GeolCarp_Vol53_No1_3

GEOLOGICA CARPATHICA, 53, 1, BRATISLAVA, FEBRUARY 2002

3 — 13

SULPHUR ISOTOPES OF SELECTED HERCYNIAN GRANITIC AND

SURROUNDING ROCKS FROM THE WESTERN CARPATHIANS

(SLOVAKIA)

MILAN KOHÚT

and CLEMENTE RECIO

Geological Survey of Slovak Republic, Mlynská dolina 1, 817 04 Bratislava, Slovak Republic; milan@gssr.sk

Departamento de Geología, Universidad de Salamanca, E-37008 Salamanca, Spain

(Manuscript received April 2, 2001; accepted in revised form October 5, 2001)

Abstract: A reconnaissance sulphur isotopic study has been carried out on selected Hercynian granites and related rocks
to test the applicability of such data in constraining the relative contribution of igneous and sedimentary protoliths to the
West-Carpathian granitic rocks. Chemical separation techniques yielded enough sulphide sulphur for analysis in 22 out
of 26 selected whole rock samples. In general, more mafic rocks, showing higher whole-rock bulk sulphur content,
yielded more sulphide for isotopic analysis than more felsic ones. The

S values obtained range from —0.9 to +5.7 ‰

(average +2.5 ± 2.3 ‰) for granites of S-type affinity, while results for I-type granites are lower, ranging between —2.9
and +2.3 ‰ (average —0.7 ± 1.9 ‰). Medium grade metamorphic rocks (gneisses ± mica schist) in the area gave values
between —2.0 to +4.6 ‰ (average +0.8 ± 2.1‰) similar to S-type granites, while basic igneous rocks, and metamorphic
rocks of obvious mantle affinity have a narrow span of values between —0.3 and +1.9 ‰ (averaging +0.7 ± 0.9 ‰).
Despite the lithological variability implied above, the range of

(CDT)

values measured is rather narrow when com-

pared with other granitic provinces elsewhere. The results presented here for the West-Carpathian granites fit better
within a collisional orogenic setting than in a volcanic arc and/or oceanic subduction scenario. Sulphur isotopic results
would be more easily explained within the frame of the I-/S-type model, while other data, such as magnetic susceptibil-
ity, could both fit the above and the magnetite-/ilmenite-series typology. Despite this, the data obtained could also be
explained within a model in which some sulphur is of deep-seated igneous origin, having a distinctive isotopic composi-
tion, and some additional sulphur would be derived from the country rock via assimilation processes that resulted in the
Central Western Carpathians granitoid rocks.

Key words: Western Carpathians, Hercynian orogeny, sulphur isotopes, granitic rocks, country rocks, granite typology.

Introduction

An  important  question  in  granite  petrogenesis  is  whether  a
granite  was  derived  from  an  igneous  or  a  sedimentary  pro-
tolith. Since Read (1948) pointed out that there are “granites
and  granites”,  many  typologies  have  been  proposed  (e.g.
Chappell  &  White  1974;  Ishihara  1977;  Debon  &  Le  Fort
1983;  Pitcher  1983;  Pearce  et  al.  1984;  Maniar  &  Piccoli
1989; Barbarin 1990; among others). There are many tools to
explore this query; e.g. field relations, mineralogy and petrolo-
gy,  physical  and  geochemical  parameters.  Determinations  of
radiogenic  and  stable  isotope  ratios  have  become  useful  for
this purpose as well. It was Coleman (1977) and Sasaki & Ish-
ihara (1979) who first recommended the study of sulphur iso-
topes in granite petrology. Sulphur is an important element to
be considered when trying to understand the genesis of an ig-
neous rock due to a unique set of geochemical characteristics.
In most igneous rocks, sulphur is present as a trace element,
which  usually  forms  discrete  S-rich  phases  –  in  granites,
mostly  sulphides,  e.g.  pyrite,  pyrrhotite,  chalcopyrite,  and
scarce  sulphates,  e.g.  anhydrite;  although  sulphur  may  also
substitute  into  other  phases,  e.g.  biotite,  muscovite,  horn-
blende and apatite. Indeed, sulphur, as a volatile element, is a
sensitive  indicator  of  the  degree  of  interaction  between  the
magma  and  any  S-bearing  country  rocks  into  which  it  is  in-

truded, since sulphur is much more susceptible to mobilisation
than other commonly used elements and/or isotopic ratios, e.g.
REE’s, Rb/Sr, Sm/Nd and Pb (Poulson et al. 1991). Sulphur
can be studied by stable isotope techniques, which help to pro-
vide information about a number of physico-chemical process-
es that might have taken place. Magmas formed by partial
melting of the mantle, and the rocks and fluids that may evolve
from them, should have

S values close to their mantle pro-

tolith (Ohmoto 1986). If this protolith is homogeneous, their

S values should be close to zero, relative to the reference

standard – the troilite from Cañon del Diablo meteorite
(CDT). However, actual igneous rocks have variable

(CDT)

values (Coleman 1977; Sasaki & Ishihara 1979; Kubilius 1983
in Ohmoto 1986; Ishihara & Sasaki 1989; Laouar et al. 1990;
Poulson  et  al.  1991;  Recio  et  al.  1991).  Since  at  magmatic
temperatures, no significant isotopic fractionation is to be ex-
pected among different S-bearing phases, nor as a result of de-
gassing, this was interpreted by Ohmoto (1986) and Ohmoto
&  Goldhaber  (1997)  as  the  result  of  assimilation  of  upper
crustal rocks by magmas of mantle or lower crustal derivation.
The  sulphur  content  of  granites  and  granodiorites  frequently
exceeds the amount that would be expected purely as a result
of the solubility of sulphide sulphur in the pertinent magmas,
and this, coupled with the fact that frequently the

S values

of sulphides in the granites and their country rocks are very

SULPHUR ISOTOPES OF HERCYNIAN GRANITIC ROCKS FROM WESTERN CARPATHIANS 5

sociations (magnetite + allanite and monazite + ilmenite) allow
distinction of two granite groups (I & S) in the CWC (Broska
& Gregor 1992; Petrík & Broska 1994). The occurrence of ma-
fic  microgranular  enclaves  (MME)  in  the  magnetite-bearing
granites, and presence of host (metamorphic) rock xenoliths in
the magnetite-free granites supports this division. In response
to varying geotectonic settings, different genetic types of gran-
ites  formed:  Lower  Carboniferous  crustal  thickening,  Upper
Carboniferous  thermal  events,  and  Permian  transtension  re-
spectively  resulted  in  S-,  I-  and  A-type  granite  formation
(Petrík & Kohút 1997, and references therein).

Analytical methods

Geochemical analyses (major and minor elements) were

done by XRF at the University of Ottawa, and by the classical
wet technique at the Geological Survey of the Slovak Republic,
Bratislava. The S

Tot

was measured at the Geological Survey

Spišská Nová Ves by ICP—AES. REE were analysed at the Me-
morial University of Newfoundland, St. John’s by ICP-MS
(Jenner et al. 1990) and at the MEGA Inc. Stráž pod Ralskem,
by INAA. The measurements were verified against natural, in-
ternational standards (GM and BM from ZGI Berlin). Basic
chemical data are presented in Table 1.

S ratios were de-

termined at the Stable Isotope Laboratory of Salamanca Uni-
versity (Spain) on fresh samples, none of which was obviously
mineralized.  Petrographic  examination  revealed  some  minor
sulphide  minerals,  mainly  within  biotite  flakes,  occasionally
along mica’s cleavages as well. Sulphides were also found in-
terstitially between quartz, feldspars and/or hornblende grains,
but only sporadically were these observed within these grains.
Electron  probe  microanalysis  (EDAX)  allowed  identification
of mainly pyrrhotite and pyrite ± chalcopyrite in the granitic
rocks.  Additionally,  scarce  chalcopyrite  and  sphalerite  were
identified within surrounding rocks. The generally low sulphur
content and small grain sizes prevented physical separation of
sulphides.  Instead,  we  have  used  a  chemical  extraction  tech-
nique that is based on the works of Zhabina & Volkov (1978),
Canfield et al. (1986) and Hall et al. (1988), but with modifica-
tions as described by Recio et al. (1991). This technique uses a
digestion apparatus designed by Canfield et al. (1986) to mea-
sure  the  amount  of  reduced  inorganic  sulphur  in  a  powdered
sample, and the principles described by Hall et al. (1988) for
sample  preparation  for  isotopic  analysis.  Successive  use  of
HCl and CrCl

on sample weights that varied between 1 and 25

gr. allowed us to separate sulphur (as H

S) derived from acid

soluble sulphides (in this case pyrrhotite; in some samples with
very minor sphalerite) from that derived from non-acid soluble
sulphides (here mainly pyrite, with a minor contribution of
chalcopyrite). During the time to complete the reaction, the
evolved H

S is collected over zinc acetate plus NH

solution,

and the ZnS produced is converted into Ag

S by addition of

0.1 M AgNO

. The Ag

S is preferred for isotopic analysis be-

cause it gives higher and more consistent yields during conver-
sion to SO

than the ZnS, as well as being more easily recover-

able from solution. The yield of clean SO

needed for isotopic

analysis is prepared by a method similar to that described by
Robinson & Kusakabe (1975). The

S ratios were deter-

mined in a VG-Isotech SIRA-II™ mass spectrometer. Repli-
cate analyses, including chemistry, of reference standards
NBS-123 and NZ-1 (presently referred to as IAEA-S

) gave

an average reproducibility better than ±0.2 ‰. Results are re-
ported in the familiar

notation, relative to CDT (Cañon del

Diablo troilite) in Table 2.

Review of existing data

Despite a long history of application of sulphur isotope data

in granite petrogenesis, relatively few

S studies have been

carried out when compared with other stable and radiogenic
isotopic  systems  (O,  Rb/Sr,  Sm/Nd,  Pb/Pb).  However,  from
these few studies, a useful pattern emerges. Coleman (1977)
has  shown  that  granites  from  SE  Australia  (New  England
Batholith)  have  sulphur  isotope  ratios  which  fall  into  two
groups: those within a small range of

(CDT)

from —3.6‰

to +5.0‰, representing I-type granites in the sense of Chap-
pell & White (1974), and those which are generally higher
(

(CDT)

> +5.0 ‰) or lower (

(CDT)

= —9.4 to —3.6 ‰),

reflecting S-type granites. The two series of granitic rocks de-
fined by Ishihara (1977) in Japan showed two specific isotope
trends in the work of Sasaki & Ishihara (1979). The magne-
tite-series granites all had positive

(CDT)

values from

+1 ‰ to +9 ‰, while the ilmenite-series rocks were dominat-
ed by negative

(CDT)

values between —11 ‰ and +1 ‰. In

comparison, results from the Sierra Nevada Batholith, as de-
termined by Ishihara & Sasaki (1989), were

(CDT)

from

+1.6 ‰ to +4.0 ‰ for magnetite-series granites and from
—5.3 ‰ to —3.7 ‰ for ilmenite-series rocks. Two groups, de-
rived from contrasting protoliths, have been identified by La-
ouar et al. (1990) for the British Caledonian granites. Group I
granites (I-type) have

S values within the range —4.5 ‰ to

+4.4 ‰, while group II granites (S-type) are strongly positive
at

(CDT)

= +6.2 ‰ to +16.0 ‰. Peraluminous S-type gran-

odiorites and granites from the South Mountain Batholith
(Nova Scotia) resulted in a wide range of

S values from

+1.6 ‰ to +15.0 ‰, indicating that these rocks were influ-
enced by assimilation of the country rocks (Kubilius 1983 in
Ohmoto 1986; Poulson et al. 1991). The Proterozoic granitic
rocks of Northeastern Brazil, of calc-alkaline and ultrapotas-
sic to shoshonitic affinity, all display positive

S values

ranging from +1.0 ‰ to +12.3 ‰ (Sial & Ferreira 1990). Her-
cynian cordierite-bearing granites of the Central Iberian Zone,
Iberian Massif of Spain, have

(CDT)

values from —3.9 ‰ to

+4.8 ‰ (Recio et al. 1991). The

S values ranged from

+2 ‰ to +9 ‰ for the granitoids hosting porphyry cooper
mineralization in Chile, while host rocks of identical mineral-
ization from Philippines gave

S values from —1.4 ‰ to

+9.5 ‰, indicating a volcanic arc setting for these magnetite-
series rocks and/or deposits (Sasaki et al. 1984). The bulk of
data from altered granitic rocks of Bonnet Batholith – Mani-
toba, with

S values from —1.2 ‰ to +7.5 ‰ (Krouse &

Ueda 1987), fall into the range associated with I-type granites,
according with Coleman (1977). Cretaceous-Tertiary grani-
toids of the Kohistan arc – Northern Pakistan, have

S val-

ues from —0.6 ‰ to +5.4 ‰, while Cambrian granites of this
same arc display higher positive

S from +8.1 ‰ to +9.0 ‰,

6 KOHÚT

and RECIO

although both groups belong to the ilmenite-series (Ishihara et
al. 1996). The isotopic composition of sulphidic sulphur from
the Žulová massif (NE Bohemian Massif), described by Losos
et al. (1994) as a typical ilmenite-series pluton, is relatively
homogeneous, with

(CDT)

values ranging from —4.0 ‰ to

+3.0 ‰, which are typical values for sulphur derived from
deep-seated sources (Hoefs 1997). The sulphur isotope signa-
ture of the Hercynian West-Carpathian granites has not been
known till present. There were sparse isotopic data from sepa-
rated sulphide minerals only, from the Cretaceous Rochovce
Granite (Repčok et al. 1990), with

(CDT)

values from

—0.47 ‰  to  +1.88 ‰,  documenting  an  I/A  character  for  this
granite.  Various  poorly  identified  Hercynian  granitic  rocks
from  Central  Europe  are  reported  to  have  a  large  spread  of

S values from —4 ‰ to +12 ‰ (Siewers 1974 in Nielsen

1978).

Unfortunately, little attention has been paid in the literature

to the sulphur isotope signature of granite’s host-rocks. The
sedimentary hosts of some granitic terranes in Japan display
strictly negative

S values from —1.4 ‰ to —21.5 ‰ (Sasaki

& Ishihara 1979). The metamorphic rocks from the South
Mountain Batholith (Nova Scotia) showed a wide range of

S values from —3.7 ‰ to +26.3 ‰, without major differenc-

es reported from greenschist to amphibolite facies, or between

former pelites and psammites (Poulson et al. 1991). The Dal-
radian metasediments from Scotland have

S mostly be-

tween +11 ‰ and +17 ‰ (Hall et al. 1989). Low-P, high-T
metamorphic rocks (nebulites) of the Central Iberian Zone of
the Iberian Massif yielded exclusively positive

(CDT)

val-

ues between +1.1 and +10.6 ‰ (Recio et al. 1991). It is inter-
esting that greywackes from this area gave both positive and
negative

S values of +7 ‰ and around —5 ‰, while inter-

mediate to basic enclaves within the granite were mainly close
to 0 ‰, exception made of one quartzdioritic enclave that has
a value of

S = +13.4 ‰. Pelitic rocks of the Kohistan arc

showed negative

S values from —3.6 ‰ to —7.9 ‰, while

metamorphosed pelites have positive

S values from +2.3 ‰

to +10.2 ‰, and amphibolitic rocks reveal

S values from

+0.6 ‰ to +3.2 ‰ (Ishihara et al. 1996). High-grade metamor-
phic rocks of the Ivrea Zone (stronalites and kinzigites; am-
phibolite- to granulite-facies gneisses) are highly variable,
with

S values from —23 ‰ to +13 ‰, typical of marine sed-

iments (Schnetger 1994). Because of the large variation of sul-
phur isotopic composition, of likely primary sedimentary ori-
gin, no difference between groups of metamorphites can be
seen. Granulites from Southern Norway also have a large
spread of

S from —4 ‰ to +17 ‰, with values around +5 ‰

most frequent (Andreae 1974 in Nielsen 1978). In contrast to

Table 1: Chemical composition (major + trace elements and REE) of the studied Carpathian samples. Explanations: abT – amphibole-
biotite tonalite, mbGD – muscovite-biotite granodiorite, mG – muscovite granite, baD – biotite-amphibole diorite, Gabb – gabbro,
b Gn – biotite gneiss, Msch – mica schist, Amph – amphibolite etc. Major elements are in wt. %, trace elements and REE are in ppm.

Sample

VF-43

VF-639

VF-700

TL-117

VT-2/96

ZK-4

VVM-129

VF-356

T-88

VG-45

NT-487

V-9039

KV-3/1222

S-type

I-type

I/A-type

Type

mbG

bGD

mbGD

bGD

bmG

abT

baD

bGD

SiO

72.66

66.33

73.94

71.24

68.85

73.31

76.09

68.76

66.02

63.66

54.84

69.77

70.31

TiO

0.21

0.58

0.16

0.25

0.87

0.08

0.11

0.51

0.75

0.82

1.03

0.38

0.30

14.64

15.70

13.27

14.56

14.79

14.07

12.75

15.59

17.00

16.78

14.78

14.05

14.06

0.47

1.62

0.94

1.24

1.18

0.73

0.41

0.81

1.13

1.97

2.01

2.21

1.08

FeO

1.43

1.93

1.25

1.56

2.02

1.35

0.98

2.33

2.89

2.73

5.38

2.06

1.87

MnO

0.03

0.05

0.02

0.04

0.05

0.06

0.03

0.04

0.07

0.06

0.18

0.07

1.16

MgO

0.61

1.21

0.15

0.77

0.96

0.55

0.13

1.22

1.64

2.64

8.32

0.90

0.06

CaO

1.42

2.89

0.69

2.26

2.75

1.10

0.49

2.83

3.36

3.68

5.58

1.53

2.58

3.74

5.01

4.39

4.48

4.33

4.00

2.99

4.04

3.89

3.13

2.67

5.82

3.45

3.52

2.94

3.98

1.87

2.47

3.47

4.76

2.24

2.08

2.30

2.63

2.04

4.01

0.13

0.24

0.21

0.16

0.18

0.21

0.20

0.23

0.46

0.11

0.28

O+

0.75

1.24

0.76

1.10

1.32

0.78

0.94

0.88

1.54

1.88

0.87

0.58

O-

0.18

0.13

0.08

0.18

0.45

0.04

0.11

0.14

0.18

0.21

0.16

0.05

0.25

Total

99.79

99.87

99.84

99.76

99.98

100.24

99.81

99.66

100.09

99.75

99.92

99.86

99.99

tot

200

320

150

230

320

220

385

850

800

600

900

259

365

103

449

565

122

563

852

851

680

160

520

110

177

108

158

448

102

864

641

405

880

821

316

826

1015

1021

650

782

848

112

203

159

168

185

263

249

150

845

159

12.36

11.50

6.36

7.00

13.32

14.99

17.73

6.98

15.18

18.00

16.00

69.00

26.00

8.79

8.34

6.00

10.00

11.21

9.19

19.65

8.56

12.32

14.00

15.00

40.00

20.00

0.79

0.44

0.33

0.29

0.40

1.24

5.46

0.62

0.59

0.62

0.25

2.00

0.20

2.96

4.62

1.21

4.10

4.64

0.91

2.08

4.30

5.32

6.03

4.74

25.90

4.60

6.40

8.90

2.95

6.30

11.23

5.50

9.55

6.26

9.10

12.00

10.20

15.20

28.60

2.50

2.20

3.80

2.60

4.50

3.40

6.40

4.10

2.70

3.00

3.50

1.90

9.20

20.79

31.20

5.36

26.67

34.77

6.45

7.67

24.56

43.66

86.91

43.95

110.30

73.05

42.99

66.34

11.04

54.56

71.63

13.40

17.99

51.11

87.90

179.40

96.62

200.30

144.20

19.73

29.52

4.84

25.67

31.67

5.81

9.51

23.07

38.47

68.79

42.34

106.00

53.84

4.20

5.41

1.27

3.91

5.98

1.82

2.68

4.17

6.45

10.03

7.28

20.00

9.72

0.76

1.09

0.42

0.95

1.14

0.45

0.13

1.19

1.58

1.93

1.95

4.83

1.53

3.32

3.85

1.22

2.89

4.15

2.05

2.20

2.98

4.61

6.07

7.68

6.61

0.47

0.49

0.21

0.36

0.54

0.43

0.48

0.35

0.60

0.70

1.15

2.30

0.90

0.16

0.15

0.08

0.13

0.18

0.24

0.08

0.21

0.12

0.35

0.43

0.94

0.95

0.51

0.71

1.03

1.65

1.34

0.51

1.27

0.75

1.95

10.10

2.75

0.13

0.07

0.12

0.14

0.24

0.18

0.08

0.19

0.14

0.40

1.67

0.42

SULPHUR ISOTOPES OF HERCYNIAN GRANITIC ROCKS FROM WESTERN CARPATHIANS 7

Sample

VF-244

BT-253

BT-217

BT-2222

ZT-1/97

BT-11

ZT-2/92

BT-218

KV-3/622

Type

b Gn

ab Gn

Msch

Amph

Gab

SiO

65.07

60.18

65.65

60.67

59.89

58.29

52.65

48.65

48.78

TiO

0.76

1.18

0.87

0.47

0.85

0.59

1.08

1.61

0.78

16.63

16.39

14.47

15.87

18.82

15.69

14.67

14.43

11.22

2.07

1.82

1.14

1.59

4.25

3.07

4.05

2.40

5.16

FeO

3.95

4.63

4.92

4.65

3.82

3.38

6.69

6.79

6.12

MnO

0.10

0.07

0.10

0.16

0.11

0.18

0.14

0.16

MgO

1.91

3.24

2.52

3.98

2.21

4.48

6.72

11.62

15.21

CaO

1.31

3.11

1.51

6.06

1.78

6.14

8.84

8.37

7.44

3.20

3.38

2.74

2.94

2.11

3.19

2.74

1.92

1.74

3.26

3.27

3.68

1.88

3.98

1.65

0.41

1.69

2.76

0.26

0.61

0.08

0.10

0.14

0.22

0.17

0.66

0.34

O+

1.27

1.43

1.55

1.07

1.47

2.27

1.11

1.03

0.19

O-

0.12

0.32

0.34

0.29

0.45

0.46

0.21

0.27

0.25

Total

99.91

99.63

99.57

99.67

99.93

99.54

99.52

99.58

100.15

tot

370

400

450

580

600

750

1150

950

1200

140

298

199

191

130

149

241

638

139

107

128

185

139

706

1051

564

254

710

284

495

635

190

296

211

100

158

123

23.00

28.00

24.00

13.75

27.00

13.00

19.80

22.00

18.00

9.00

17.00

11.00

4.75

19.00

4.00

3.85

2.00

4.80

0.35

0.80

0.90

0.88

1.35

0.70

0.13

1.00

0.50

4.90

6.00

5.00

2.85

11.00

2.00

1.79

3.00

5.10

15.40

20.00

9.00

6.00

14.00

5.00

0.93

7.00

8.80

5.80

5.60

2.10

2.90

4.00

2.30

0.52

2.00

4.00

32.94

35.12

35.33

17.63

38.26

13.08

4.45

18.24

55.58

58.82

71.20

60.46

34.38

75.33

29.11

11.15

41.53

109.70

32.06

38.34

30.08

15.43

31.92

14.96

7.21

23.07

45.84

5.70

7.51

5.07

3.23

6.30

3.56

2.32

6.13

9.90

1.11

1.45

1.10

0.66

1.31

0.65

0.85

1.65

2.05

4.95

9.82

7.89

3.44

5.36

3.15

3.04

6.65

4.69

0.65

1.50

1.28

0.61

0.88

0.52

0.55

1.05

0.68

0.39

0.55

0.60

0.34

0.48

0.25

0.31

0.45

0.27

2.85

3.05

3.12

1.83

3.08

1.50

2.18

2.38

1.40

0.41

0.45

0.48

0.27

0.51

0.22

0.32

0.36

0.19

Table 1: Continued.

Table 2: Magnetic susceptibility and sulphur isotopic ratio –

(CDT)

values of the CWC samples. M

and M

represent milligrams of

S obtained per gram of whole rocks sample reacted (1 mg = 1000 ppm). M

is the total amount of Ag

S obtained (from acid-soluble

and non acid-soluble fractions). The total

S is the bulk sulphur isotopic value as calculated by mass balance. When only “Total” values

are reported, it indicates that no separation between acid-soluble and non acid-soluble fractions was possible (i.e., the sulphide fraction is
overly dominated by disulphides), and only the bulk isotopic value for the sample is given.

Sample

Rock type

Magn.susc.

Acid soluble

Non-acid soluble

Total

κ (SI u.×10

–6

)

(mg/g)

S (‰)

(mg/g)

S (‰)

(mg/g)

S (‰)

VF-43

S-t

181.3

0.015

-0.95

VF-639

S-t

1051.0

0.026

0.56

VF-700

S-t

0.5

0.010

1.85

TL-117

S-t

890.5

0.010

3.37

VT-2/96

S-t

2154.0

0.043

0.64

0.052

4.13

0.095

2.55

ZK-4

S-t

0.5

0.144

5.70

VVM-129

S-t

57.9

0.053

4.48

VF-356

I-t

3051.0

0.147

-1.50

T-88

I-t

4580.0

0.084

-2.86

VG-45

I-t

4509.0

0.024

0.13

3.598

2.35

3.622

2.33

NT-487

I-t

4695.0

8.909

0.70

V-9039

I/A-t

9645.0

0.765

-0.69

KV-3/1222

I/A-t

19575.0

3.263

-2.01

VF-244

958.0

0.021

0.19

0.011

0.71

0.032

0.37

BT-253

1245.0

0.041

2.62

0.085

0.57

0.126

1.24

BT-217

467.5

0.009

4.17

0.152

4.63

0.161

4.60

BT-2222

1425.0

4.860

-0.11

ZT-1/97

Msch

564.5

0.448

-2.08

2.034

-1.93

2.482

-1.96

BT-11

Amph

6960.0

0.018

-0.34

0.362

-0.26

0.380

-0.26

ZT-2/92

Amph

11710.0

0.021

0.69

14.889

1.87

14.910

1.86

BT-218

Gab

6155.0

0.005

0.11

0.627

0.85

0.632

0.85

KV-3/622

Gab

4635.0

0.102

-3.47

6.942

0.36

7.044

0.31

8 KOHÚT

and RECIO

the above, gneisses from Central Europe have a narrower
spread of

S values from —4 ‰ to +6 ‰, while mica schist

from the area have positive

S from +2 ‰ to +9 ‰ (Siewers

1974 in Nielsen 1978). In summary (Figs. 2 and 3), no system-
atic behaviour for the sulphur isotopic characteristics of partic-
ular granites and their host-rocks emerges from review of the
literature.

Results

Major and trace element contents, including REE, of the

studied samples are given in Table 1. Given the limitations of
our  work,  we  selected  a  few  samples  representative  of  the
whole  CWC  crystalline  basement,  focusing  mainly  on  the
Hercynian granitic rocks. One sample (KV-3/1222) of the Al-
pine-Cretaceous Rochovce Granite (Hraško et al. 1999; Poller
et al. 2001) is included for comparison. It is obvious from Ta-
ble 1 that for this research we chose an extremely variegated
set of granitoids, from diorite to leucocratic granite, and their
host-rocks  (represented  by  gneisses,  mica  schists,  amphibo-
lites and/or gabbro).

The

(CDT)

data of sulphidic sulphur obtained in this

work are given in Table 2, and plotted in histogram form in
Fig. 4. Chemical separation techniques from whole rock yield-
ed sulphur enough for analysis only in 22 out of the 26 origi-
nally selected samples. From Table 2 it can be seen that the
sulphur content (expressed as mg Ag

S per g of whole-rock

sample  treated)  of  S-type  granites  is  generally  low  between
0.010 and 0.144 mg/g (average 0.05 ± 0.05), which is several
times lower than sulphur content of I-type granites, that ranges
between 0.084 and 8.909 mg/g (average 2.80 ± 3.37). Sulphur
content in the gneissic rocks, from 0.032 to 4.860 mg/g (aver-
age 1.53 ± 2.13) is within the range of both granite groups. Sul-
phur  content  of  basic  rocks  and  their  metamorphosed  ana-
logues  (gabbro  and  amphibolites)  is  generally  high  in
comparison  with  felsic  crustal  rocks.  As  expected,  samples
with higher bulk sulphur content (expressed as S

Tot

in Table 1)

yielded more sulphur on chemical treatment for isotopic analy-
sis (Table 2), thus confirming that sulphur-bearing phases are
essentially  sulphides.  Oxidized  (I-type;  Magnetite-series)
granites whose oxygen fugacity is above the NNO buffer may
have sulphates; most likely anhydrite, while reduced (S-type,
Ilmenite-series) granites carry most of its sulphur in reduced
form,  as  pyrrhotite  (Ohmoto  1986;  Ohmoto  &  Goldhaber
1997). A way of testing the reduced/oxidized character of sul-
phur forms in the rocks under consideration is to plot sulphur
content  against  FeO  content.  If  S  is  present  in  reduced  form
only a positive correlation is to be expected. There is a good
correlation between both parameters plotted (Fig. 5), and even
I-type rocks plot in trend, suggesting that most sulphur is in a
reduced form. Generally distribution of FeO is controlled by
presence of biotite within CWC granitic rocks, whereas horn-
blende is rather scarce in the I-type rocks. Higher content of
Fe-Mg  silicic  minerals  is  connected  with  greater  amounts  of
bulk sulphur mainly in the form of minute inclusions within
them and vice versa. However, some of the I-type rocks show
evidence  for  additional  sulphur  phases,  most  likely  oxidized
ones, that would have been unaccounted for by our analytical

Fig. 3. Summary of

(CDT)

values for the host-rocks of the gra-

nitic suites of Fig. 2. Sources of data in the text. Explanations:
Box – psammite (greywackes) and their metamorphic equiva-
lents. Diamond – pelites and their metamorphic equivalents.

Fig. 2. Ranges of

(CDT)

values for granites worldwide. Sources

of  data  in  the  text.  Explanations:  Doted  line  –  S-type  and/or  Il-
menite-series  granites.  Solid  line  –  I-type  and/or  Magnetite-se-
ries granites. The applicability of this classification to rocks other
than  those  originally  used  to  define  it  is  controversial,  however;
its use here is for illustrative purposes and does not mean endorse-
ment by the authors. Granites from Central Europe (Siewers 1974
in Nielsen 1978) were not classified by the original author.

Fig. 4. Histogram of

(CDT)

values from the West-Carpathian

rocks. I-t – I-type granites, S-t – S-type granites, Gn – gneiss-
es, Amph – amphibolites, Gab – gabbros.

-3

-2

-1

S (‰)

S-t

I-t

Amph

Gab

SULPHUR ISOTOPES OF HERCYNIAN GRANITIC ROCKS FROM WESTERN CARPATHIANS 9

2.3 ‰), while I-type granites have

S values in the vicinity

of zero, from —2.86 to +2.33 ‰ (average —0.67 ± 1.9 ‰), in
good agreement with a possible derivation from lower crustal
or mantle sources (Ohmoto 1986). Heavier

S values from

—1.96 to +4.60 ‰ (average +0.83 ± 2.1‰) characterize the sur-
rounding medium-grade metamorphic rocks (gneisses ± mica
schist), in good agreement with S-type granites. Basic igneous
and metamorphic rocks of obvious mantle origin have a nar-
row span of

S values from —0.26 to +1.86 ‰ (average

+0.69 ± 0.9 ‰). However, chemical and petrographical varia-
tions within the samples studied are large (Table 1), which
contrasts with the rather narrow spread of

(CDT)

, and with

isotopic values in other granite areas worldwide. Although our
research  was  limited  in  scope,  there  is  evidently  a  general
overlap of isotopic compositions between both groups of gra-
nitic rocks and nearby felsic and mafic rocks (Fig. 4). The sul-
phur  isotopic  composition  has  been  plotted  against  sulphide
content of the samples in Fig. 6. S-type granites are character-
ized by low sulphur content and heavier isotopic values, while
I-type rocks are isotopically lighter, but have more sulphur. In
terms  of  sulphur  content  and  isotopic  composition,  samples
plot correctly on each side of the proposed Carpathians I/S line
of Fig. 6.

Discussion

Coleman (1977) realized that, in contrast with common be-

lief, S-type granites of the New England Batholith contained
higher bulk sulphur that I-types, and used

S values as dis-

criminating criteria, thus introducing sulphur isotopes in gran-
ite typology. Considering that the correlation between S

Tot

determined by chemical analysis, and Ag

S content, as deter-

mined during sulphur extraction for isotopic analysis is signifi-
cant (r = 0.732, for n = 22), we have plotted the sulphur content
versus the isotopic values in Fig. 7, and have included Cole-
man’s (1977) divide between I- and S-type granites. Surpris-
ingly, all samples from the CWC, including evidently peralu-
minous leucogranites and biotite paragneisses, lie within the
field for I-type granites in this diagram. However, an I/S line

Fig. 5. Plot of total sulphur content versus FeO content according
Ohmoto & Goldhaber (1997) for testing the presence of sulphide
and sulphate phases in silicate rocks. Symbols as are marked: Box
– S-type granites, Grey circle – I-type granites, Diamond –
gneisses, Triangle – amphibolites, Black circle – gabbros.

100

1000

10000

0.1

1.0

10.0

100.0

FeO (wt%)

(ppm)

S-t

I-t

Amph

Gab

Granitoid magmas

650

870

1025

1200 °C

Basaltic magmas

"FeS" species limit

scheme (that is specific for reduced sulphur; see Canfield et al.
1986; Hall et al. 1988). This should, however, not affect no-
ticeably our main inferences, since according to Ohmoto &
Goldhaber (1997; pg. 587) “... observed isotopic fraction-
ations between sulfate and sulfide from I-type volcanic rocks
are in most cases disequilibrium values at magmatic tempera-
tures …”. S-type granites, except for one sample, show posi-
tive

S values between —0.95 and +5.70 ‰ (average +2.51 ±

Fig. 7. Plot of

(CDT)

values versus total sulphur content (ppm) for

the studied CWC rocks. Solid line dividing S-type and I-type gran-
ites is after Coleman (1977); doted line represents the suggested I/S
line for the Carpathians granitic rocks. Symbols as in Fig. 5.

Fig. 6.

(CDT)

values versus sulphur content of samples from the

Central Western Carpathians. M

is yield in mg of Ag

S (as evolved

from total acid-soluble + non acid-soluble sulphides) per g of whole
rock sample used. The

(CDT)

value reported is the bulk sulphidic

sulphur isotopic composition of the rock as calculated by mass bal-
ance, from the results obtained for the acid soluble and non-acid
soluble fractions (if available); data from Table 2. Symbols as in
Fig. 5.

10 KOHÚT

and RECIO

for  the  Carpathian  samples  can  still  be  drawn.  This  “Car-
pathians  I/S  line”  is  a  better  discriminant  of  supposed  sedi-
mentary and/or igneous protoliths of the CWC granitic rocks;
indeed, the limited number of metamorphic rocks falls in the
correct  side  of  the  dividing  line.  Interestingly  enough,  when
this line is projected onto Sasaki & Ishihara’s (1979) Fig. 2,
there is better agreement with the Japanese ilmenite-/magne-
tite-series classification than with Coleman’s (1977) I/S divid-
ing  line.  Hence,  we  cannot  exclude  a  potentially  important
contribution of metasedimentary rocks resulting from assimi-
lation (AFC) and/or stoping processes in the genesis of these
two main CWC granite groups.

The accessory minerals dichotomy (magnetite + allanite &

monazite  +  ilmenite)  of  the  West-Carpathian  granitic  rocks
(Broska & Gregor 1992; Petrík & Broska 1994) is similar to
Japanese granitoids, where Ishihara (1977) defined magnetite-
and  ilmenite-series  granites.  The  magnetite-series  rocks  are
characterized  by  magnetite,  hematite,  ilmenite,  and  pyrite  or
chalcopyrite as opaque minerals, while ilmenite-series grani-
toids are practically devoid of opaque oxide minerals, but con-
tain varying amounts of pyrrhotite in addition to ilmenite. This
is in good agreement with observations by Whalen & Chappell
(1988), who reported dominantly pyrite in I-type granites, with
minor contributions of chalcopyrite and pyrrhotite, whereas S-
type  granites  contained  mainly  pyrrhotite,  with  subordinate
pyrite  and  chalcopyrite.  Although  both  classifications  share
many similarities, it was stated by Takahashi et al. (1980) and
Ishihara (1981) that they are not equivalent; the main differ-
ence being the tectonic setting; e.g. subduction under a volca-
nic arc, or collisional thickening, and/or redox state of source-
rocks. The ilmenite- and magnetite-series rocks in Japan were
well  characterized  by  magnetic  susceptibility  as  well  as  by
their sulphur isotopic ratio (Ishihara 1977; Sasaki & Ishihara
1979). The use of magnetic susceptibility as a petrogenetic pa-
rameter  has  tradition  in  granite  studies  in  the  Western  Car-
pathians (Broska & Gregor 1992; Kohút 1992; Kohút & Janák
1994, among others). The use of Ishihara’s value of

= 3

—3

SI units gives good discrimination. Those rocks having

—3

SI u. are generally considered as magnetite-series

rocks (I-type), while granites with lower susceptibility are
classified as ilmenite-series (S-type) granites. Since both types
of data are available for this work, we have plotted

versus

S (Fig. 8), following Ishihara & Sasaki (1989), to see how it

applies to the CWC rocks. The disagreement in values be-
tween West-Carpathian and Japanese rocks is evident. Even
when magnetic susceptibility data are in good agreement,

values are not. The CWC granitic rocks plot all over Ishihara
& Sasaki’s (1989) diagram, although predominantly in oppo-
site quadrants than granitoid data from Circum-Pacific orogen-
ic  belts  (Fig.  8).  Despite  the  above,  CWC  peraluminous
leucogranites  represent  analogues  of  magnetite-series  rocks,
while  nearly  all  calc-alkaline  biotite  (±  amphibole—biotite)
bearing tonalite can be regarded as ilmenite-series in terms of
its sulphur isotopic composition (Sasaki & Ishihara 1979). In
spite of the limitations of our data set, it can be envisaged that
the  misfit  of  the  West-Carpathian  Hercynian  granitic  rocks
within  the  Japanese  classification  as  ilmenite-/magnetite-se-
ries rocks may well be related with much different geotectonic
setting (subduction under a volcanic arc in Japan, and a conti-

Fig. 8.

(CDT)

versus magnetic susceptibility for the West-Car-

pathian samples. Doted areas are the fields of “true” Magnetite-
and Ilmenite-series granitoids from the Circum-Pacific orogenic
belts, according to Ishihara & Sasaki (1989). Symbols as in Fig. 5.

nental collisional processes in the Western Carpathians). The
most  of  geochemical  features  suggest  that  the  CWC  granitic
rocks are analogous to igneous suites commonly generated by
subduction  in  an  Andean-type  active  continental  margin.
However, field evidence documents a collisionally thickened
crust, with inverted structure of the CWC basement, intruded
by  a  lensoid  (sheet-like)  granite  body  within  its  upper  unit
(Janák 1994; Kohút & Janák 1994). P-T conditions in the sur-
rounding metamorphic rocks association indicate either an in-
tracontinental  subduction  or  a  collisional  setting,  involving
high-grade metasedimentary and metaigneous rocks at lower-
to  mid-crustal  conditions  (Janák  1994;  Ludhová  &  Janák
1999).  A  similar  situation  has  been  described  for  a  classical
convergent  orogen  –  the  Himalaya  (Le  Fort  1981;  France-
Lanord & Le Fort 1988; Harrison et al. 1998). It is generally
accepted that the CWC granitic rocks were formed as a result
of  Hercynotype  oblique  continental  collisional  processes
(Petrík et al. 1994; Kohút & Janák 1994; Petrík & Kohút 1997
among  others).  The  collision  induced  melting  of  a  vertically
zoned  lower  crust,  consisting  of  various  metapelitic  and
metaigneous rocks, including an old greenstone belt with to-
nalitic greywacke gneisses as an important constituent.

As already mentioned, there are no major differences in sul-

phur isotopic compositions between arc- and collision-related
granitic rocks (Fig. 2). Similarly, there are no big differences
between psammitic and pelitic rocks and/or their metamorphic
equivalents within these two tectonic settings (Fig. 3). Howev-
er, in both cases contamination of granitic magmas by partial
melting  of  surrounding,  mainly  sedimentary,  rocks  has  been
widely reported (see for example Ugidos 1990). Assimilation
of country rocks is a common process operating during mag-
matic and final solidification stages of granitic rocks, and can
significantly modify granite composition. The incorporation of
sedimentary  material  into  the  granitic  magmas  could  have
been a major reason leading to the reduced character of these
granitic  rocks.  In  fact,  interaction  with  pelitic  rocks  with  a
high sedimentary organic carbon content can change the char-
acter of an originally oxidised, I-type, granitic magma to an il-
menite-series like, reduced, S-type, magma (Ishihara & Sasaki
1989). Similarly, magmas may increase their ore-forming po-

SULPHUR ISOTOPES OF HERCYNIAN GRANITIC ROCKS FROM WESTERN CARPATHIANS 11

tential by acquiring excess sulphur from the country rocks dur-
ing emplacement in the upper crust. There are several mecha-
nisms through which the magmas, or an igneous rock, can gain
country-rock sulphur, e.g. a) bulk assimilation of volatile and
non-volatile elements transfer from country-rocks to magma,
b)  selective  assimilation  of  country—rock,  volatilized,  sul-
phides by the magma, and c) subsolidus transfer via fluids that
circulated  through  the  country-rock  and  the  igneous  rock
(Ohmoto  &  Goldhaber  1997).  Peraluminous,  S-type  granitic
rocks are generally inferred to be produced by crustal anatexis
of clastic sedimentary material, such as shales or greywackes,
while  calc-alkaline,  I-type  granites  are  commonly  generated
by  melting  of  an  old  (meta)igneous,  lower  crustal  protolith.
Recycled  crustal  sedimentary  material  is  characterized  by
variable

(CDT)

values from —50 ‰ to +20 ‰, in marked

contrast with homogenized lower crustal sources, having

(CDT)

values around 0 ‰ ±1 ‰ (Ohmoto & Goldhaber

1997). The sulphur isotope data from the Western Carpathians
are consistent with a hypothesis according to which magmas
generated by partial melting of a protolith producing calc-alka-
line I-type granitic rocks, encountered protoliths typical of per-
aluminous S-type rocks at higher crustal levels during ascent
within  the  context  of  the  Hercynian  collisional  orogeny.  In-
deed, we cannot ignore the finding that most of sulphur in gra-
nitic  rocks  was  actually  acquired  during  their  emplacement
(Ohmoto  1986;  Recio  et  al.  1991;  Poulson  et  al.  1991),  and
this  fact  can  partly  explain  the  general  similarity  of  isotopic
compositions  for  both  groups  of  granitic  rocks,  with  narrow
spreads  of

(CDT)

values, similar to those of surrounding

felsic and mafic rocks in the Western Carpathians.

Conclusion

The sulphur isotope study of selected granitic and surround-

ing rocks from the Western Carpathians reveals that the more
basic rocks, having higher whole-rock bulk sulphur contents,
yielded more sulphide for isotopic analysis. Our results repeat-
edly contradict the old opinion that S-type granitic rocks con-
tain greater bulk sulphur than I-type granites. The limited sul-
phur isotope data-base reveals a relatively narrow spread,
when compared with other granite suites worldwide, of

(CDT)

, ranging from —2.86 ‰ in I-type tonalites to

+5.70 ‰ in peraluminous S-type leucogranites. Isotopic val-
ues of CWC granitic rocks generally overlap with values from
surrounding felsic and mafic rocks, which span from —1.96 ‰
to +4.60 ‰. The isotopic results reported favour an origin for
the West-Carpathian Hercynian granitic rocks within a colli-
sional setting, rather than in a volcanic arc. The

(CDT)

val-

ues seem to fit better within the frame of the I-/S-type classifi-
cation, rather than within an ilmenite-/magnetite-series type of
classification. However, even part of the sulphur may certainly
be of igneous derivation, it seems highly plausible that CWC
granitic rocks may have been involved in assimilation process-
es of their upper crustal hosts, which would have contributed
additional sulphur.

Acknowledgments: We are grateful to Dr. Igor Broska, and
Dr. ubomír Hraško, who have kindly donated part of the

samples used for this study and permitted publishing primary
chemical data. Professor Petr Černý (The University of Mani-
toba, Winnipeg) and Dr. Pavel Uher (SAS Bratislava) are
thanked for major and trace element analyses, financed by
NSERC Grant #311-1727-17. Thoughful reviews by Professor
Jana Hladíková, Dr. Karel Žák and Dr. Igor Petrík greatly im-
proved the manuscript, and the authors wish to express grati-
tude to them. This article is a contribution to the IGCP Project
No. 373.

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SULPHUR ISOTOPES OF HERCYNIAN GRANITIC ROCKS FROM WESTERN CARPATHIANS 13

Number
Sample

rock type location

Latitude

(°N)

Longitude

(°E)

Altitude

(m)

VF- 43

— muscovite-biotite granite, natural outcrop Vyšná Krivá,

49°01´23˝01

19°11´33˝20

1035

VF-639

— biotite granodiorite, natural outcrop Blatná valley,

49°00´17˝11

19°09´29˝40

742

VF-700

— muscovite granite, natural outcrop Nižné Matejkovo,

49°00´09˝26

19°15´54˝23

825

TL-117

— muscovite-biotite granodiorite, nat.o., Prostredný ridge,

49°11´24˝19

20°01´31˝23

1920

VT-2/96

— biotite granodiorite, nat.outcrop, Velická valley,

49°09´47˝38

20°09´17˝44

1925

ZK-4

— muscovite granite, natural outcrop Vyšná Boca,

48°55´28˝56

19°44´28˝57

1045

VVM-129

— biotite-muscovite granite, drill well Peklisko,

48°48´40˝58

20°33´39˝49

596

VF-356

— biotite tonalite, quarry Vyšné Matejkovo,

48°59´47˝22

19°15´03˝59

812

T-88

— amphibole-biotite tonalite, nat.o., Javorový Hill,

48°46´08˝05

18°52´30˝05

715

VG-45

— amphibole-biotite tonalite, quarry, Kamenistá valley,

48°35´23˝11

19°36´59˝36

855

NT-487

— amphibole-biotite diorite, natural outcrop, Bôr ridge,

48°58´27˝53

19°32´43˝48

1715

V-9039

— biotite granodiorite, natural outcrop, Turčok,

48°36´15˝10

20°10´08˝22

425

KV-3/1222

— biotite granite, drill well Rochovce,

48°42´04˝06

20°17´39˝21

408

VF-244

— biotite gneiss, natural outcrop, Smrekovica ridge,

48°58´07˝55

19°15´01˝18

1035

BT-217

— biotite gneiss, natural outcrop, Patria ridge,

49°00´53˝30

20°54´03˝41

905

BT-253

— biotite gneiss, natural outcrop, Zvoľanská ridge,

49°00´40˝32

20°53´12˝35

955

BT-2222

— amphibole-biotite gneiss, road tunnel, Svinka valley,

49°00´21˝53

20°52´54˝05

750

ZT-1/97

— mica schist, natural outcrop, Žiarská valley,

49°09´12˝26

19°42´53˝38

1015

BT-11

— amphibolite, natural outcrop, Zvoľanská ridge,

49°00´11˝21

20°53´57˝03

920

ZT-2/92

— amphibolite, natural outcrop, Žiarská valley,

49°09´04˝42

19°42´35˝18

985

BT-218

— gabbro, natural outcrop, Patria ridge,

49°00´51˝53

20°53´57˝03

915

KV-3/622

— gabbro, drill well Rochovce.

48°42´04˝06

20°17´39˝21

408

Appendix: Sample description and location