1.978
P n. a. n. a. n. a. n. a. 0.004 0.004 0.018 0.002

*: Analyzed at the Earth Science Department of the Carleton University, Canada (Molnár and Pécskay 2000); +: Analyzed at the Laboratory for
Geochemical Research, Budapest; n. a.: not analyzed
 Mineralogy and genesis of primary alunites from epithermal systems of Hungary 113

occurrences in the Tokaj Mountains also confirmed the diversified compositional

pattern of these crystals (Dobosi 1978).
Alunites from the Velence Mountains show zoning due to the different content
of Na replacing K in the alunite structure (Fig. 4C). Alunites contain 1.14 to 2.35%
Na2O (Table 2), which is usually higher than the Na-content of the alunites from
the Tokaj Mountains. Several alunite crystals from the Velence Mountains show
a bright, irregular-ragged core on the BSE images (Fig. 4C, D). The core is mostly
composed of Ca, Al, S and P elements with minor amounts of Ba, K and
sometimes Sr. REE (Ce, La) enrichments occur in the rim of these cores (alunites
from Templom and Nyíri Hills Fig 4D).

Stable isotope compositions of alunites

The sulfate sites of alunites from the Tokaj Mountains have O and S isotope
compositions between 11.6 and 13.6‰ and between 4.7 and 8.9‰, respectively
(Table 3). Alunites from the Velence Mountains also have very similar δ18O values
(10.6 to 13.0‰), but the δ34S values are significantly different (24.2 to 25.3‰)
(Table 3). A coexisting alunite-pyrite pair from the Velence Mountains has δ18O
and δ34S values of 11.9 and –5.3‰, respectively, which implies a formation
temperature of 390°C (Rye et al. 1992).

Table 3
Stable O and S isotope compositions (relative to SMOW and CDT, respectively)
of alunites from the Tokaj and the Velence Mountains. δ34S value of
rhombohedral alunite from Mogyorós Hill of Mád is from Itaya et al. (1996)

Sample δ18OSO4 δ34S

Mád, Mogyorós Hill, comb alunite 13.6 6.4
Mád, Mogyorós Hill, rhombohedral alunite - 4.7
Mád, Király Hill, rhombohedral alunite 12.3 6.7
Regéc, comb alunite 11.6 8.9
Telkibánya, rhombohedral alunite 13.4 8.6
Telkibánya, platy alunite 12.2 8.5
Templom Hill, tabular alunite 12.7 25.3
Nyíri Hill, tabular alunite 13.0 24.4
Csúcsos Hill, tabular alunite 10.6 24.2

Discussion
Analyses indicate that alunites from the Velence Mountains usually have
higher Na2O content (1.14 to 2.35%) than alunites from the Tokaj Mountains (0.02
to 1.82%). K replacement by Na is very common in the alunite solid solution
shifting the composition toward the natroalunite end-member; however, all of
the studied samples can be regarded as alunite.

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114 B. Bajnóczi et al.

Differences in the pattern of the OH-stretching region in the infrared spectra

of alunites are the result of the effect of the monovalent cation (Serna et al. 1986).
The intensity of the higher frequency band at about 3500 cm-1 seems to correlate
with the degree of Na replacement for K: the higher the Na2O content, the lower
the intensity of the band (Fig. 3).
Alunite from the Tokaj Mountains has various crystal habits (pseudocubic
rhombohedral, platy and comb), which seems to correlate with composition.
Rhombohedral and platy alunites mostly contain <1–8% of Na at the 12-
coordinated site. The appearance of different amounts of Ba in the growth zones
of alunites from Telkibánya shows transitional composition towards walthierite
(Ba0,5o0,5Al3(SO4)2(OH)6), since complete solid solution is assumed between
these two end-members (Li et al. 1992). Two comb alunite aggregate samples
from Regéc and Mogyorós Hill of Mád contain up to 26% Na at the 12-
coordinated site, resulting in Na-K zoning in crystals similarly to alunites from
the Velence Mountains.
Beside the significant Na content and Na-K zoning in tabular alunites from the
Velence Mountains these crystals also contain dissolved phosphate-bearing
analogs in their core. The dominant end-member in these phosphate-sulfate
minerals is Ca-bearing woodhouseite. A minor amount of K, Ba, and Sr besides
Ca can be present due to the complete solid solution within the woodhouseite
group and limited solid solution between alunite and woodhouseite group
minerals and woodhouseite and crandallite group minerals, respectively (Wise
1975). The REE content on the rim of woodhouseite indicates intermediate
transition towards florencite (Wise 1975).
Similar phosphate-bearing minerals (woodhouseite, svanbergite, florencite,
crandallite) were also found in the core of hypogene alunite crystals from other
high-sulfidation ore deposits, e.g. Summitville, Colorado, USA (Stoffregen and
Alpers 1987), Asarel, Bulgaria (Velinov et al. 1991), Baguio district, Philippines
(Aoki et al. 1993), Nansatsu, Japan (Hedenquist et al. 1994), Rodalquilar, Spain
(Arribas et al. 1995) and Lepanto, Philippines (Hedenquist et al. 1998).
The presence of Ca-phosphate-sulfate phase in the core of alunites from the
Velence Mountains may indicate that dissolution of magmatic apatite by acidic
magmatic-hydrothermal fluids at high temperatures induce the precipitation of
phosphate-bearing minerals (Stoffregen and Alpers 1987):

Ca5(PO4)3(OH) + 7H+ = 5Ca2+ + 3H2PO4 + H2O

The dissolution of the early Ca-phosphate-sulfate phase and precipitation of

REE-bearing phosphate-sulfate minerals on the rim of the core may develop in
the waning stage of hydrothermal alteration (Dill et al. 2000). After the complete
dissolution of apatite the subsequently formed minerals are Na-enriched
alunites, because at higher temperatures Na rather than K tends to be
incorporated into alunite (Stoffregen and Cygan 1990).

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 Mineralogy and genesis of primary alunites from epithermal systems of Hungary 115

The higher 34S content (δ34S = 24.2–25.3‰) of alunites from the Velence
Mountains compared to that of alunites from the Tokaj Mountains (d34S = 4.7–
8.9‰) is consistent with isotope fractionation within the hydrothermal fluid.
Isotope fractionation occurs during the formation of magmatic-hydrothermal
alunite when HCl and SO2-bearing magmatic vapor condenses in the
groundwater and disproportionate amounts of SO2 results in formation of 34S-
enriched H2SO4 and 34S-depleted H2S (Rye et al. 1992). Alunites of steam-heated,
supergene or magmatic steam origin have significantly lower δ34S values (usually
less than 15‰), because they inherit the isotopically light sulfur isotopic
composition of H2S derived from boiling (steam-heated), δ34S of the primary
sulfides (supergene) or the bulk sulfur isotope composition of magmatic steam
(Rye et al. 1992).
Compared with the S and O isotope compositions of hydrothermal alunites
from other epithermal deposits (Fig. 5, compiled from data of Rye et al. 1992),
alunites from the Tokaj Mountains correspond to steam-heated alunites and
alunites from the Velence Mountains are magmatic-hydrothermal alunites. This
is consistent with their geologic environment and occurrence.
According to the results of earlier investigations on the hydrothermal minerals
of epithermal deposits the study of alunites from the Velence Mountains
confirms that magmatic-hydrothermal alunites usually contain phosphate-
bearing minerals in their cores. No similar minerals were found in the core of
steam-heated alunites from the Tokaj Mountains. This feature is not typical for
steam-heated or supergene type of alunite; however, there is evidence of small
amounts of sulfate-phosphates in supergene alunite from Riaza, Spain (A.
Arribas, written communications).
In the steam-heated environment the sulfate-bearing fluids have lower
temperatures (150–200°C) and lower acidity (pH=2–3) compared to magmatic-
hydrothermal fluids, and contain CO2. Apatite is less soluble in fluids of higher
pH and in the presence of CO2 (Gieré 1996). In absence of external source for
phosphorus the low solubility of apatite in such conditions may explain the
absence of phosphate-bearing minerals in the core of steam-heated alunites from
the Tokaj Mountains.

Conclusions
A comparative study of alunites from the low-sulfidation epithermal systems
of the Tokaj and the high-sulfidation epithermal systems of the Velence
Mountains revealed some differences in chemical and stable isotope
compositions.
Na-enriched (1.14 to 2.35% Na2O) tabular alunites from the magmatic-
hydrothermal environment of the Velence Mountains contain phosphate-sulfate-
bearing analogs (woodhouseite series) in their core. This feature has not been
encountered in the steam-heated type of alunites from the Tokaj Mountains,

Acta Geologica Hungarica 45, 2002

116 B. Bajnóczi et al.

Fig. 5
Stable O and S isotope compositions (relative to SMOW and CDT, respectively) of epithermal alunites
from Hungary compared to the main genetic types of hydrothermal alunites (data from Rye et al.
1992). l: Tokaj Mountains, n: Velence Mountains

where rhombohedral and platy alunites contain minor amounts of Na (0.02 to

0.61% Na2O) and only the two comb alunite samples have significant Na content
(1.55 to 1.82% Na2O). It is indicated that the habit of the crystals is related to the
Na-content and primary alunites with different compositions, even within the
same locality (e.g. Mogyorós Hill of Mád) can be found.
Alunites from the Velence Mountains have much higher δ34S values compared
to the alunites from the Tokaj Mountains, whereas the O isotope compositions
are similar. The difference is due to high-temperature isotope fractionation
during formation and coincides with the magmatic-hydrothermal character of
alunites from the Velence Mountains.
These mineralogical and O and S isotope results are consistent with data
published earlier and support differences in the formation conditions (such as
temperature, pH, CO2 content), which influence the characteristics of epithermal
alunites in these systems.

Acknowledgements
This study was supported by the Hungarian–Japanese Intergovernmental
Science and Technology Cooperation Program supervised by F. Molnár and J. W.
Hedenquist. K. Maeda carried out stable isotope measurements under the
Visiting Researcher's Program of the Institute for Study of the Earth's Interior of
the Okayama University. Prof. M. Kusakabe is greatly appreciated for his help.
The SEG BHP Student Research Grant provided financial support for B. Bajnóczi
to carry out stable isotope studies at the Dept. of Geochemistry, University of
Tübingen. G. Stoschek and T. Tütken are thanked for their help in O and S

Acta Geologica Hungarica 45, 2002

 Mineralogy and genesis of primary alunites from epithermal systems of Hungary 117

isotope analyses. XRD and IR spectroscopy measurements are acknowledged to

M. Tóth (Lab. for Geochem. Res., HAS) and E. Vass (Dept. of Organic Chemistry,
Eötvös L. University), respectively. P. C. Jones (Dept. of Earth Sciences, Carleton
University) is thanked for the microprobe analyses of alunites from the Tokaj
Mountains. Backscattered electron images and energy-dispersive spectra are
acknowledged to K. Gál-Solymos (Dept. of Petrology and Geochemistry, Eötvös
L. University). Suggestions from referees (A. Arribas, Jr. and A. Demény) greatly
improved the quality of the manuscript.

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