www.geologicacarpathica.sk
GEOLOGICA CARPATHICA, FEBRUARY 2010, 61, 1, 3—17 doi: 10.2478/v10096-009-0040-1
Introduction
Biotite, which is defined as a member of quadrilateral isomor-
phic system annite—flogophite—siderophyllite—eastonite accord-
ing to nomenclature of micas (Rieder et al. 1998), has an
important role in detection of the magma evolution. Despite the
biotite tendency to re-equilibrate significantly during granite so-
lidification, biotite-bearing assemblages still can actually reflect
the physico-chemical conditions of the primary melt. Besides
muscovite, cordierite, garnet and Al
2
SiO
5
polymorphs or feld-
spars, biotite is the most important aluminium concentrator and
in biotite-dominated granitoids it directly determines the peralu-
minosity of magma (Zen 1988; Shabani et al. 2003). Biotite is
also a very useful and suitable indicator of the oxidation-reduc-
tion state in a melt (Wones & Eugster 1965; Burkhard 1991,
1993). In this sense it can play an important role as discrimina-
tive tool in identification of some tectono-magmatic events un-
ravelling the granitoid petrogenesis (Barriére & Cotton 1979;
El Sheshtawi et al. 1993; Lalonde & Bernard 1993; Abdel-Rah-
man 1994; Hecht 1994; and others). Generally, biotite in the as-
sociation with K-feldspar and magnetite – through its annite
activity – may be used to calculate the temperature, oxygen
fugacity and water fugacity in the parental magma.
Geochemistry of biotite in the Western Carpathian granitoids
studied in numerous contributions pointed to differences among
various Variscan granitoid massifs (Ďurkovičová 1966; Petrík
1980; Fejdi & Fejdiová 1981). Petrík (1980) and Buda et al.
Biotite from Čierna hora Mountains granitoids (Western
Carpathians, Slovakia) and estimation of water contents
in granitoid melts
KATARÍNA BÓNOVÁ
1
, IGOR BROSKA
2
and IGOR PETRÍK
2
1
Institute of Geography, Faculty of Sciences, Pavol Jozef Šafárik University, Jesenná 5, 040 01 Košice, Slovak Republic;
katarina.bonova@upjs.sk
2
Geological Institute of the Slovak Academy of Sciences, Dúbravská cesta 9, 840 05 Bratislava, Slovak Republic;
igor.broska@savba.sk; igor.petrik@savba.sk
(Manuscript received February 9, 2009; accepted in revised form June 25, 2009)
Abstract: Biotite is the dominant ferromagnesian mineral in different granites from the Čierna hora Mountains, in the
Western Carpathians (Slovakia). A higher content of Fe
3+
(up to 20 %) is characteristic for the biotites from I-type Soko
and Sopotnica granitoid bodies in contrast to the biotites from S-type Ťahanovce granitoids showing decreased Fe
3+
amount
(around 5 %). The Fe/(Fe + Mg) ratio in biotites from the Soko and Sopotnica massifs between 0.47 and 0.54 is rather low
with respect to that in biotite from the Ťahanovce [Fe/(Fe + Mg) = 0.55—0.63] and Miklušovce [Fe/(Fe + Mg) = 0.73—0.81]
granite body. Water fugacities and contents calculated using Wones’ (1981) calibration of biotite stability equation and
Burnham’s (1994) water dissolution model yield relatively similar values of 4—5 wt. % in remaining melts at 400 MPa and
various levels of f
O
2
and activities of annite for magnetite-bearing assemblages. This suggests an effective buffering role of
biotite in both oxygen and water fugacities. Comparison of the peraluminosity index (A/CNK) of biotite with the same
index in whole-rock shows distinctly higher A/CNK values for biotite indicating its aluminous character and important
role as a significant aluminium carrier. The biotite composition indicates that granitoids in the Čierna hora Mts can be
primarily derived from the lower crust; their protolith was influenced by mixing and/or assimilation process.
Key words: Variscan orogeny, Western Carpathians, water content, granitoids, biotite, oxygen fugacity, Mössbauer
spectroscopy.
(2004) determined the genetic relations between biotite compo-
sitions using its Fe/Mg ratio and crystallizing magma. The eval-
uation of water content in magma of granitoid rocks based on
biotite composition was carried out by Petrík & Broska (1994)
in Tribeč Mts. The first data on biotites from the Čierna hora
granitoids were introduced by Jacko (1984) who assumed
the presence of Fe-biotite in these granitoid rocks. From the cor-
relation between biotite composition and morphology of zircon
(sensu Pupin 1985) Jablonská et al. (1995) inferred that grani-
toids from the Miklušovce Complex and the Ťahanovce area are
derived from crustal melting due to regional anatexis and/or
melting induced by rising of granitic or more basic melts. Bi-
otite composition from the Soko and Sopotnica granitoids cor-
responds to that of biotites from hybrid granites (l.c.).
In this paper, new mineralogical, petrological and geochem-
ical data on biotite from the Čierna hora granitoids are pre-
sented. The purpose of this study is to discuss new and
existing biotite data in terms of oxygen and water fugacity in
parental magmas. These have been used to calculate their wa-
ter contents and derive information on melting processes rele-
vant to the origin and evolution of the Čierna hora granitoids.
I- and S-type granitoids in the Western Carpathians
The Variscan granitic cores of the Tatric Unit and the Vepor
pluton of the Veporic Unit represent separate intrusions with
4
BÓNOVÁ, BROSKA and PETRÍK
independent histories. Geochemical and petrological studies
revealed criteria, which enabled their subdivision into S-, I-
and A-type groups (Fig. 1a) (Cambel & Petrík 1982; Petrík et
al. 1994; Petrík & Kohút 1997; Kohút et al. 1999; Broska &
Uher 2001). These include mineralogical criteria – character
of rock-forming minerals (Petrík & Broska 1994), accessory
mineral assemblage including zircon typology and allanite-
monazite dichotomy (Broska & Uher 1991), magnetite-ilmenite
(Broska & Gregor 1992), the presence or absence of dark mi-
crogranular enclaves (Broska & Petrík 1993a). The S-type
granite group is generally characterized by ferruginous, Al-
and Ti-rich biotite containing 0—8 % (typically 3—5 %) of fer-
ric iron component, which, together with lacking magnetite,
indicate reducing conditions during magma crystallization
(Petrík & Broska 1994). The suite of S-type granitoids is dated
to the period 360—340 Ma (Finger et al. 2003).
The biotite from I-type granitoids, in amount typically
10—15 vol. %, is Mg-dominant [Fe/(Fe + Mg) = 0.4—0.5] and
oxidized (15 % of ferric iron). It associates with magnetite, al-
lanite and titanite indicating the oxidized character of this
group (Petrík & Broska 1994; Petrík & Kohút 1997). The
suite of I-type granitoids seems to have originated in two sepa-
rate events: the first, coeval with S-type granitoids, emplaced
in the Late Devonian—Mississippian period (360—340 Ma) as
Fig. 1. a – Schematized map of the distribution of Variscan West-Carpathian granitoids. Explanations: MK – Malé Karpaty Mts, T – Tribeč
Mts, PI – Považský Inovec Mts, SMM – Suchý and Malá Magura Mts, Z – Žiar Mts, MF – Malá Fatra Mts, VF – Ve ká Fatra Mts,
NT – Nízke Tatry Mts, VT – Vysoké Tatry Mts, V – Vepor Mts, B – Branisko Mts, CH – Čierna hora Mts. b – Schematic geological map
of the Čierna hora Mts (Bezák et al. 2004a) partly modified. Stars show sample location. Explanations: 1 – sedimentary filling (Neogene—Quater-
nary), 2 – sedimentary filling (Paleogene—Upper Cretaceous). Hronicum: 3 – Čierny Váh development, 4 – clastic and volcanic sequences.
Tatricum: 5 – Mesozoic formations with J—C
1
shallow water sediments, 6 – clastic sediments (Upper Paleozoic). Variscan tectonic units in
crystalline basement: 7 – Upper lithotectonic unit, 8 – Middle lithotectonic unit. Veporicum: 9 – sequence of Ve ký Bok (T—C
1
), 10 – cover
sequence (Upper Paleozoic), 11 – Suite of I-type granitoids, 12 – Suite of S-type granitoids. Lodiná, Miklušovce and Bujanová Complexes are
retired according to Jacko (1985).
5
BIOTITE AND WATER CONTENTS IN GRANITOID MELTS FROM ČIERNA HORA MTS (W CARPATHIANS)
the result of partial melting in the thickened Variscan colli-
sional-accretionary wedge (Broska & Uher 2001; Finger et
al. 2003). The intrusion of the second group between ca.
320—300 Ma (the middle/Late Carboniferous; Broska et al.
1990; Bibikova et al. 1990) was probably associated with
crustal collapse and following a thermal event was contribut-
ed by infracrustal or mantle material (Kohút et al. 1999;
Petrík 2000; Broska & Uher 2001; Gawęda et al. 2005; Poller
et al. 2005). The Variscan S- and I-type magmatism was fol-
lowed by a Permian event producing distinct A-type and spe-
cialized S-type granite magmas of the Veporic and Gemeric
Units, respectively (Petrík et al. 1994, 1995; Uher & Broska
1996; Finger et al. 2003).
The above S/I-type subdivision is supported by isotope
data, which indicate different source material and different
melting conditions for the I- and S-type granitoids (Krá 1994;
Kohút & Nabelek 1996; Kohút et al. 1999; Petrík 2000; Poller
et al. 2001, 2005; Kohút & Recio 2002).
Geological setting
The Čierna hora Mts is the easternmost morphostructural
elevation of the Veporic Unit in the Central Western Car-
pathians (Fig. 1b). This unit is composed of the basement
rocks and Upper Paleozoic-Mesozoic cover sequences. The
characteristic basement rocks are medium- to high-grade
metamorphosed schists and gneisses intruded by granitoids.
Granitoid rocks are represented by several types involving
biotite granodiorites to tonalites, biotite-muscovite granites
and leucogranites. Jacko (1985) distinguished three litho-
structural complexes within the Čierna hora crystalline base-
ment: 1 – the Lodiná, 2 – the Miklušovce and 3 – the
Bujanová Complex. The selected complexes as well as con-
tacts between the crystalline basement and cover envelope
sequences are tectonic (l.c.). According to the Variscan
structure of the Central Western Carpathians (sensu Bezák
1994; Bezák et al. 1997), the granite-free Lodiná Complex
belongs to the Middle lithotectonic unit, whereas the Miklu-
šovce and Bujanová Complexes with presence of granitoids
belong to the Upper lithotectonic unit (Jacko et al. 1995).
The Miklušovce Complex is built by strongly diaphtorized
migmatites, gneisses, amphibolites and intrafolial leucogran-
ite bodies. The best exposed aplitic granites are known in the
Vyšná dolina Valley and Predná dolina Valley. The K/Ar
muscovite dating of aplitic granite from the Predná dolina
Valley locality shows the age of 259 Ma (cf. Cambel et al.
1990).
On the basis of existing datings, the Bujanová Complex is
characterized by the presence of Neo-Variscan (Bujanová,
Sopotnica, Ve ká Lodina, Soko ) and Meso-Variscan grani-
toids (Ťahanovce). The Rb/Sr biotite dating from the Soko
area (borehole SGR-V-10; Grecula et al. 1977) shows age of
310 ± 21 Ma (Kovach et al. 1986). The age 309 Ma (K/Ar dat-
ing) for these granitoids was reported by Jacko & Petrík
(1987). The age of around 350 Ma was obtained by CHIME
monazite dating from granitoids in the Ťahanovce area
(Bónová 2006). Detailed petrographic characteristics of the
crystalline basement of the Bujanová Complex were given by
Jacko (1975, 1978), and the granitoid rocks were described by
Jacko & Petrík (1987).
Investigated samples
The investigated samples cover all main granitoid massifs
in the Bujanová Complex. Samples ČH-SK1 and ČH-SK2
(Soko massif) have been taken from the Uhrinče Valley ap-
proximately 1.5 km NW from the village of Soko . Samples
ČH-SP and ČH-150 (Sopotnica massif) are from the Sopotnica
Valley approximately 1.75 km NE of the village of Ve ká
Lodina. The ČH-BJN sample (Bujanová massif) was collected
from the road cut of Košické Hámre—Ružín, ca. 950 m NE of
elevation point 780.8. The samples ČH-TH1 and ČH-TH2 are
the biotite granodiorites (Ťahanovce massif) taken from a
large quarry situated ca. 2 km NW from Košice. The sample
ČH-HAG (Miklušovce Complex) comes from the Predná doli-
na Valley locality, approximately 800 m E of elevation
point 689 (Fig. 1b).
Analytical methods
The chemical composition of biotite was obtained by the
electron microprobe (CAMECA SX-100 housed in the labora-
tories of the State Geological Institute of Dionýz Štúr in Bra-
tislava) and the analyses were supplemented from the literature
(Jacko & Petrík 1987; Jablonská 1992). Operating conditions
included an accelerating voltage of 15 kV and beam current of
20 nA. Analyses of individual elements in biotite were carried
out using the following standards: K – orthoclase, Na – albi-
te, Si and Ca – wollastonite, Al—Al
2
O
3
, Mg—MgO, Fe – he-
matite, Ti—TiO
2
, Cr – chromite, and Mn – rhodonite.
Calculation of biotite structural formula was based on 22 (O)
or 24 (O, OH).
The concentrates of biotite were obtained using standard
mineral separation procedures: rock crushing, sieving, prelim-
inary concentration on a Wilfley table, heavy liquid and final-
ly magnetic separation.
Mössbauer spectroscopy technique (Department of Nuclear
Physics and Technics, Slovak Technical University, Bratislava)
was used on six biotite concentrates with purity better than
99.9 %. All spectra were obtained at room temperature using a
57
Co rhodium matrix source. Data were collected on 512
channels. To minimize possible oxidation of iron the minerals
were not pulverized. The adverse effects of preferred orienta-
tion on relative intensities of peaks in spectrograms were elim-
inated according to Dyar & Burns (1986). The biotites, in
which the oxidation state of iron was determined namely two
biotite separates (ČH-TH1, ČH-TH2) from the Ťahanovce
area, two biotite separates (ČH-SK1, ČH-SK2) from the Soko
massif and the same number of samples (ČH-SP, ČH-150)
from the Sopotnica massif, were analysed in the course of this
study by electron microprobe (see above). On the basis of
Mössbauer spectroscopy results the total FeO content was
divided into Fe
2
O
3
and FeO values.
Major and trace element analyses of whole rocks were de-
termined by ICP-MS spectrometry at the ACME Analytical
Laboratories (Vancouver) Ltd., Canada.
6
BÓNOVÁ, BROSKA and PETRÍK
Sample
Pl
Qtz
Kfs
Bt
Ms
Ep Ttn Ap Mt
ČH-TH2 51.8 25.3 8
9.4 2.7 0.7 0.1 2.3 0.1
ČH-SP
52.4 26.8 2.1
14.6 0.2 1.3 0.9 1.6 0.7
ČH-SK2 65.9 17.7 1.7
10.3 0.13 1.1 1.4 1.8 1.1
ČH-HAG 22.8 39.2 23.8
3.4 10.1
–
– 0.4 0.1
Results
Petrographical and geochemical characteristics of granitoids
Soko , Sopotnica and Bujanová granite bodies. The main
rock types in the Soko , Sopotnica and Bujanová granite
massifs are represented by medium-grained undeformed bi-
otite granodiorite to tonalite. Dominant are plagioclase,
quartz, biotite and K-feldspar and accessories such as zircon,
apatite, titanite, allanite and magnetite (Table 1). Plagioclase
forms euhedral to subhedral prismatic crystals and occasion-
ally encloses biotite flakes or accessories. It is commonly
zoned: rim An
27
, core An
33
(Bónová 2006). Some plagio-
clases exhibit a reversed zoning indicating mixing processes
(Słaby et al. 2007). Alkali feldspar occurs as a minor intersti-
tial phase with An-content usually < 1. Biotite forms subhe-
dral sporadically euhedral dark brown flakes which vary in
size from 0.3 to 2 mm. It commonly encloses scattered pri-
mary accessories – apatite and zircon. The presence of nu-
merous minute inclusions of primary accessories trapped
during biotite growth, suggests, along with biotite intersticial
grain position, its primary magmatic origin. The magmatic
origin is also supported by their chemical composition
(Fig. 2). An incipient chloritization alters biotite crystals
from their margins or along cleavage. Secondary Ca-rich
mineral phases, such as epidote and titanite, crystallize at the
expense of biotite resulting in the loss of TiO
2
(the B field in
Fig. 2). However, primary euhedral titanite also occurs in the
tonalites. Early-crystallized apatite is abundant in biotite, the
apatite crystals located inside and on rims of the primary ti-
tanite probably represent a younger generation (Broska et al.
2004, 2006). Late-magmatic magnetite occurs in characteris-
tic aggregates with titanite and apatite (Fig. 3a). It is almost
Table 1: Modal analyses of representative Čierna hora granitoids.
Fig. 2. Composition of biotites in the 10 TiO
2
—FeO*—MgO ternary
diagram (Nachit et al. 2005). A – domain of primary magmatic bi-
otites, B – domain of reequilibrated biotites, C – domain of neo-
formed biotites.
Fig. 3. a – BSE image of magnetite overgrown by titanite and enclos-
ing apatite (Soko , ČH-SK2). b – BSE image of titanomagnetite over-
grown by magnetite and enclosing apatite (Soko , ČH-SK2). c – BSE
image of strongly altered ilmenite to rutile (Ťahanovce, ČH-TH2).
7
BIOTITE AND WATER CONTENTS IN GRANITOID MELTS FROM ČIERNA HORA MTS (W CARPATHIANS)
pure, typically unzoned and shows a maximum TiO
2
content
of 0.17 wt. % (i.e. 0.5 % Usp). Early titanomagnetite is ex-
tensively oxy-exolved (fine exsolution lamellae of ilmenite
within titanomagnetite as a breakdown product are typical
features) (Fig. 3b). The predominating morphological zircon
types from tonalites according to Pupin (1980) are S
12
and
S
17
; S
22—24
types (Jablonská 1993). Zircon grains display os-
cillatory zoning, typical of the magmatic growth.
Major and trace elements in the investigated rocks are list-
ed in Table 2. The content of SiO
2
in tonalite ranges from
61.6 to 63.4 wt. %. Their main feature is a metaluminous to
Granite
type
S I/S I I I
ČH-HAG ČH-TH2 ČH-BJN ČH-SK2
ČH-SP
SiO
2
75.22 65.08
65.68
61.62
63.42
Al
2
O
3
13.59 16.8
15.84
17.19
17.11
Fe
2
O
3
1.14 4.09
3.87
5.1
4.36
MgO
0.27 1.55
1.41
2.22
1.86
CaO
0.33 2.66
2.7
3.54
3.5
Na
2
O
2.99 4.42
4.08
4.34
4.45
K
2
O
4.92 2.35
3.01
2.43
2.18
TiO
2
0.10 0.60
0.58
0.92
0.76
P
2
O
5
0.19 0.30
0.25
0.33
0.28
MnO
0.01 0.07
0.06
0.07
0.07
LOI
1.0
1.8
2.2
1.9
1.6
Total
98.76 97.93
97.48
97.76
97.99
Ba
1605
1117
1323
1073
1247
Be
1
3
2
2
2
Sc
5
8
7
6
6
Co
0.6
9.1
8
11.3
9.9
Cs
4.6
1.6
3.1
1.6
1.8
Ga
17.4
22.2
21.9
19.5
23.6
Hf
5.4
7.2
7
5.9
6.9
Nb
7
10.1
7.1
6.6
9.5
Rb
267.8
65.7
74.5
66.5
54.2
Sn
6
2
3
2
2
Sr
58.6
707.6
674.7
924.4
1030
Ta
1.2
0.6
0.4
0.4
0.5
Th
6.8
18.1
13
14.6
10.9
U
9.9
2.8
2
1.3
1.6
V
9
65
72
113
92
W
4.1
14.7
<0.5
<0.5
<0.5
Zr
160.7
248.4
239
224.4
244.7
Y
26.7
22
12.5
8.8
20
Mo
0.3
0.4
0.2
<0.1
0.2
Cu
8.4
11.2
7.8
9.5
6.2
Pb
6.3
10
11
10.2
8
Zn
8
78
84
100
99
Ni
1.3
5.1
6.9
8.9
7.9
As
81.5
2.6
1.1
1.1
1.7
Sb
2.8
0.3
1.2
<0.1
0.2
La
9.4
70
48
82.5
54.7
Ce
20.9
137.9
91.5
157.9
108.2
Pr
2.61 15.93
10.08
17.49
12.37
Nd
8.2
58.4
36.3
61.7
43.9
Sm
2.4
9.07
5.08
7.96
6.35
Eu
0.21 1.78
1.36
1.86
1.85
Gd
2.29 5.9
2.79
3.29
3.48
Dy
3.18 4.43
1.82
2.35
2.92
Tb
0.56 0.91
0.39
0.56
0.61
Ho
0.67 0.83
0.3
0.33
0.59
Er
1.84 1.86
0.64
0.73
1.6
Tm
0.34 0.3
0.11
0.17
0.25
Yb
2.14 1.79
0.68
2.37
1.46
Lu
0.31 0.25
0.11
0.35
0.2
Table 2: Chemical composition of the investigated granitoids. Ox-
ides in wt. %, trace elements in ppm.
subaluminous character (A/CNK = 0.93 to 1.07), predomi-
nance of Na
2
O over K
2
O as well as elevated CaO, MgO and
TiO
2
contents. High concentrations of Zn (ca. 100 ppm) re-
flect significant modal abundance of opaque oxides. The
REE patterns do not show negative Eu anomaly (Eu/Eu* ~ 1)
reflecting the higher temperature and fugacity O
2
in magma
(Drake 1975) or a cumulate character of the studied rocks
caused by accumulation of plagioclase crystals (Cambel &
Vilinovič 1987; Jacko & Petrík 1987). Geochemistry fea-
tures as well as rock-forming and accessory mineral assem-
blage confirm the I-type affinity of these rocks.
Ťahanovce granitoid massif. Medium- to coarse-grained
biotite granodiorite is characteristic of this massif. The pri-
mary magmatic minerals are plagioclase, quartz, K-feldspar,
biotite and accessory minerals – apatite, zircon, monazite,
ilmenite, magnetite ± titanite ± allanite. Epidote, sericite, cal-
cite and chlorite present in small quantities are the secondary
phases.
Plagioclase forms euhedral to subhedral prismatic crystals
twinned according to albite law. It locally encloses quartz
and biotite. It is commonly zoned with anorthite component
between An
6
in
rim and An
17
in core. Alkali feldspar occurs
as a minor interstitial phase enclosing quartz, plagioclase oc-
casionally biotite. Biotite (maximum 1.7 mm in size) forms
subhedral dark brown flakes which are often pressure-
kinked. The biotite is locally fully replaced by chlorite form-
ing pseudomorphs. Biotite commonly encloses primary
accessories – apatite, zircon and monazite indicating its pri-
mary magmatic origin. Magnetite is rare, a single grain was
found in the matrix. Ilmenite grains are altered to rutile (leu-
coxenization). The dissolution-reprecipitation mechanism
seems to be responsible for such breakdown being docu-
mented by the formation of numerous pores (Fig. 3c). Zircons
are mainly represented by low morphological S subtypes
(S
1
,
2
,
7
) less by S
12
,
17
and L
2
,
3
types with the mean point rep-
resented by subtype S
7
(Jablonská 1993).
The biotite granodiorite in comparison to Soko and Sopot-
nica granitoids is more peraluminous (A/CNK ratio from
1.15 to 1.3), with low Th, U, Nb and Sr. The peraluminous
character of these granitoids is rather due to secondary alter-
ation than to primary peraluminous character of the protolith.
The SiO
2
content throughout the rocks ranges widely between
65.1 and 71.1 wt. %. Chondrite-normalized REE patterns of
rocks are not significantly different from the pattern of tonalites
(Fig. 4) with negligible Eu anomaly (Eu/Eu* ~ 0.7). The gran-
ite shows S-type affinity.
Granites of the Miklušovce Complex. The Miklušovce
Complex contains abundant aplitic granite dykes exposed
mainly in the Predná dolina Valley locality, in thickness
reaching several tens of centimeters to several meters.
The leucogranite is fine-grained, massive-textured rock
sporadically with features of cataclastic brittle deformation.
It consists of K-feldspar, plagioclase (An
6
), quartz, biotite
and muscovite. The muscovite I is primary magmatic, mus-
covite II clearly grows at the expense of feldspar and biotite.
It is commonly intergrown with vermicular quartz. Biotite is
frequently baueritized. Apatite, zircon (S
7
, S
2,3—7
, S
12
and L
1—4
morphological types; Jablonská 1993) garnet and negligible
opaque minerals occur as accessories. The representative mi-
8
BÓNOVÁ, BROSKA and PETRÍK
croprobe analyses of some rock-forming minerals (wt. %)
are listed in Table 3.
Geochemistry of leucogranite from the Miklušovce Complex
indicates more a fractionated magma with higher SiO
2
~75.2 wt. %, Rb, Y and lower MgO, CaO, TiO
2
contents. The
more pronounced Eu-negative anomaly (ca. 0.3) and the low-
est value of the LREE (La
N
/Yb
N
= 2.96) are characteristic. A
slight tetrad effect observable in the REE chondrite normal-
ized pattern indicates the presence of strong fluid activity dur-
ing cooling of the magma system. Granites from the
Miklušovce Complex are probably the derivates of an S-type
granite suite.
Biotite chemistry
Čierna hora biotite chemistry corresponds to other granitoid
massifs of the Western Carpathians: while I-type tonalites
contain Mg-biotite (Fe-phlogopite to Mg-siderophyllite after
Rieder et al. 1998) with Fe/(Fe + Mg) = 0.44—0.54 and low alu-
mina (total Al = 2.7—3.1, Al
IV
= 2.5), the S-type granodiorites
contain Fe-biotite [Fe/(Fe + Mg) = 0.55—0.62 Ťahanovce], and
Fig. 4. Plot of REE patterns for the investigated granitoids normal-
ized according to Evensen et al. (1978).
Sample
ČH-SK2
ČH-TH2
ČH-HAG
point Ilm
Mag
Pl
Kfs
Pl
Pl Kfs
SiO
2
0.00 0.00
61.12
64.39 61.56 67.77 65.40
TiO
2
47.57 8.40
0.03
0.00 0.01 0.00 0.00
Al
2
O
3
0.02 0.03
24.50
18.51 24.39 20.29 18.36
Fe
2
O
3
10.15 49.89
–
–
–
–
–
FeO 34.14 38.13
0.09
0.18 0.20 0.08 0.06
MnO 8.34 0.40
0.00
0.00 0.01 0.00 0.01
MgO 0.09 0.02
0.00
0.00 0.02 0.00 0.00
CaO 0.04 0.02
5.77
0.00 5.37 1.32 0.04
BaO
n.a.
n.a.
0.13
0.62 0.05 0.00 0.00
Na
2
O
n.a.
n.a.
7.98
0.35 8.15 10.61 0.58
K
2
O
n.a.
n.a.
0.27
16.06 0.40 0.11 16.30
P
2
O
5
n.a.
n.a.
0.08
0.00 0.07
n.a.
n.a.
Cr
2
O
3
0.00 0.06
n.a.
n.a.
n.a.
n.a.
n.a.
ZnO 0.15 0.00
n.a.
n.a.
n.a.
n.a.
n.a.
V
2
O
5
0.10 0.36
n.a.
n.a.
n.a.
n.a.
n.a.
Total 100.6
97.30
99.9
100.1
100.2
100.2
100.8
3 O 4 O 8 O
Si 0.000 0.000
2.717 2.986 2.728 2.959 3.001
Ti
0.901 0.248
0.001 0.000 0.000 0.000 0.000
Al 0.001 0.001
1.284 1.012 1.274 1.044 0.993
Fe
3+
0.192 1.474
Fe
2+
0.719 1.251 Fe
tot
0.003 0.007 0.007 0.003 0.002
Mn 0.178 0.013
0.000 0.000 0.000 0.000 0.000
Mg 0.003 0.001
0.000 0.000 0.002 0.000 0.001
Ca 0.001 0.001
0.275 0.000 0.255 0.062 0.002
Ba
0.002 0.011 0.001 0.000
Na
0.688 0.032 0.701 0.898 0.051
K
0.015 0.950 0.023 0.006 0.955
P
0.003 0.000 0.003 0.000
Cr 0.000 0.002
Zn 0.003 0.000
V 0.002 0.009
Total 2.000 3.000
4.988 4.998 4.994 4.972 5.005
X
ilm
0.893
X
Ab
0.700 0.030 0.720 0.930 0.050
X
hem
0.107
X
An
0.280 0.000 0.260 0.060 0.000
X
usp
0.251 X
Or
0.020 0.960 0.020 0.010 0.950
X
mt
0.749 X
Cs
0.000 0.010 0.000 0.000 0.000
Table 3: Representative microprobe analyses of rock-forming minerals (in wt. %)
from the Čierna hora granitoids. n.a. – not analysed. Ferrous and ferric ratio in
Fe-Ti oxides calculated according to Droop (1987).
leucogranite (Miklušovce) with Fe-rich biotite
Fe/(Fe + Mg) ~ 0.74. Proportions of octahedral
cations are shown in diagram (Fig. 5) after Foster
(1960). Compared to the Tribeč I-type tonalite,
the primary biotites from the Soko and Sopotni-
ca massifs are relatively rich in TiO
2
: 2.4—3.6,
2.1—3.6 wt. %, respectively (Jablonská 1992;
Table 4). This is consistent with the less abun-
dant titanite than in the Tribeč tonalite. The
lower TiO
2
content (2.7 wt. %) in biotite from
the Miklušovce Complex corresponds to more
evolved granite. A slightly elevated TiO
2
is
found in biotite from the Ťahanovce massif (to
2.6—3.7 wt. %). The increasing biotite Fe/Mg
ratio correlates well with total alumina concen-
tration (Figs. 5, 6) reflecting the increased activ-
ity of alumina from biotite tonalite to two mica
leucogranite.
The composition of biotites from the Soko ,
Sopotnica and Bujanová granitoid massifs im-
plies high Mg values and a relatively low Al
VI
content (Fig. 7). The centres of grains are slightly
more Mg-rich compared to crystal margins in
Soko biotite. The trend of iron enrichment in
rims indicates a decrease in temperature and/or
an increase in the water content. The composi-
tions of biotite in leucogranite from the Miklu-
šovce Complex are the most Fe-rich and show
low Mg and high Al
VI
amounts.
Comparison of the peraluminosity index (A/
CNK) of biotite with the same index in whole
rock (Fig. 8) shows distinctly higher A/CNK
values for biotites indicating their aluminous
character and important role as a significant alu-
minium carrier in Čierna hora granitoids, since
cordierite, garnet or the Al
2
SiO
5
polymorphs are
missing in these rocks. The subordinate amount
of muscovite in granodiorites and tonalites,
which occasionally forms symplectitic intergrowths with
quartz, is a product of secondary alterations. An exception is
9
BIOTITE AND WATER CONTENTS IN GRANITOID MELTS FROM ČIERNA HORA MTS (W CARPATHIANS)
Fig. 5. Octahedral cations of biotites from granitoids shown in the
Foster (1960) diagram.
Fig. 6. Composition of biotites from Čierna hora granitoids plotting
Fe/(Fe + Mg) vs. Al diagram; Fe = Fe
2+
+ Fe
3+
. Biotite compositions
from the Miklušovce Complex are taken from Jablonská (1992).
Symbols are the same as in Fig. 2.
Fig. 7. Al
VI
vs. Mg diagram for biotites from Čierna hora grani-
toids. Biotite compositions from the Miklušovce Complex and part-
ly Bujanová Complex are taken from Jablonská (1992). Symbols
are the same as in Fig. 2.
Fig. 8. Plot of A/CNK ratio (molar Al
2
O
3
/(CaO + Na
2
O + K
2
O)) of
biotite vs. whole-rock values for all studied samples.
the highest Al
VI
in biotite of the Miklušovce granite which
results from the presence of primary magmatic muscovite. In
the biotite discrimination diagrams of Abdel-Rahman (1994),
Sopotnica, Soko and Bujanová granitoid massifs fall in the
calc-alkaline field. On the other hand, biotites from Ťahanovce
massifs are plotted between the calc-alkaline and peralumi-
nous fields and, biotites from Miklušovce Complex leucog-
ranites in the peraluminous field (Fig. 9).
Biotite as an indicator of oxygen and water fugacity
On the basis of contraction of the c-axis of the biotite unit cell
with increasing Fe
3+
, Wones & Eugster (1965) suggested posi-
tions of the biotite solid solution in the system Fe
2+
—Fe
3+
—Mg,
which since then have been used for a crude estimate of f
O
2
if
we know primary Fe
3+
/Fe
tot
biotite ratios. Our results of bi-
otite Mössbauer spectroscopy indicate more oxidized condi-
tions for Soko and Sopotnica granitoids (Table 5):
Mg-biotites with respective Fe
3+
contents 16.3 %, and to
21.1 %. The Fe-biotites from the Ťahanovce granitoid body
imply more reducing conditions (Fe
3+
~4.9 % of Fe
tot
). Rep-
resentative Mössbauer spectra of two contrasting biotite
samples are shown in Fig. 10.
In the Fe
2+
—Fe
3+
—Mg ternary diagram (Wones & Eugster
1965) (Fig. 11), the comparison of biotite compositions with
common oxygen buffers (quartz—fayalite—magnetite, QFM,
nickel—nickel oxide, NNO and hematite—magnetite, HM)
shows biotites from the Soko and Sopotnica granitoids plot-
ted above the NNO buffer. In contrast, biotites from the Ťaha-
novce massif fall mainly on the QFM buffer.
The importance of granitoid biotite rests in its assemblage
with K-feldspar and magnetite, which acts as a buffer of oxy-
gen and water fugacities in the magma (Wones & Eugster
1965; Czamanske & Wones 1973):
KFe
3
AlSi
3
O
10
(OH)
2
+
1
/
2
O
2
= KAlSi
3
O
8
+ Fe
3
O
4
+ H
2
O (1)
ann Kfs mag
Through its annite activity (a
ann
) biotite reflects sensitively
the fugacities of oxygen and water in magma. In a solidify-
ing magma the a
H
2
O
increases with decreasing T due to crys-
tallization of anhydrous phases. Concomitantly, when f
O
2
of
10
BÓNOVÁ, BROSKA and PETRÍK
the magma is buffered, a
ann
in biotite increases through reac-
tion of K-feldspar with magnetite, with resulting growth of
the Fe
2+
/ (Fe
2+
+ Mg) ratio. When f
O
2
is allowed to decrease,
at the same temperature and f
H
2
O
, biotite also reacts by in-
crease of a
ann
, either by decrease of Fe
3+
/ Fe
tot
or by increase
of Fe
2+
/ (Fe
2+
+ Mg) ratios. Therefore, less oxidized, more leu-
cocratic S-type granitoid melts always contain more iron-rich
Table 4: Chemical composition of biotites from selected Čierna hora granitoids. c – core, c/r – transitional zone, r – rim.
biotites (coexisting with ilmenite rather than magnetite). For
buffered biotite compositions the relative content of Fe
3+
(i.e. Fe
3+
/ Fe
tot
) is approximately constant its percentage de-
pending on the f
O
2
(buffer). If we are able to estimate the f
O
2
in the magma (best through coexisting Fe-Ti oxides, which
may provide precise estimates of both oxygen fugacity and
temperature) and activities of magnetite and K-feldspar with
Fig. 9. The plot of biotites from Čierna hora granitoids on the Abdel-Rahman (1994) discrimination diagrams. Oxides are in wt. %. Sym-
bols are the same as in Fig. 2.
Locality Sokoľ massif
Sopotnica massif
Ťahanovce massif
Bujanová massif
Miklušovce
Complex
Sample
ČH-SK2
ČH-SP
ČH-TH2
ČH-BJN
ČH-HAG
Point
Bt c
Bt c/r
Bt r
Bt 1
Bt 2
Bt 1
Bt 2
Bt c
Bt r
Bt c
Bt r
SiO
2
37.06 36.78 37.01 36.63
36.33
36.25 35.44 36.24 36.12 35.83 36.30
TiO
2
3.55
3.53
3.58
3.10
3.01
2.80
2.61
3.28
2.78
2.74
2.70
Al
2
O
3
16.13 15.97 15.73 16.17
15.59
16.82 16.95 16.48 16.04 16.33 16.98
FeO
tot
–
–
–
–
–
–
–
21.61 22.58 26.31 26.00
Fe
2
O
3
3.47
3.55
3.63
4.38
4.39
1.13
1.23
–
–
–
–
FeO
16.06 16.42 16.79 14.76
14.79
19.82 21.45 –
–
–
–
MnO
0.35
0.33
0.46
0.28
0.33
0.30
0.27
0.20
0.25
0.00
0.05
MgO
10.65
10.39
9.89
11.07
10.65
9.01
8.56
9.50
9.67
5.39
5.20
CaO
0.00
0.02
0.02
0.07
0.05
0.01
0.03
0.03
0.08
0.02
0.01
Na
2
O
0.08
0.10
0.07
0.00
0.01
0.12
0.13
0.13
0.07
0.08
0.02
K
2
O
9.80
9.68
9.86
9.14
9.54
9.38
8.78
9.50
9.33
9.55
9.48
Cr
2
O
3
0.00
0.00
0.02
0.03
0.00
0.01
0.00
0.00
0.00
0.00
0.00
NiO
0.00
0.11
0.01
0.00
0.00
0.00
0.02
0.00
0.00
0.05
0.02
F
0.26
0.59
0.61
0.46
0.43
0.69
0.23
0.00
0.25
0.57
0.48
Cl
0.05
0.05
0.05
0.04
0.04
0.03
0.05
0.07
0.06
0.03
0.04
Total
97.11 97.17 97.36 95.69
94.72
96.27 95.61 97.04 97.22 96.91 97.28
calculated on the basis 24 O
Si
2.758 2.752 2.771
2.751
2.768
2.767 2.729
2.746 2.752
2.797 2.806
Al
IV
1.242 1.248 1.229
1.249
1.232
1.233 1.271
1.254 1.248
1.203 1.194
Al
VI
0.173 0.161 0.160
0.182
0.168
0.280 0.267
0.218 0.192
0.299 0.353
Ti
0.199 0.199 0.201
0.175
0.172
0.161 0.151
0.187 0.159
0.161 0.157
Fe
3+
0.194 0.200 0.204
0.248
0.252
0.065 0.071
0.000 0.000
0.000 0.000
Fe
2+
0.999 1.027 1.051
0.927
0.943
1.265 1.381
1.369 1.438
1.718 1.681
Mn
0.022 0.021 0.029
0.018
0.021
0.019 0.017
0.013 0.016
0.000 0.003
Mg
1.181 1.159 1.104
1.240
1.209
1.025 0.983
1.073 1.098
0.627 0.600
Cr
0.000 0.000 0.001
0.002
0.000
0.001 0.000
0.000 0.000
0.000 0.000
Ni
0.000 0.007 0.001
0.000
0.000
0.000 0.001
0.000 0.000
0.003 0.001
Ca
0.000 0.002 0.002
0.005
0.004
0.001 0.002
0.003 0.006
0.002 0.001
Na
0.012 0.015 0.011
0.000
0.001
0.018 0.019
0.019 0.010
0.012 0.004
K
0.931 0.924 0.942
0.876
0.927
0.913 0.862
0.918 0.907
0.951 0.935
Total cat.
7.710 7.714 7.707
7.672
7.697
7.748 7.756
7.800 7.828
7.773 7.733
F
0.061 0.140 0.144
0.109
0.103
0.167 0.056
0.000 0.060
0.141 0.118
Cl
0.006 0.006 0.006
0.005
0.005
0.004 0.007
0.009 0.008
0.004 0.005
OH
3.933 3.854 3.850
3.886
3.892
3.830 3.937
3.991 3.933
3.855 3.876
X
Fe
2+
0.333 0.342 0.350
0.309
0.314
0.422 0.460
–
–
–
–
Fe/Fe+Mg 0.503 0.514 0.532
0.487
0.497
0.565 0.596
0.560 0.570
0.733 0.737
11
BIOTITE AND WATER CONTENTS IN GRANITOID MELTS FROM ČIERNA HORA MTS (W CARPATHIANS)
Fig. 10. Mössbauer spectra of two contrasting biotite samples from Ťahanovce (TH) and Sopotnica (SP) granitoids of the Čierna hora Mts.
Fig. 11. Composition of biotites from granitoids projected in Fe
2+
—
Fe
3+
—Mg diagram along with the three common f
O
2
buffers (Wones
& Eugster 1965). Symbols are the same as in Fig. 2.
or in a later calibration (Wones 1981):
log f
H
2
O
= 4819/T + 6.69+0.5log f
O
2
+ log a
ann
—log a
Kf
—log a
mag
—0.011(P-1)/T (3)
where T is in °K, and activities are shown rather than molar
fractions. The activity of annite in biotite is not easy to calcu-
late, it was discussed by many authors who suggested various
ideal activity models, for example:
More complicated non-ideal models are presented by In-
dares & Martingole (1985) or Benisek et al. (1996). The ac-
tivity of K-feldspar is 0.6 for magmatic temperatures
(Czamanske & Wones 1973) and activity of most re-equili-
brated magnetites is close to 1. The f
H
2
O
then can be calculat-
ed from (2, 3) for a series of temperatures. The calculated
water fugacity in magma also gives the water activity
through the relation:
a
H
2
O
= f
H
2
O
/ f
0
H
2
O
(4)
where the f
0
H
2
O
is the standard state water fugacity. On the
basis of water solubility models (Burnham 1979; Stolper 1982
or Burnham & Nekvasil 1986) it is possible to convert the
a
H
2
O
to X
H
2
O
, which can then be expressed in wt. % (e.g.
Clemens 1984). Here we use Burnham’s model as presented
in Burnham (1994) and Holloway & Blank (1994). The k val-
ue is calculated by eq. 7 of Burnham (1994) assuming the hap-
logranite composition for the late crystallizing melt
equilibrated with biotite. This is based on the observation that
biotite in succession always comes after An-rich plagioclase
cores and coexists with albite enriched rims.
Table 5: Mössbauer parameters of the measured biotites: QS – qua-
drupole splitting, IS – isomer shift. Localities: ČH-TH: Ťahanovce,
ČH-SK: Soko , ČH-SP: Sopotnica, ČH-150: Sopotnica.
some certainty, the activity of annite in biotite may be used
to derive the water fugacity through the reaction (Wones
1972; Czamanske & Wones 1973):
log f
H
2
O
=7409/T+4.25+0.5log f
O
2
+log a
ann
—log a
Kf
—log a
mag
(2)
Fe
2+
Fe
3+
QS
1
IS
1
QS
2
IS
2
QS
3
IS
3
Fe
2+
Fe
3+
Sample
mm/s mm/s mm/s mm/s mm/s mm/s sum% sum%
ČH-150
2.63
1 2.22 0.98 0.61 0.35 80.1 19.9
ČH-SP
2.62
1 2.21 0.97 0.61 0.34 78.9 21.1
ČH-SK1
2.63 1.01 2.23 0.98
0.6 0.34 84.1 15.9
ČH-SK2
2.62
1 2.21 0.98 0.63 0.36 83.7 16.3
ČH-TH1
2.69 1.01 2.18
1
0.46 0.37 95.7
4.3
ČH-TH2
2.69 1.01 2.42 1.01 0.56 0.32 95.1
4.9
a
ann
=(X
Fe
2+
)
3
(Mueller 1972; Wones 1972),
a
ann
=(X
Fe
2+
)
3
(X
OH
)
2
(Czamanske & Wones 1973),
a
ann
=(X
Fe
2+
)
3
(X
K
)(X
Al
)(X
Si
)
3
(X
OH
)
2
/(X
0
Al
)(X
0
Si
)
3
(Bohlen et al.
1980, X
0
refers to pure annite),
a
ann
=4X
Fe
M1
2+
(X
Fe
M2
2+
)
2
X
Al
T1
X
Si
T1
(Holland & Powell 1990),
a
ann
=(X
Fe
2+
)
3
(X
K
)(X
OH
)
2
(Nash 1993),
a
ann
=256/27(X
Fe
M2
)
2
X
Fe
M1
X
Al
IV
(X
Si
)
3
X
K
(X
OH
)
2
(Pati
ń
o Douce
1993).
ñ
12
BÓNOVÁ, BROSKA and PETRÍK
Discussion
Estimation of oxygen fugacity
In Figure 11, the most reducing biotites from the Ťaha-
novce granitoid body plot on the QFM buffer, while the
more oxidized biotite analyses from the Soko and Sopotnica
tonalites are shifted between the NNO and HM buffers. The
oxidizing conditions of the tonalite magma are also support-
ed by the presence of titanomagnetite and euhedral titanite
(Ishihara 1977; Wones 1989) in Soko tonalite. The f
O
2
vs. T
relationship was estimated for two samples: Soko and
Sopotnica tonalites. The conditions for the Soko magma
were calculated for a magnetite—ilmenite pair using the con-
version of atomic proportions to molar fractions according to
Stormer (1983) and calibrations of Andersen & Lindsley
(1985) as presented in the ILMAT program (Lepage 2003). The
pair indicates an increased log f
O
2
= — 13.94 to —14.07 at
temperatures T = 768—784 °C. The fugacity is above the NN
buffer (
∆NN ranges between 0.27 and 0.52), which is in accord
with the oxidized character of the Soko biotite (16.3 % Fe
3+
).
This fugacity was used for calculations of the Soko biotite
stability curve (Table 6). The f
O
2
in another tonalite from So-
potnica could not be calculated by oxybarometry because of
the re-equilibrated nature of magnetite. This re-equilibration
involved oxidation of the ulvöspinel component in Ti-magne-
tite producing titanite and magnetite (cf. Broska et al. 2006).
The f
O
2
was therefore approximated by the buffer TMQA (ti-
tanite—magnetite—quartz—amphibole; Noyes et al. 1983) which
is ca. 1.45 log unit above the NNO buffer. The high oxidation
conditions of this buffer are consistent with the highest Fe
3+
in
this biotite (0.211 %).
The derivation of water content in magma
The water content is calculated for the above two samples
which contain the required assemblage biotite + K-feldspar
+magnetite: ČH-SK2 (Soko ) and ČH-SP (Sopotnica), both
representing I-type tonalites. The other two granites (ČH-TH,
ČH-HAG) either do not contain magnetite or K-feldspar in
sufficient amounts (Table 1). The pressure estimate, 400 MPa,
for both samples is obtained from the mineral assemblage of
surrounding metamorphic rocks which were formed during
the periplutonic tectonothermal event (cf. Jacko et al. 1990).
This value is similar to other pressure estimates from similar
metamorphic rocks intruded by granite (Strážovské vrchy
Mts, Vilinovičová 1990; or Ve ká Fatra Mts, Janák & Kohút
1996). The derivation of T and H
2
O is based on the concept of
minimum water content in the melt of haplogranite composi-
tion (Clemens & Vielzeuf 1987; Johannes & Holtz 1996),
which allows us to obtain both parameters from intersection of
the minimum water content curve with the biotite stability
curve in the T-H
2
O space calculated by the above procedure
(Fig. 12). Comparison of three biotite activity – composition
models: Czamanske & Wones (1973), Bohlen et al. (1980)
and Pati
ń
o Douce (1993) shows that they result in the maxi-
mum of 10—23 % difference in final water contents depending
mostly on F concentrations. Fabbrizio et al. (2006) recently
experimentally tested several annite activity models and con-
cluded that the partly ionic model of Czamanske & Wones
[a
ann
= ( X
Fe
2+
)
3
(X
OH
)
2
] most closely follows experimental
data. This activity model was used in the calculations. For the
K-feldspar activity the value 0.6 was used following Czaman-
ske & Wones (1973). Using the higher value a
Kfs
= 0.8 would
change the intersection to a lower water content by ca. 0.35 %
and higher T by 10 °C.
ČH-SK2: Biotite analyses from this tonalite show slightly
more Fe-rich compositions for rim compared to centre (Ta-
ble 4, ČH-SK2, Bt-c and Bt-r) probably recording an effect
of cooling. The oxygen fugacity derived for this sample is
log f
O
2
= —14.07 at T = 768 °C. This temperature is lower than
zircon saturation (T = 799 °C for Soko ), which is in accord
with textural relations with zircon being enclosed in biotite.
The calculated water contents of the intercepts are 3.99 and
4.05 wt. % at T = 772 and 769 °C for biotite core and rim, re-
spectively (Fig. 12, Table 6), close to the Fe-Ti oxide temper-
ature. Although the difference is negligible and certainly
within the error of the estimate, the biotite rim seems to record
an increase in the water content of crystallizing melt at a slight
decrease in T. The derived H
2
O amounts refer to the remain-
ing melt coexisting with biotite, K-feldspar and magnetite.
The growth of the biotite rim may record the build-up of H
2
O
resulting from concomitant feldspar + quartz crystallization.
ČH-SP: This tonalite has high magnetite and titanite con-
tents (0.7, 0.9 %, respectively) but only 0.1 % of K-feldspar
(Table 1). It contains the most Mg-rich and most oxidized bi-
otite from the Čierna hora Mts. The magnetite is mostly pure
and commonly overgrown by titanite. Assuming equilibrium
among biotite, K-feldspar and magnetite the intersection of
the curves (Fig. 12, Table 6) gives 4.76 % H
2
O at 744 °C
(with a
mag
= 1). The highest H
2
O estimate at the lowest T corre-
sponds to the high degree of crystallization necessary for the
precipitation of K-feldspar.
Table 6: Calculated melt and magma water contents for Čierna hora
granitoid biotite compositions using a
K—f
= 0.6, a
mag
= 1 (except in
Soko with a
mag
= 0.853 (sensu model of Woodland & Wood 1994)
and f
O
2
= NNO+0.52 according to mag-ilm oxybarometry),
P= 400 MPa (Jacko et al. 1990), Mössbauer based Fe
3+
contents and
biotite stability curve (3) after Wones (1981). See text for details on
a
ann
and buffers.
Sample
ČH-SK2
core
ČH-SK2
rim
ČH-SP T88
Locality Sokoľ Sokoľ Sopotnica Tribeč
a ann
1
0.0345 0.0368 0.0262 0.0295
Fe
3+
/Fe
tot
0.163 0.163 0.211 0.157
X mag
0.75
0.75
1
1
a mag
2
0.852 0.853 1
1
a san
0.6
0.6
0.6
0.6
T zir °C
799.8
799.8
811
796
T °C by intersection 772
769
744
739
Buffer
NN+0.52 NN+0.52 TMQA
3
TMQA
3
P (MPa)
400
400
400
400
H
2
O (T) wt. %
3.99
4.05
4.76
4.94
Notes:
1
— Annite activity after Czamanske & Wones (1973), cf. Fabbrizio et al.
(2006).
2
— After Woodland & Wood (1994). The calculations assume constant
H
2
O in biotite 3.6 %.
3
— TMQA ~ NN+1.45. Tribeč tonalite also shown for
comparison. The annite activity in T88 recalculated with 0.3 % F in biotite
analysis.
ñ
13
BIOTITE AND WATER CONTENTS IN GRANITOID MELTS FROM ČIERNA HORA MTS (W CARPATHIANS)
Fig. 12. Intersections of the calculated biotite stability curves with
the curve of minimum water content in the haplogranite system (af-
ter Johannes & Holtz 1996: fig. 2.24, 2.25).
A procedure similar to that described above was used by
Petrík & Broska (1994) to derive melt water contents for two
types of biotite tonalite from the Tribeč Mts. Contrasting bi-
otite compositions along with accessory assemblages (magne-
tite vs. ilmenite) indicated different f
O
2
in individual magmas
and higher water contents estimated for the I-type tonalite (ca.
5.2 %, TMQA buffer, 350 MPa) compared with the peralumi-
nous S-type biotite tonalite with only 2.3 % H
2
O (FMQ buffer,
250 MPa) both at 700 °C and using earlier calibration by
Wones (1972). The recalculation of Tribeč I-type tonalite us-
ing the present procedure (Table 6) results in a slightly lower
water content of 4.94 % at a higher temperature of 739 °C.
Generally small differences in the water contents of all to-
nalites (Soko , Sopotnica and Tribeč) indicate the buffering role
of biotite in the system annite—K-feldspar—magnetite—H
2
O. Bi-
otite effectively reacts to different oxygen fugacities by chang-
ing its annite activity and buffers water content in the melt.
Total water in the system
The above estimates refer to the remaining melt, the total
water content in the system crystals+melt is lower than that in-
dicated by biotite composition. From the modal compositions
(Table 1) it follows that because of low content of K-feldspar
the assemblage biotite—magnetite—K-feldspar may have equil-
ibrated only at high degrees of crystallinity, namely when
much of plagioclase, quartz and biotite had crystallized. If we
estimate that after 80—85 % crystallization ca. 20—15 % of
melt remains and the K-feldspar joined the assemblage, the to-
tal water in magma would be in the range 1—1.5 wt. % H
2
O.
Biotite and parental magma
Biotite composition may be a reliable indicator of the origin
of the parental magma (Burkhard 1993; Lalonde & Bernard
1993; Aydin et al. 2003; Machev et al. 2004; and others). The
composition of biotite from the Soko and Sopotnica massifs
– relatively high Mg and low Al
VI
contents – reflects a
slightly fractionated magma (Hecht 1994). This is typical of
the I-type granitoids, where a contribution of mantle material
to melt and mixing process is assumed. The inverse zoning of
some feldspars in the Soko tonalite confirms this presump-
tion. The higher Al
VI
content in cores combined with higher
Mg concentration in rims of some investigated biotites proba-
bly resulted from later transformation by fluids during late-
magmatic events. It may be interpreted by the increasing
partial water pressure from separated fluids, which evolved
during magma crystallization, emphasizing a more oxidizing
regime (Czamanske & Wones 1973; Chivas 1981; Burkhard
1993; Johannes & Holtz 1996). A subsequent increase of the
f
O
2
in melt is suggested by the almost pure magnetite growing
during later stages of magma evolution (Fig. 3b). The biotite
in granodiorite from the Bujanová massif reflects almost iden-
tical features.
The higher Al
IV
content in biotite from the Ťahanovce gran-
itoids (cf. Jablonská 1992; Table 4) compared to the Soko
and Sopotnica biotites supposes its precipitation from more
Al-rich magma. It would be consistent with melt which was
generated from a metapelitic source with important crustal
material contamination (Batchelor 2003).
The Fe content increases in primary biotites from all investi-
gated granitoids with magma crystallization which can be
seen related to the solidification index of rock (cf. Speer 1984;
Fig. 13). While in Soko and Sopotnica the host rock FeO
tot
/
(MgO + FeO
tot
) ratio is higher compared to the same ratio in
biotite, both ratios are similar in Ťahanovce, and biotite ratio
is significantly higher in the Miklušovce Complex. The dif-
ferences are explained by the iron bound in magnetite (0.66—
1.1 vol. %) at increased f
O
2
and f
H
2
O
(e.g. Broska et al. 2006)
in the first case, the lack of the abundant magnetite in the sec-
ond case, and the presence of Mg-rich chlorite in the last case.
Lower Mg and higher Al
VI
contents in biotites from the
Ťahanovce granites and especially from aplitic granites in the
Miklušovce Complex suggest a more advanced degree of
magmatic fractionation (cf. Hecht 1994). High total Al and Fe
concentrations indicate a crustal source for the parental mag-
ma. The Fe, Al-rich, Si-poor biotite crystallized from a peralu-
minous melt originating mostly from the partially melted
Al-rich continental crust (Buda et al. 2004). The presence of
Fig. 13. Relationship between Fe/(Fe + Mg) ratio in biotites (empty
symbols) and their host rocks (full symbols) and the solidification
index of rock 100*MgO/(MgO + FeO + Fe
2
O
3
+ Na
2
O + K
2
O) (cf.
Speer 1984).
14
BÓNOVÁ, BROSKA and PETRÍK
subsolidus (autometamorphosed) biotite, in which Al
VI
con-
tent increases markedly and TiO
2
amount partly decreases, is
also characteristic for these rocks.
Tectono-magmatic implication of biotite compositions
Consequently the biotite chemistry, granitoid rocks from
the Čierna hora Mts could belong to two different granitoid
suites: (1) Granodiorites to tonalites from the Soko , Sopotni-
ca (and Bujanová) massifs (the Bujanová Complex) with the
affinity to the I-type granitoid suite with Mg-rich biotites, as
was assumed by Broska & Petrík (1993b), or to the magnetite
series of magmatic rocks (Ishihara 1977) suggested by Gregor
(1990). The I-type character of these granitoids is also docu-
mented in the discrimination diagrams of Abdel-Rahman
(1994). (2) Granitoid rocks from Ťahanovce massif (the Bu-
janová Complex) and mainly granitoids from the Miklušovce
Complex display affinity to the S-type granitoid suite as
shown by their Fe-rich biotites. The Al-rich biotites coexisting
with primary muscovites in the Miklušovce granites indicate
their S-type character. A progressive increase of Fe and total
Al values in biotites is interpreted as reflecting conditions of
low oxygen fugacity caused by significant contributions of
metasedimentary material to the magma, either by assimila-
tion or anatexis (Neiva 1981; Shabani et al. 2003).
However, the chondrite-normalized REE patterns of the
Ťahanovce granitoids are not significantly different from the
pattern of tonalites from the Soko and Sopotnica massifs.
The major element composition of these rocks, the chemistry of
apatite namely its low Mn and Fe content (cf. Jablonská 1992)
and monazite/allanite antagonism point to mixed I/S-type
character of granitoids. Such (rather metaluminous) granitoids
with affinity to I/S-type were proposed by Kohút & Janák
(1994) in the Tatra Mountains (Western Carpathians) as a re-
sult of contamination of originally acid melts of I-type origi-
nating by dehydration melting of basic protolith by the
material of middle crust. A similar granitoid suite (I/S-type)
Fig. 14. a – Multicationic discrimination diagram for investigated granitoids sensu Batchelor & Bowden (1985). b – Rb—(Y + Nb) discrimi-
nation diagram for investigated granitoids sensu Pearce et al. (1984) compared with granitoids from adjacent regions of the Veporic Unit.
was also described in the Vepor pluton. Its age allocation is
Late Devonian—middle Carboniferous (cf. Broska in Bezák et
al. 2004b). According to tectonic setting discrimination
(Batchelor & Bowden 1985), the Ťahanovce granitoids repre-
sent a pre-plate collision environment (Fig. 14a). A volcanic
arc setting is suggested by the plot of Pearce et al. (1984),
(Fig. 14b). The tectonic environment cannot be identified with
certainty on the basis of the present data set and more detailed
study is necessary. On the other hand, the granite composition
of the Miklušovce Complex on the diagram of Batchelor &
Bowden (l.c.) indicates its post-orogenic character (Fig. 14a).
The S-type granite magma could have formed by heating of
the protolith due to the thermal effect of an earlier hot I-type
melt. This was suggested by Hraško et al. (2000) in the Ve-
poric Unit and an analogous process could have participated
in the formation of the Miklušovce Complex granites.
Summarizing data on the origin of the granite in the Čierna
hora Mts it is concluded that they are primarily derived from
the lower crust, their protolith being influenced by a mixing
and/or assimilation process (I- or I/S-type characteristics).
More than one magmatic event occurred in the Čierna hora
area. The different character of the Western Carpathian grani-
toids can be related to various source rocks (Petrík et al. 1994;
Petrík 2000; Kohút & Nabelek 2008). The Nd isotopes indi-
cate a variable proportion of crustal material during the deri-
vation of host rocks of S-type granitoid suite (l.c.).
Conclusions
The biotites from various granitoids of the Čierna hora Mts
show contrasting compositions: biotite from the I-type Soko ,
Sopotnica and Bujanová massifs are Mg-rich. In contrast, bi-
otite compositions from the S-type Ťahanovce massif and es-
pecially from the Miklušovce Complex show a remarkable
increase in Fe. The various oxygen fugacity values indicated
by variable Fe
3+
contents suggest the primary differences in
15
BIOTITE AND WATER CONTENTS IN GRANITOID MELTS FROM ČIERNA HORA MTS (W CARPATHIANS)
redox state of the host magmas. Water fugacities and contents
calculated using Wones’ (1981) calibration of the biotite sta-
bility equation and Burnham’s (1994) water dissolution model,
yield relatively uniform values of 4—5 wt. % in residual melt
at 400 MPa and various levels of f
O
2
and activities of annite
for magnetite-bearing assemblages. This suggests an effective
buffering role of biotite in both oxygen and water fugacities.
In magnetite-lacking assemblages (S-type) the procedure used
in the present paper cannot be applied. However, if this phase
is considered as consumed, the values of water fugacities and
percentages would represent lower limits. The melt water con-
tents provided by biotite differ from those in the magma
(crystals + melt), and depending on the melt proportion they
range from 1—1.5 wt. % H
2
O.
Acknowledgments: The research was supported by Grants
VEGA SAV 7076 and 4031. Ing. I. Tóth and Prof. P. Lipka
are acknowledged for measuring Mössbauer spectra and inter-
preting biotite data. We also thank Dr. I. Holický and Dr. P.
Konečný for making most of the electron microprobe analyses
and Prof. S. Jacko for providing some whole-rock specimens.
Comments by anonymous reviewers, and by Dr. V. Hurai and
Dr. M. Janák greatly improved the manuscript.
References
Abdel-Rahman A.-F.M. 1994: Nature of biotites from alkaline, calc-
alkaline, and peraluminous magmas. J. Petrology 35, 525—541.
Andersen D.J. & Lindsley D.H. 1985: New (and final!) models for
the Ti-magnetite/ilmenite geothermometer and oxygen barome-
ter. Eos Transactions 66, 18, 416.
Aydin F., Karsli O. & Sadiklar M.B. 2003: Mineralogy and chemistry
of biotites from Eastern Pontide granitoid rocks, NE-Turkey:
Some petrological implications for granitoid magmas. Chem.
Erde 63, 163—182.
Barriére M. & Cotton J. 1979: Biotites and associated minerals as
markers of magmatic fractionation and deuteric equilibration in
granites. Contr. Mineral. Petrology 70, 183—192.
Batchelor R.A. 2003: Geochemistry of biotite in metabentonites as an
age discriminant, indicator of regional magma sources and po-
tential correlating tool. Mineral. Mag. 67, 807—817.
Batchelor R.A. & Bowden P. 1985: Petrogenetic interpretation of
granitoid rock series using multicationic parameters. Chem.
Geol. 48, 43—55.
Benisek A., Dachs E., Redhammer G., Tippelt G. & Amthauer G.
1996: Activity-composition relationship in Tschermak’s substi-
tuted Fe biotites at 700 °C, 2 kbar. Contr. Mineral. Petrology
125, 85—99.
Bezák V. 1994: Proposal of the new dividing of the West Carpathian
crystalline based on the Hercynian tectonic building reconstruc-
tion. Miner. Slovaca 26, 1—6 (in Slovak).
Bezák V., Jacko S., Janák M., Ledru P., Petrík I. & Vozárová A.
1997: Main Hercynian lithotectonic units of the Western Car-
pathians. In: Grecula P., Hovorka D. & Putiš M. (Eds.): Geolog-
ical evolution of the Western Carpathians. Miner. Slovaca—
Monograph, Bratislava, 261—268.
Bezák V. (Ed.), Broska I., Ivanička J., Reichwalder P., Vozár J.,
Polák M., Havrila M., Mello J., Biely A., Plašienka D., Potfaj
M., Konečný V., Lexa J., Kaličiak M., Žec B., Vass D., Elečko
M., Janočko J., Pereszlényi M., Marko F., Maglay J. & Pristaš J.
2004a: Tectonic map of Slovak Republic 1 : 500,000. MŽP SR,
ŠGÚDŠ, Bratislava.
Bezák V. (Ed.), Broska I., Ivanička J., Reichwalder P., Vozár J.,
Polák M., Havrila M., Mello J., Biely A., Plašienka D., Potfaj
M., Konečný V., Lexa J., Kaličiak M., Žec B., Vass D., Elečko
M., Janočko J., Pereszlényi M., Marko F., Maglay J. & Pristaš J.
2004b: Explanations to the Tectonic map of Slovak Republic
1 : 500,000. MŽP SR, ŠGÚDŠ, Bratislava, 1—71.
Bibikova E.V., Korikovsky S.P., Putiš M., Broska I., Goltzman Z.V.
& Arakeliants M.M. 1990: U-Pb, Rb-Sr, K-Ar dating of Sihla
tonalities of Vepor pluton (Western Carpathians Mts.). Geol.
Zbor. Geol. Carpath. 41, 427—436.
Bohlen S.R., Peacor D.-R. & Essene E.J. 1980: Crystal chemistry of a
metamorphic biotite and its significance in water barometry.
Amer. Mineralogist 65, 55—62.
Bónová K. 2006: Geochemical-petrographical-mineralogical char-
acteristics of granitoids from the Branisko and Čierna Hora
Mts. and their petrological and geotectonic interpretation.
PhD. Thesis, Institute of Geo-science, Technical University,
Košice, 1—131 (in Slovak).
Broska I. & Uher P. 1991: Regional typology of zircon and relation-
ship to allanite/monazite antagonism (on an example of Hercyn-
ian granitoids of Western Carpathians). Geol. Carpathica 42, 5,
271—277.
Broska I. & Gregor T. 1992: Allanite-magnetite and monazite-il-
menite granitoid series in the Tríbeč Mts. In: Vozár J. (Ed.):
Western Carpathians, Eastern Alps, Dinarides. Conf. Symp.
Sem., Bratislava, 25—36.
Broska I., Bibikova E.V., Gracheva T.V., Makarov V.A. & Caňo F.
1990: Zircon from granitoid rocks of the Tríbeč-Zobor crystal-
line complex: its typology, chemical and isotopic composition.
Geol. Carpathica 41, 4, 393—406.
Broska I. & Petrík I. 1993a: Magmatic enclaves in granitoid rocks of
the Western Carpathians. Miner. Slovaca 25, 2, 104—108 (in Slo-
vak with English summary).
Broska I. & Petrík I. 1993b: Tonalite of Sihla type sensu lato:
Variscan plagioclase-biotite magmatic rock of I-type in Western
Carpathians. Miner. Slovaca 25, 1, 23—28 (in Slovak).
Broska I., Petrík I. & Williams C.T. 2000: Coexisting monazite and
allanite in peraluminous granitoids of the Tribeč Mountains,
Western Carpathians. Amer. Mineralogist 85, 22—32.
Broska I. & Uher P. 2001: Whole-rock chemistry and genetic typolo-
gy of the West-Carpathian Variscan granites. Geol. Carpathica
52, 2, 79—90.
Broska I., Vdovcová K., Konečný P., Siman P. & Lipka J. 2004: Ti-
tanite in Western Carpathian’s granitoids – distribution and
composition. Miner. Slovaca 36, 237—246 (in Slovak).
Broska I., Harlov D., Tropper P. & Siman P. 2006: Formation of
magmatic titanite and titanite-ilmenite phase relations during
granite alteration in the Tribeč Mountains, Western Carpathians,
Slovakia. Lithos 95, 1—2, 58—71.
Buda G., Koller F., Kovácz J. & Ulrych J. 2004: Compositional vari-
ation of biotite from Variscan granitoids in Central Europe:
a statistical evaluation. Acta Mineral. Petrogr. 45, 1, 21—37.
Burkhard D.J.M. 1991: Temperature and redox path of biotite-bear-
ing intrusives: a method of estimation applied to S- and I-type
granites from Australia. Earth Planet. Sci. Lett. 104, 89—98.
Burkhard D.J.M. 1993: Biotite crystallization temperatures and redox
states in granitic rocks as indicator for tectonic setting. Geol. En
Mijnb. 71, 337—349.
Burnham C.W. 1979: The importance of volatile constituents. In: The
evolution of igneous rocks. Princeton University Press, Prince-
ton, 1077—1084.
Burnham C.W. 1994: Development of the Burnham model for predic-
tion of H
2
O solubility in magmas. In: Carroll M.R. & Holloway
J.R. (Eds.): Volatiles in magmas. Rev. Mineralogy 30, 123—129.
Burnham C.W. & Nekvasil H. 1986: Equilibrium properties of gran-
ite pegmatite magmas. Amer. Mineralogist 71, 239—263.
16
BÓNOVÁ, BROSKA and PETRÍK
Cambel B. & Petrík I. 1982: The West Carpathian I/S classification and
genetic implications. Geol. Zbor. Geol. Carpath. 33, 255—267.
Cambel B. & Vilinovič V. 1987: Geochemistry and petrology of
granitoid rocks from the Malé Karpaty Mts. VEDA, Bratislava,
1—248 (in Slovak with English summary).
Cambel B., Krá J. & Burchart J. 1990: Isotope geochronology of the
Western Carpathian crystalline basement rocks. VEDA, Bratisla-
va, 1—183 (in Slovak).
Candela P.A. 1997: A review of shallow, ore-related granites: Tex-
tures, volatiles, and ore metals. J. Petrology 38, 1619—1633.
Clemens J.C. 1984: Water contents of silicic to intermediate magmas.
Lithos 17, 273—287.
Chivas A.R. 1981: Geochemical evidence for magmatic fluids in porphy-
ry cooper mineralization. Part I. Mafic silicates from the Kolou-
la igneous complex. Contr. Mineral. Petrology 78, 389—403.
Czamanske G.K. & Wones D.R. 1973: Oxidation during magmatic
differentiation, Finnmarka complex, Oslo area, Norway 2. The
mafic silicates. J. Petrology 14, 349—380.
Drake M.J. 1975: The oxidation state of europium as an indicator of
oxygen fugacity. Geochim. Cosmochim. Acta 39, 55—64.
Dropp G.T.R. 1987: A general equation for estimating Fe
3+
concen-
tration in ferromagnesian silicates and oxides from microprobe
analyses. Mineral. Mag. 51, 431—435.
Dyar M.D. & Burns R.G. 1986: Mössbauer spectral study of ferrug-
inous one-layer trioctahedral micas. Amer. Mineralogist 71,
955—965.
Ďurkovičová J. 1966: Mineralogical-geochemical investigation of bi-
otites from granitoid rocks of Western Carpathians. Geol. Práce,
Zpr. 39, 53—68 (in Slovak).
El Sheshtawi Y.A., Salem A.K.A. & Aly M.M. 1993: The geochem-
istry of ferrous biotite and petrogenesis of Wadi El-Sheikh gran-
itoid rocks Southwestern Sinai, Egypt. J. African Earth Sci. 16,
4, 489—498.
Evensen N.M., Hamilton P.J. & O’Nions R.K. 1978: Rare-earth
abundances in chondritic meteorites. Geochim. Cosmochim.
Acta 42, 1199—1212.
Fabbrizio A., Rouse P.J. & Carroll M.R. 2006: New experimental
data on biotite + magnetite+sanidine saturated phonolitic melts
and application to the estimation of magmatic water fugacity.
Amer. Mineralogist 91, 1863—1870.
Fejdi P. & Fejdiová V. 1981: Chemical study of biotites from some
Veporide granitoid rocks. Geol. Zbor. Geol. Carpath. 32, 3,
375—380.
Finger F., Broska I., Haunschmid B., Hraško ., Kohút M., Krenn E.,
Petrík I., Riegler G. & Uher P. 2003: Electron-microprobe dat-
ing of monazites from Western Carpathian basement granitoids:
plutonic evidence for an important Permian rifting event subse-
quent to Variscan crustal anatexis. Int. J. Earth Sci. 92, 86—98.
Foster M.D. 1960: Interpretation of the composition of trioctahedral
micas. U.S. Geol. Surv. Prof. Pap. 354-B, 1—49.
Gawęda A., Doniecki T., Burda J. & Kohút M. 2005: The petrogene-
sis of quartz diorites from the Tatra Mountains (Central Western
Carpathians): an example of magma hybridization. Neu. Jb.
Mineral. Abh. 181, 95—109.
Grecula P., Dianiška I., Ďu a R., Hurný J., Kobulský J., Kusák B.,
Malachovský P., Matula I. & Rozložník O. 1977: Geology, tec-
tonics and metalogeny of Eastern part of the SGR Mts. SGR
Mts. – East, Cu + complex appreciation. Manuscript—Geofond,
Bratislava, 1—390 (in Slovak).
Gregor T. 1990: Magnetite and ilmenite series of the Western Car-
pathian granitoids. Geol. Zbor. Geol. Carpath. 4, 41, 443—451.
Hecht L. 1994: The chemical composition of biotite as an indicator of
magmatic fractionation and metasomatism in Sn-specialised
granites of the Fichtelgebirge (NW Bohemian Massif, Germa-
ny). In: Seltmann R., Kämpf H. & Möller P. (Eds.): Metallogeny
of collisional orogens. Czech Geol. Surv., Praha, 295—300.
Holland T.J.B. & Powell R. 1990: An enlarged and updated inter-
nally consistent thermodynamic dataset with uncertainties and
correlations: the system K
2
O-Na
2
O-CaO-MgO-MnO-FeO-
Fe
2
O
3
-Al
2
O
3
-TiO
2
-SiO
2
-C-H
2
-O
2
. J. Metamorph. Geology 8,
89—124.
Holloway J.R. & Blank J.G. 1994: Application of experimental re-
sults to C-O-H species in natural melts. In: Carroll M.R. & Hol-
loway J.R. (Eds.): Volatiles in magmas. Rev. Mineralogy 30,
187—230.
Holtz F. & Johannes W. 1994: Maximum and minimum water con-
tents of granitic melts: implications for chemical and physical
properties of ascending magmas. Lithos 32, 149—159.
Hraško ., Broska I. & Bezák V. 2000: Upper Carboniferous grani-
toid stage in the Veporic: transition from I- to S-type magmatic
events. Slovak. Geol. Mag. 6, 4, 431—440.
Indares A. & Martignole J. 1985: Biotite-garnet geothermometry in
the granulite facies: the influence of Ti and Al in biotite. Amer.
Mineralogist 70, 272—278.
Ishihara S. 1977: The magnetite-series and ilmenite-series granitic
rocks. Mining Geol. 27, 293—305.
Jablonská J. 1992: Mineralization connecting with granitoids from
Čierna hora Mts. PhD. Thesis, Institute of Geo-science, Techni-
cal University, Košice, 1—211 (in Slovak).
Jablonská J. 1993: Characteristics of zircons from granitoids of the
Čierna hora Mts. Miner. Slovaca 25, 3, 157—171 (in Slovak).
Jablonská J., Pupin J.P. & Timčák G.M. 1995: Morphological and
microchemical assessment of zircons in granite specimens from
Čierna hora Mts. (Western Carpathians). Geol. Carpathica 46,
4, 241—251.
Jacko S. 1975: Lithological-structural development of Southern part
of crystalline basement of Bujanová massif. PhD. Thesis, Insti-
tute of Geo-science, Technical University, Košice, 1—304 (in
Slovak).
Jacko S. 1978: Lithological-structural characteristics of Central part
of the Čierna Hora belt. Západ. Karpaty, Sér. Geol. 3, 59—80 (in
Slovak).
Jacko S. 1984: Structural-metallogenetic study of the Branisko
and Čierna Hora Mts. Manuscript, Geofond, Bratislava, 1—295
(in Slovak).
Jacko S. 1985: Lithostratigraphical complexes of the crystalline base-
ment of the Čierna Hora Mts. Geol. Práce, Spr. 87, 19—25 (in
Slovak).
Jacko S. & Petrík I. 1987: Petrology of the Čierna hora Mts. granitoid
rocks. Geol. Zbor. Geol. Carpath. 38, 5, 515—544.
Jacko S., Korikovskij S.P. & Boronichin V.A. 1990: Equilibrium
assemblages of gneisses and amphibolites of Bujanová com-
plex (Čierna Hora Mts.), Eastern Slovakia. Miner. Slovaca 22,
231—239 (in Slovak).
Jacko S., Vozár J. & Polák M. 1995: New knowledge about geological
composition of the Branisko and Čierna Hora Mts. Miner. Slo-
vaca 27, 6, 417—418 (in Slovak).
Janák M. & Kohút M. 1996: Cordierite-bearing migmatites from the
Ve ká Fatra Mts., Western Carpathians: geothermobarometry
and implications for Variscan decompression. Geol. Carpathica
47, 6, 359—365.
Johannes W. & Holtz F. 1996: Petrogenesis and experimental petrol-
ogy of granitic rocks. Springer, Berlin—Heidelberg—New York,
1—335.
Kohút M. & Janák M. 1994: Granitoids of the Tatra Mts., Western
Carpathians: Field relations and petrogenetic implications. Geol.
Carpathica 45, 5, 301—311.
Kohút M. & Nabelek P.I. 1996: Sources of the Ve ká Fatra granitoid
rocks, Slovakia – isotopic constrains or contradiction? Mineral.
Soc. Pol., Spec. Pap. 7, 47—50.
Kohút M., Kovach V.P., Kotov A.B., Salnikova E.B. & Savatenkov
V.M. 1999: Sr and Nd isotope geochemistry of Hercynian gra-
17
BIOTITE AND WATER CONTENTS IN GRANITOID MELTS FROM ČIERNA HORA MTS (W CARPATHIANS)
nitic rocks from the Western Carpathians: field relations and
petrogenetic implications. Geol. Carpathica 50, 477—487.
Kohút M. & Recio C. 2002: Sulphur isotopes of selected Hercynian
granitic and surrounding rocks from the Western Carpathians
(Slovakia). Geol. Carpathica 53, 3—13.
Kohút M. & Nabelek P.I. 2008: Geochemical and isotopic (Sr, Nd
and O) constrains on sources of Variscan granites in the Western
Carpathians – implications for crustal structure and tectonics.
J. Geosci. 53, 307—322.
Kovách A., Svingor E. & Grecula P. 1986: Rb-Sr isotopic ages from
granitoide rocks from Spišsko-gemerské Rudohorie Mts., West
Carpathians, Eastern Slovakia. Miner. Slovaca 18, 1, 1—14.
Krá J. 1994: Strontium isotopes in granitic rocks of the Western Car-
pathians. Mitt. Österr. Geol. Gesell. 86, 75—81.
Lalonde A.E. & Bernard P. 1993: Composition and color of biotite
from granites: two useful properties in the characterization of
plutonic suites from the Hepburn internal zone of Wopmay oro-
gen, Northwest Territories. Canad. Mineralogist 31, 203—217.
Lepage L.D. 2003: ILMAT: an excel worksheet for ilmenite-magne-
tite geothermometry and geobarometry. Comp. & Geosci. 29, 5,
673—678.
Machev P., Klain L. & Hecht L. 2004: Mineralogy and chemistry of
biotites from the Belogradchik pluton – some petrological im-
plications for granitoid magmatism in North-West Bulgaria.
Bulgarian Geol. Soc., Ann. Sci. Conf. “Geology 2004”, 16.—17.
12. 2004, 48—50.
Montel J.M. 1993: A model for monazite/melt equilibrium and appli-
cation to the generation of granitic magmas. Chem. Geol. 110,
127—146.
Mueller R. 1972: On the stability of biotite. Amer. Mineralogist 57,
300—316.
Nachit H., Ibhi A., Abia El H. & Ohoud M.B. 2005: Discrimination
between primary magmatic biotites, reequilibrated biotites and
neoformed biotites. C.R. Geoscience 337, 1415—1420.
Nash W.P. 1993: Fluorine iron biotite from the Honeycomb Hills
rhyolites, Utah: The halogen record of decompression in a silicic
magma. Amer. Mineralogist 78, 1031—1040.
Neiva A.M.R. 1981: Geochemistry of hybrid granitoid rocks and of
their biotites from Central Northen Portugal and their petrogene-
sis. Lithos 14, 149—163.
Noyes H.J., Wones D.R. & Frey A. 1983: A tale of two plutons: pet-
rographic and mineralogical constraints of the petrogenesis of
the Red Lake and Eagle Peak plutons, central Sierra Nevada. J.
Geol. 91, 353—379.
Pati
ń
o Douce A.E. 1993: Titanium substitution in biotite: an empiri-
cal model with applications to thermometry, O
2
and H
2
O barom-
etries, and consequences for biotite stability. Chem. Geol. 108,
133—162.
Pearce J.A., Harris N.B.W. & Tindle A.G. 1984: Trace element dis-
crimination diagrams for the tectonic interpretation of granitic
rocks. J. Petrology 25, 4, 956—983.
Petrík I. 1980: Biotites from granitoid rocks of the West Carpathians
and their petrogenetic importance. Geol. Zbor. Geol. Carpath.
31, 215—230.
Petrík I. 2000: Multiple sourses of the West-Carpathian Variscan
granitoids: A review of Rb/Sr and Sm/Nd data. Geol. Carpathi-
ca 51, 3, 145—158.
Petrík I. & Broska I. 1994: Petrology of two granite types from the
Tríbeč Mountains, Western Carpathians: an example of allanite
( + magnetite) versus monazite dichotomy. J. Geol. 29, 59—78.
Petrík I., Broska I. & Uher P. 1994: Evolution of the Western Car-
pathian granite magmatism: age, source rock, geotectonic setting
and relation to the Variscan structure. Geol. Carpathica 45, 5,
283—291.
Petrík I., Broska I. & Uher P. 1995: The Hrončok type granite, a
Hercynian A-type granite in shear zone. Miner. Slovaca 27,
351—363 (in Slovak with English summary).
Petrík I. & Kohút M. 1997: The evolution of granitoid magmatism
during the Hercynian orogen in the Western Carpathians. In:
Grecula P., Hovorka D. & Putiš M. (Eds.): Geological evolution
of the Western Carpathians. Miner. Slovaca—Monograph, Bra-
tislava, 235—252.
Poller U., Kohút M., Todt W. & Janák M. 2001: Nd, Sr, Pb isotope
study of the Western Carpathians: implications for Palaeozoic
evolution. Schweiz. Mineral. Petrogr. Mitt. 81, 159—174.
Poller U., Kohút M., Gaab A.S. & Todt W. 2005: Pb, Sr and Nd iso-
tope study of two co-existing magmas in the Nízke Tatry Moun-
tains, Western Carpathians (Slovakia). Mineral. Petrology 84,
215—231.
Pupin J.-P. 1980: Zircon and granite petrology. Contr. Mineral. Pe-
trology 73, 207—220.
Pupin J.P. 1985: Magmatic zoning of Hercynian granitoids in
France based on zircon typology. Schweiz. Mineral. Petrogr.
Mitt. 65, 29—56.
Rieder M., Cavazzini G., D’Yakonov Y.S., Frank-Kamenetskii V.A.,
Gottardi G., Guggenheim S., Kova P.V., Muller G., Neiva
A.M.R., Radoslovich E.W., Robert J.-L., Sassi F.P., Takeda H.,
Weiss Z. & Wones D.R. 1998: Nomenclature of the micas. Ca-
nad. Mineralogist 36, 905—912.
Shabani A.A.T., Lalonde A.E. & Whalen J.B. 2003: Composition of
biotite from granitic rocks of the Canadian Appalachian orogen:
A potential tectonomagmatic indicator? Canad. Mineralogist
41, 1381—1396.
Słaby E., Galbarcyzk-Gąsiorowska L., Seltmann R. & Müller A.
2007: Alkali feldspar megacryst growth: Geochemical model-
ling. Mineral. Petrology 89, 1—29.
Speer J.A. 1984: Micas in igneous rocks. In: Bailey S.W. (Ed.): Mi-
cas. Rev. Mineralogy 13, 299—356.
Stolper E. 1982: The speciation of water in silicate melts. Geochim.
Cosmochim. Acta 46, 2609—2620.
Stormer J.C., Jr. 1983: The effects of recalculation on estimates of
temperature and oxygen fugacity from analyses of multi-compo-
nent iron-titanium oxides. Amer. Mineralogist 68, 5—6, 586—594.
Uher P. & Broska I. 1996: Post-orogenic Permian granitic rocks in
the Western Carpathian-Pannonian area: geochemistry, mineral-
ogy and evolution. Geol. Carpathica 47, 311—321.
Vilinovičová . 1990: Petrogenesis of gneisses and granitoids from the
Strážovské vrchy Mts. Geol. Zbor. Geol. Carpath. 41, 335—376.
Watson E.B. & Harrison T.M. 1983: Zircon saturation revisited: tem-
perature and composition effects in a variety of crustal magma
types. Earth Planet. Sci. Lett. 64, 295—304.
Woodland A.B. & Wood B.J. 1994: Fe
3
O
4
activities in Fe-Ti spinel
solid solution. Eur. J. Mineral. 6, 23—37.
Wones D.R. 1972: Stability of biotite: a reply. Amer. Mineralogist
57, 316—317.
Wones D.R. 1981: Mafic silicates as indicators of intensive variables
in granitic magmas. Mining Geol. 31, 191—212.
Wones D.R. 1989: Significance of the assemblage titanite + magnet-
ite + quartz in granitic rocks. Amer. Mineralogist 74, 744—749.
Wones D.R. & Eugster H.P. 1965: Stability of biotite: experiment,
theory and application. Amer. Mineralogist 50, 1228—1272.
Zen E. 1988: Phase relations of peraluminous granitic rocks and
their petrogenetic implications. Ann. Rev. Earth Planet. Sci.
16, 21—51.
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