GeolCarp_Vol69_No5_483

GEOLOGICA CARPATHICA

, OCTOBER 2018, 69, 5, 483–497

doi: 10.1515/geoca-2018-0028

www.geologicacarpathica.com

Accessory minerals and evolution of tin-bearing

S-type granites in the western segment

of the Gemeric Unit (Western Carpathians)

IGOR BROSKA



and MICHAL KUBIŠ

Earth Science Institute of the Slovak Academy of Sciences, Dúbravská cesta 9, 840 05 Bratislava;



igor.broska@savba.sk

(Manuscript received May 27, 2018; accepted in revised form October 4, 2018)

Abstract: The S-type accessory mineral assemblage of zircon, monazite-(Ce), fluorapatite and tourmaline in the cupolas

of Permian granites of the Gemeric Unit underwent compositional changes and increased variability and volume due to

intensive volatile flux. The extended S-type accessory mineral assemblage in the apical parts of the granite resulted in

the formation of rare-metal granites from in-situ differentiation and includes abundant tourmaline, zircon, fluorapatite,

monazite-(Ce), Nb–Ta–W minerals (Nb–Ta rutile, ferrocolumbite, manganocolumbite, ixiolite, Nb–Ta ferberite,

hübnerite), cassiterite, topaz, molybdenite, arsenopyrite and aluminophosphates. The rare-metal granites from cupolas in

the western segment of the Gemeric Unit represent the topaz–zinnwaldite granites, albitites and greisens. Zircon in these

evolved rare-metal Li–F granite cupolas shows a larger xenotime-(Y) component and heterogeneous morphology

compared to zircons from deeper porphyritic biotite granites. The zircon Zr/Hf

ratio in deeper rooted porphyritic granite

varies from 29 to 45, where in the differentiated upper granites an increase in Hf content results in a Zr/Hf

ratio of 5.

The cheralite component in monazite from porphyritic granites usually does not exceed 12 mol. %, however, highly evolved

upper rare- metal granites have monazites with 14 to 20 mol. % and sometimes > 40 mol. % of cheralite. In granite cupo-

las, pure secondary fluorapatite is generated by exsolution of P from P-rich alkali feldspar and high P and F contents may

stabilize aluminophosphates. The biotite granites contain scattered schorlitic tourmaline, while textural late-magmatic

tourmaline is more alkali deficient with lower Ca content. The differentiated granites contain also nodular and dendritic

tourmaline aggregations. The product of crystallization of volatile-enriched granite cupolas are not only variable in their

accessory mineral assemblage that captures high field strength elements, but also in numerous veins in country rocks that

often contain cassiterite and tourmaline. Volatile flux is documented by the tetrad effect via patterns of chondrite normal-

ized REEs (T1,3 value 1.46). In situ differentiation and tectonic activity caused multiple intrusive events of fluid-rich

magmas rich in incompatible elements, resulting in the formation of rare-metal phases in granite roofs. The emplacement

of volatile-enriched magmas into upper crustal conditions was followed by deeper rooted porphyritic magma portion

undergoing second boiling and re-melting to form porphyritic granite or granite-porphyry during its ascent.

Keywords: S-type granite, zircon, fluorapatite, monazite, tourmaline, cassiterite, rare-metal granites, Gemeric Unit.

Introduction

The presence of boron in felsic melt significantly changes

the rheological character in density and viscosity (Dingwell et

al. 1996), and decreases the solidus temperature (Manning

1981; Pichavant 1981; Pollard et al. 1987). Effective melt

depolymerization by boron and fluorine resulted in melt

mobility and differentiation, which enables the concentration

of lithophile elements, such as Rb, Li, Sn, Nb, Ta (Dingwell et

al. 1985). F-rich source magma became more enriched in

incompatible elements with increase of heavy rare earth ele-

ments (O’Neill et al. 2017). The high volatile flux is an impor-

tant phenomenon with regard to easier differentiation, empla-

cement of melt to the shallow crustal level, formation of

various rare-metal accessory mineral phases and increase in

the metallogenetic capacity. But the behaviour of the high

field strength elements is also strongly controlled by the ASI

(molar Al / Na + K) parameter (Aseri et al. 2015).

This study presents the characterization of the accessory

mineral assemblage in the volatile-rich granite system of

Permian granites in the Gemeric Unit (uppermost Alpine tec-

tonic nappe unit of the Western Carpathians). These granites

crop out as small bodies in Lower Paleozoic low-grade

metavolcano–sedimetary rocks and, according to geophysical

data, represent cupolas of a large hidden granite massif with

a thickness of ~ 5 km (Šefara et al. 2017). The Alpine Gemeric

Unit was stacked onto the Veporic Unit during the Cretaceous,

probably wedging the Hronic Unit in between (e.g., Vozár et

al. 2015; Plašienka 2018). The tourmaline is a more typical

accessory phase for the Gemeric granites, with its concentra-

tion increasing towards the granite cupolas (Rub et al 1977;

Broska et al. 2002; Kubiš & Broska 2005). The apical parts of

the Gemeric granites, due to high primary concentration of

volatiles, contain various accessory minerals of Sn, Nb, Ta,

W, B, F and Li and, therefore, Uher & Broska (1996) classi-

fied the Gemeric granites as “specialized S-type granites”.

The special mineralization in granitic rocks is expressed by

the pre sence of cassiterite, Nb–Ta oxides, wolframite, fluo-

rite (Kamenický & Kamenický 1955; Baran et al. 1970;

Malachovský et al. 1983, 2000; Broska et al. 2002, Uher et al.

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, 2018, 69, 5, 483–497

and a high

Sr/

Sr initial ratio (>

0.720 Kovách et al. 1986;

Cambel et al. 1990). The high initial Sr isotope ratios, as well

as Nd and S isotopic data (Kohút et al. 1999; Kohút & Reccio

2002), indicates a melting of a mature metasedimentary mica-

rich feldspathic and pelitic protolith, which resulted in high K,

Rb and B contents. Albitization and local greisenization took

place in cupolas enriched in volatiles (Dianiška et al. 2002).

The highly evolved felsic melt differentiated in-situ in cupolas

forms tourmaline-bearing Li-biotite granite at the bottom,

topaz–zinnwaldite granite in the middle, and quartz-albitite to

albitite at the top of the cupola (Breiter et al. 2015).

The porphyritic granites contain more then 1 cm large sub-

hedral crystals of K-feldspar with perthitic structure and large

grains of quartz. Strongly sericitized albite with An

cores and

biotite flakes with accessory phases correspond to magmatic

origin. The fine-grained rare-metal granite contains almost

pure albite. All granites contain ubiquitous tourmaline.

The upper parts of stocks contain medium-grained protolithio-

nite granite with local K-feldspars up to 1 cm, topaz and acces-

sory Sn–W–Nb–Ta phases are in the matrix. Topaz–zinnwaldite

granites are found in cupolas below the albite part with fissu-

res of greisens (Fig. 2a). The uppermost part contains quartz–

mica veinlets with some ore phases like Nb–Ta oxides or

cassiterite (Fig. 2b).

The Permian ages of these granites were confirmed by dating

of monazite (Finger & Broska 1999), MS TIMS method

(Poller et al. 2002), SHRIMP geochronology (Radvanec et al.

2009) and LA–ICP–MS (Kubiš & Broska 2010). Kohút and

Stein (2005) dated molybdenite in the Hnilec area by Re–Os

isotopes and obtained ages of 262 ± 0.9 and 264 ± 0.8 Ma,

clearly demonstrating a link between granite evolution and

associated metallogenetic processes. SHRIMP dating, indi-

cates the presence of separate granite bodies in the Gemeric

Unit because of the time span for their genesis, ~ 275 Ma for

southern Betliar area vs ~ 258 Ma for the northern Hnilec area

(Radvanec et al. 2009; Radvanec & Grecula 2016). Granite

bodies are overprinted by Alpine metamorphism making

it hard to evaluate their composition (Breiter et al. 2015).

The calculated PT conditions of medium-grade Alpine meta-

morphism reached 600 –700 MPa at a temperature of 400 °C

(Petrasova et al. 2007). The talc deposit exploited in Gemerská

Poloma near Betliar probably originated by fluid activity from

the Permian Gemeric granites, which led to the steatitization

of carbonate roof rocks and talc formation (Radvanec et al.

2004; see also Grecula et al. 2000).

Results

Characteristics of principal accessory minerals such as

zircon, monazite, tourmaline and Sn–W–Nb–Ta-oxides are

present in terms of distribution in the two granite settings:

(1) porphyritic deep-seated and (2) rare-metal-rich cupolas.

The rare-metal granites from cupolas are carriers of economic

mineral phases, the deep-seated porphyritic granites are barren

and contrast in composition.

Zircon

Zircon morphology according to Pupin’s classification

(Pupin 1980) typically shows a high amount of S

zircon sub-

types where pyramid and prismatic faces are equal (see Pupin

1980). Partial zircon edge corrosion is typical, resulting from

percolated alkali fluids. Other typical zircon morphological

subtypes are S

, S

(see also

Jakabská & Rozložník

1989). The late magmatic zircon generation consists mainly of

metamict crystals with prevalence of G

and P

subtypes.

The less evolved porphyritic granites show higher I.T. values,

as in sample GK-6 where I.A. = 480 and I.T. = 364, but inten-

sively differentiated rare-metal granites show more heteroge-

neous zircon morphology and often high I.A parameter, as in

sample GK-7 where I.A. = 524 and I.T. = 342 (Fig. 3).

The Zr/Hf

zircon ratio varies from 29 to 45 in biotite gra-

nite, but fractionated granites in cupolas have a typical increase

in Hf content towards a smaller Zr/Hf

ratio, as much as 5.

Rims of some zircon grains from highly fractionated Li–F

Fig. 2. Microphotos from optical microscope: A — topaz and Li-mica in the granite (DD3 570 m); B — cassiterite in the greisenized albitite

(DD3 489 m).

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, 2018, 69, 5, 483–497

granites have very high Hf concentrations

with more than 9 wt. % HfO

, increased P

content (0.1–2.5 wt. % P

), up to 2 wt. %

and 0.9 wt. % Y

(Table 1). Substitution

mechanisms, except typical HfZr

-1

substitution,

suggests a wide acceptance of the xenotime

mole cule (Y,REE)

-1

, Si

-1

(Fig. 4 a, b).

Phosphates

Fluorapatite (typically up to 3.5 wt. % Mn)

and less monazite and xenotime-(Y) are phos-

phate phases in deeper-seated barren granites.

Fluorapatite may not to be stable enough in

the upper rare-metal granites, where low Ca

and high F granites stabilize aluminophos-

phates such as arrojadite, lacroixite, goyazite,

gorceixite and viitaniemiite (see Petrík et al.

2011, 2014). Fluorapatite in the upper rare-

metal granites precipitated mainly as a secon-

dary, tiny, pure phase exsolved from alkali

feldspars (Fig. 5a). In addition Sr-rich fluor-

apatite is present, from percolated fluids from

country rocks, with a rim of the secondary

fluor apatite (Fig. 5b). Upper evolved granites

concentrate P into feldspars via the berlinite

molecule where mainly the rims of alkali feld-

spars are P-enriched (Fig. 6).

Monazite-(Ce) only exists with enlarged

cheralite molecules in the evolved granites.

The most important cheralite component in

monazite — CaTh(PO

)

— from Gemeric gra-

nites, usually does not exceed 12 mol. %, how-

ever, highly evolved rare-metal granites in

the Betliar and Dlhá dolina valley contain

monazites with 14 to 20 mol. % and sometimes

> 40 mol. % of the cheralite molecule (Table 2).

Sample

DD3-594/2

DD3-594/7

GK-8A/2

GK-9/1

ZK-31/2-2

ZK-31/1-2

Rock

rare metal

granite

rare metal

granite

rare metal

granite

Ms granite

Locality Dlhá dolina

Dlhá dolina

Hnilec

Čučma

1.79

0.60

n.a.

0.21

0.09

SiO

31.65

32.37

33.38

31.12

32.49

32.57

ZrO

53.99

58.82

63.71

66.05

65.19

65.07

HfO

9.31

6.34

1.83

1.62

1.46

1.01

ThO

bdl

0.08

0.01

0.02

bdl

0.69

0.35

0.05

n.a.

bdl

0.04

bdl

0.03

0.21

0.01

bdl

0.10

bdl

n.a.

0.15

bdl

n.a.

0.02

0.01

bdl

0.02

n.a.

bdl

0.05

n.a.

0.11

0.05

n.a.

0.06

bdl

0.78

bdl

n.a.

0.04

0.13

0.01

0.04

0.10

0.05

0.02

CaO

0.01

bdl

0.03

0.01

Total

98.71

98.69

99.05

99.14

99.55

98.86

Formulae based on 4 oxygen atoms
P

0.050

0.016

n.a.

0.006

0.002

1.005

1.018

1.027

0.974

0.999

1.006

0.836

0.902

0.956

1.008

0.977

0.980

0.084

0.057

0.016

0.014

0.013

0.009

bdl

0.001

bdl

0.005

0.003

bdl

n.a.

bdl

0.010

0.004

bdl

0.001

bdl

n.a.

0.002

bdl

n.a.

bdl

n.a.

bdl

0.001

n.a.

0.001

n.a.

0.001

bdl

0.008

bdl

n.a.

0.001

bdl

0.001

bdl

0.001

bdl

Sum cat.

1.993

1.999

2.001

1.999

1.998

n.a. — not analysed, bdl — below detection limit

Table 1: Representative zircon analyses from the specialized S-type granites (in wt. %).

Fig. 4. Substitution diagrams for documented zircon significance: A — HfZr

-1

substitution; B — xenotime substitution.

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Cassiterite is the most prominent ore mineral

phase in rare-metal granites, greisens and quartz

veins in Podsúľová (Dlhá dolina valley) and

Betliar, as well as in Hnilec, Zlatá Idka and

Poproč. It forms euhedral 0.1–5 mm crystals or

aggregates, and veinlets (Fig. 9b). Cassiterite

contains up to 1.2 wt. % Nb

and 2.2 wt. %

. Disseminated magmatic cassiterite and

Nb–Ta oxides crystallize in the albitic segments

of granite cupolas, whereas disseminated wol-

framite appears mainly in lower topaz-zinnwal-

dite granite. Cassiterites from the uppermost

parts contain a lower amount of minor elements.

High fluid activity is necessary for the effective

accumulation of Sn–W–Nb–Ta-oxides into

the fluid phase. Mutual compositional relation-

ships in the rare-metal phases are documented by

the Nb+Ta−Ti+Sn+W−Fe+Mn multi-cation dia-

gram (Fig. 9); selection of analyses are shown in

Table 4. These rare-metal mineral phases can

commonly form individual grains several

micrometers in size.

Discussion

Interpretation of phosphorus mobility

The fluorapatite evolution is important for

understanding the phosphorus behaviour in

the evolved granite system. Fluorapatite is

develo ped in three generations: (1) magmatic

with high Mn (2) secondary as a pure fluorapatite

exsolved from alkalic feldspars and (3) in vein-

lets from circulated fluids from country rock;

the mechanism of P incorporation into alkali feld-

spars is well known, as well as the phenomenon

of its exosolution (London et al. 1990; Breiter et

al. 2002, 2017). The absence or low amount of

primary apatite at low CaO/P

ratios in

the granite apical parts and high F activity during

late granite crystallization result in a P increase in

granite melts and P being incorporated in feld-

spars. Increasing P is buffered by precipitation of

lacroixite and topaz, which become stable at the

expense of apatite and albite (Petrík et al. 2011).

A probable decrease of pressure during the em-

placement of granite along with high fluid acti-

vity led to the P exsolution from the alkali

feldspars and formation of tiny pure secondary

apatites. The secondary apatite exsolved from

feldspars by corrosive fluids indicate the general

Sample

GK-6/2

GK-8/14 DD3-808/3-1 DD3-908/3-2 GK7-2-2

GK7-2-9 GK-8/17-1

Rock

Bt granite Bt granite

Bt granite

rare metal

granite

rare metal

granite

Ms granite

Locality Betliar

Hnilec

Dlhá dolina Dlhá dolina

Betliar

Hnilec

Mineral

Mnz

Mnz-Cher Mnz-Cher

Xtm

SiO

0.64

0.55

0.53

0.63

0.51

0.52

0.74

28.41

29.17

29.37

29.92

27.23

28.51

32.66

CaO

0.55

0.52

2.09

1.10

5.55

5.88

0.13

2.23

0.49

3.28

3.62

1.90

2.44

42.19

12.10

11.03

8.59

10.85

7.11

5.63

bdl

27.23

30.08

22.00

24.60

16.42

14.63

0.15

3.27

3.99

2.35

3.02

1.82

1.78

0.06

12.15

13.28

9.32

10.19

5.85

5.92

0.70

2.76

3.12

2.20

2.12

1.46

1.72

0.94

n.a.

0.06

bdl

n.a.

2.24

1.97

3.51

3.29

2.23

2.40

3.00

n.a.

bdl

0.20

n.a.

0.88

0.48

1.33

0.59

0.47

0.79

6.85

n.a.

0.28

0.61

0.39

0.78

n.a.

0.02

bdl

0.45

0.22

0.11

2.83

n.a.

0.34

0.25

n.a.

0.09

0.07

0.14

0.16

0.07

0.10

1.84

n.a.

0.34

bdl

n.a.

ThO

7.07

4.57

11.54

7.58

25.93

26.19

0.56

0.22

0.09

0.69

0.07

2.16

2.78

2.62

0.04

0.09

bdl

TiO

n.a.

bdl

n.a.

MnO

0.06

0.14

0.09

0.05

n.a.

0.08

FeO

0.10

bdl

0.40

0.28

n.a.

0.12

PbO

bdl

0.01

0.15

0.04

0.37

0.38

0.37

bdl

1.48

0.47

n.a.

0.05

0.02

0.04

n.a.

Total

100.09

99.67

99.49

99.72

99.89

100.76

95.85

Formulae based on 4 oxygen atoms
Si

0.102

0.087

0.082

0.097

0.083

0.082

0.026

3.837

3.914

3.839

3.915

3.742

3.816

0.970

0.095

0.089

0.346

0.182

0.965

0.996

0.005

0.189

0.041

0.270

0.298

0.164

0.205

0.787

0.712

0.645

0.489

0.619

0.426

0.328

bdl

1.590

1.745

1.244

1.392

0.976

0.847

0.002

0.190

0.231

0.132

0.170

0.108

0.103

0.001

0.692

0.752

0.514

0.562

0.339

0.334

0.009

0.152

0.170

0.117

0.113

0.082

0.094

0.011

n.a.

0.003

bdl

n.a.

0.119

0.104

0.180

0.169

0.120

0.126

0.035

n.a.

bdl

0.011

0.010

n.a.

0.045

0.024

0.066

0.029

0.025

0.040

0.077

n.a.

0.014

0.030

0.020

0.039

n.a.

0.001

bdl

0.022

0.011

0.005

0.033

n.a.

0.016

0.012

n.a.

0.004

0.007

0.008

0.003

0.005

0.020

n.a.

0.016

bdl

n.a.

0.257

0.165

0.405

0.267

0.958

0.942

0.004

0.008

0.003

0.024

0.002

0.078

0.098

0.020

0.015

0.039

bdl

n.a.

bdl

n.a.

0.007

0.015

0.010

0.005

n.a.

0.002

0.014

bdl

0.052

0.036

n.a.

0.003

bdl

0.001

0.006

0.002

0.016

0.004

bdl

0.723

0.230

n.a.

0.014

0.005

0.010

n.a.

mnz

91.223

93.633

80.178

88.48

53.48

51.40

Xbrb

6.273

4.211

17.729

9.03

44.60

46.64

Xhut

2.505

2.157

2.093

2.49

1.92

1.96

Table 2: Representative analyses of monazite from

the specialized S-type granites (in wt. %).

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, 2018, 69, 5, 483–497

high P mobility and P penetration towards granite

exocontacts.

Števko et al. (2015) described hydrothermal quartz veins

hosted by topaz–zinnwaldite leucogranite from the Dlhá

dolina area with an association of phosphates and alumino-

phosphates (fluorapatite, triplite, arrojadite-group minerals

and viitaniemiite). Such veins in host rare-metal granites is

additional evidence for the intensive mobilization of phos-

phate from alkali feldspars. Intensive mobilization of the P

towards country rocks of evolved granites led to the formation

of veins rich in apatite, monazite-(Ce), xenotime-(Y) and

U–Th phases in the Čučma ore district. Rojkovič et al. (1999)

suggested the host metasediments as element sources for

the REE–Th–P rich vein in the nearby Betliar and Čučma

granites (Grecula et al. 1995).

Interpretation of boron mobility

According to the recent tourmaline supergroup nomen-

clature (Henry et al. 2011), the tourmaline in the Gemeric

granites is predominantly schorlitic and foititic. There is

a prevalence of ferrous iron in tourmaline (Broska et al. 1998)

indicating mostly reducing conditions during precipitation.

The schorlitic tourmaline is more prevalent, but the later gene-

ration can be foititic and these may be related to a later stage

of influx by low T fluids. The multistage formation of tourma-

line has been characterized in the Hnilec area by Jiang et al.

(2008) and in the Betliar area by Kubiš & Broska (2010). Jiang

et al. (2008) described two major generations of the schorlitic–

dravitic series: (1) the M (magmatic)-stage which forms zoned

tourmaline crystals with the cores enriched in Fe, Al, and Mn,

and (2) the L (late)-stage which is more Mg-rich and Fe, Al,

Mn depleted. The L-stage occurs in small veins or irregular

patches along fractures and cracks and in the contact

metapelites. The boron isotopic compositions of the M-stage

tourmalines vary from −10.3 ‰ to −15.4 ‰; the L-stage tour-

malines have lower δ

B value of −16.0 ‰ to −17.1 ‰ (Jiang

et al. 2008). Kubiš & Broska (2010) recognized four tourma-

line types in the Betliar granite body: (1) disseminated mag-

matic tourmaline, (2) nodular tourmaline formed near solidus

temperatures, (3) quartz–schorlitic tourmaline veins, and

(4) metamorphic dravitic tourmaline in country rocks con-

nected with B escape from the granites.

The tourmaline composition can be generally typomorphic

because it reflects the host rock conditions (Dutrow & Henry

2011; van Hinsberg et al. 2011). The schorlitic chemistry of

the primary tourmaline in the granites of the Gemeric Unit is

world-wide typical although the dravitic-schorlitic series as in

the eastern Pontides are also common (Yavuz et al. 2008).

Tourmaline from leucogranites in Zamora (Spain) is schorlitic

and dravitic and their rare-metal pegmatites mostly belong to

the schorl–elbaite series (Roda-Robles et al. 2004). Tourmaline

in the rare-metal granites is schorlitic, commonly nodular and

dendritic indicating undercooling and rapid growth. For com-

parison, tourmalines from the granites in the Poproč areas of

the Gemeric Unit are more foititic (Fig. 8).

The formation of nodular tourmaline is related to magmatic

crystallization and hydrothermal fluids from penetrated gra-

nites (e.g., Samson & Sinclair 1992; Buriánek & Novák 2007).

Balen & Broska (2012) interpreted the tourmaline nodules at

Moslavačka Gora in Croatia as a result of decompression and

ascent of fluids during shallow emplacement of the granite

body or formation of vapour and boron-rich-bubbles migra-

ting through the final granite melt. In contrast, Drivenes et al.

(2015) suggest formation of larger quartz–tourmaline orbicules

Sample

GK6/4-7

GK6/4-8

GK17/11

GK17/1-3 DD3-908/2

Rock

porphyritic

bt granite

porphyritic

bt granite

rare-metal

ms granite

rare-metal

ms granite

rare metal

ms granite

Locality

Betliar

Dlhá Dolina

Mineral

schorl

SiO

34.95

34.86

35.34

34.77

35.05

TiO

0.80

0.45

0.77

0.40

0.01

10.38

10.47

10.44

10.30

10.24

33.26

35.19

34.37

34.11

33.93

bdl

0.01

FeO

12.40

11.41

12.93

15.20

13.40

MnO

0.15

bdl

0.25

MgO

2.56

2.40

1.15

bdl

0.65

CaO

0.35

0.33

0.16

0.08

0.04

2.12

1.95

1.80

1.98

1.89

0.05

0.08

0.03

0.04

0.02

O *

3.38

3.30

3.44

3.55

3.34

0.54

0.67

0.35

bdl

0.40

bdl

0.01

O = F

−0.23

−0.28

−0.15

bdl

−0.17

O = Cl

bdl

Total

100.30

100.61

100.78

100.43

99.07

Formulae normalised on 31 anions, B = 3 and OH+F = 4 atoms
Si

5.850

5.786

5.882

5.867

5.947

Al T

0.150

0.214

0.118

0.133

0.053

Sum T

6.000

3.000

Al Z

6.000

0.101

0.056

0.096

0.051

0.001

Al Y

0.411

0.670

0.625

0.651

0.733

bdl

0.001

1.685

1.584

1.800

2.145

1.902

0.021

bdl

0.036

0.639

0.505

0.285

bdl

0.164

Sum Y

2.857

2.836

2.827

2.847

2.837

tot

6.561

6.884

6.743

6.784

6.786

0.063

0.059

0.029

0.014

0.007

0.688

0.628

0.581

0.648

0.622

0.011

0.017

0.006

0.009

0.004

Sum X

0.762

0.704

0.616

0.671

0.633

Vac X

0.238

0.296

0.384

0.329

0.367

OH V

3.000

tot

3.714

3.648

3.816

4.000

3.782

OH W

0.714

0.648

0.816

1.000

0.782

−

0.286

0.352

0.184

bdl

0.215

−

bdl

0.003

Sum W

1.000

Fe/(Fe+Mg)

0.73

0.76

0.86

1.00

0.92

Table 3: Selected analyses of tourmaline from the specialized S-type

granites from Betliar and Dlhá dolina.

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Rutile
Fe-columbite
Ferberite
Hubnerite

Fe+Mn

Ti+Sn+W

Nb+Ta

(FeMn)

(NbTa)O

(FeMn)

(NbTa)

(FeMn)WO

Sample

DD3-577/1-4

DD3-577/1-6

DD3-577/1-10

DD3-577/1-11

DD3-577/6-6

DD3-577/8-1

DD3-577/1-13

DD3-577/4-2

Locality

Dlhá dolina

Mineral

Rutile

Fe-columb.

Ferberite

Hubnerite

bdl

0.26

4.80

2.31

67.78

71.52

72.25

71.34

7.37

6.84

47.60

40.39

5.96

3.08

1.02

2.28

12.52

13.11

23.98

35.06

0.94

0.19

0.44

0.54

TiO

73.90

73.18

3.64

4.00

0.32

0.22

0.72

0.70

SnO2

1.23

1.04

1.14

1.83

0.55

0.37

0.19

0.35

ThO

bdl

0.07

bdl

0.09

0.04

bdl

0.04

0.16

0.09

0.16

0.37

0.30

0.57

bdl

0.15

0.10

bdl

1.62

1.80

bdl

1.17

1.05

1.57

0.69

FeO

3.22

3.18

14.56

11.97

12.95

13.36

7.85

9.04

MnO

0.04

0.05

3.21

4.66

9.07

8.89

13.85

13.00

ZnO

0.05

bdl

0.12

bdl

Total

99.95

99.5

99.21

100.46

99.09

99.16

98.19

98.51

Formulae based on 24 oxygens and 12 cations
Fe

and Fe

calculated by charge-balancing

bdl

0.012

0.313

0.155

5.196

5.543

5.666

5.558

0.599

0.560

5.413

4.716

0.797

0.416

0.140

0.310

0.612

0.646

1.640

2.462

0.076

0.015

0.036

0.044

9.987

9.966

0.689

0.777

0.071

0.049

0.164

0.158

0.088

0.075

0.114

0.188

0.065

0.044

0.023

0.042

bdl

0.005

bdl

0.006

0.003

bdl

0.006

0.035

0.020

0.041

0.096

0.079

0.149

bdl

0.016

0.012

bdl

0.219

0.246

bdl

0.260

0.235

0.358

0.157

0.483

0.481

3.063

2.585

3.203

3.341

1.985

2.272

0.006

0.008

0.684

1.019

2.273

2.252

3.550

3.310

0.007

bdl

0.022

bdl

Total

12.001

12.000

11.973

11 .938

12.000

11 .999

12.001

12.000

Mn/(Mn+Fe)

0.008

0.011

0.183

0.283

0.396

0.386

0.602

0.577

Ta/(Ta+Nb)

0.505

0.536

0.233

0.343

0.087

0.035

0.205

0.124

bdl — below detection limit

Fig. 9. A — Nb+Ta−Ti+Sn+W−Fe+Mn diagram from accessory mineral phases in the specialized S-type granite (rare-metal type). B — BSE

of zonal cassiterite from a veinlet in the albitite associated with Nb–Ta oxide (drillcore DD3, depth 474 m).

Table 4: Analyses of Sn, W, Nb, Ta-minerals from rare-metal granites (specialized S-type granites from locality Dlhá dolina).

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, 2018, 69, 5, 483–497

the emplacement of granite from a deeper seated magma

chamber and contamination by boron, which probably took

place during the magma ascent. The fluid influence from

country rock is indicated by the presence of Sr-rich apatite

(Fig. 5b). The dolomite crystals in granite cupolas are further

a pro duct of mixing volatiles from the contact zone with

Mg-rich phases (talc, magnesite). Similar Sr mobility from

country rock into Sr-poor differentiated granites is known, for

example also in the Beauvoir massif (Charoy et al. 2003) and

in the San Elias pegmatite from Argentina (Galliski et al. 2012).

Scenario of granite evolution in the Gemeric Unit

The high flux regime in the granite cupolas also demon-

strates the tetrad effect on REE’s chondrite normalized pat-

terns (Fig. 10). According to Bau (1996) the tetrad effect is

formed by the complexation of the REEs with H

O, CO

, F

−

and Li

. The behaviour of the REEs when the tetrad effect

occurs is no longer dependent on the ionic radii, but rather on

filling stages of 4f orbitals (Irber 1999). Thus, REEs with 0/4

(La), 1/4 (Nd, Pm), 2/4 (Gd), 3/4 (Ho, Er) and 4/4 (Lu) filling

4f orbitals can be fractionated from the other REEs resulting in

the tetrad pattern. The tetrad effect occurs in highly evolved

igneous rocks as an indicator of the transition between mag-

matic to high-temperature hydrothermal systems. The separa-

tion of F-rich hydrosaline melt in granite cupolas possibly

caused the tetrad effect as described Badanina et al. (2006),

however, the REE tetrad effect may also develop before

magma evolved from a crustal source (Lee et al. 2018).

Due to high volatile flux, the evolution of the specialized

S-type granites is different from other Variscan granites in the

Western Carpathians. The preserved granite cupolas of larger

hidden granite body (Plančár et al. 1977; Šefara et al. 2017),

intensive in-situ differentiation and percolation of fluids

resulted in formation of various accessory phases in cupolas,

including those with metallogenic significance. The tin bea-

ring granite was described in detail by Malachovský et al.

(1992); Dianiška et al. (2002); Kubiš & Broska (2010); Breiter

et al. (2015) on results from a drilling programme in the Dlhá

dolina or Podsúľová area in the Gemeric Unit. The granite out-

crops in Betliar and granite emplacement in the Čučma ore

district (porphyritic and fine grained granites along minera-

lized fault — see Grecula et al. 1995) facilitates the proposed

scenario for evolution of rare-metal granites as a phase derived

from water-rich magma in granite apical part under a carapace

of host rock and underlying coarse-grained biotite granites.

These composite granite bodies comprise from the bottom

(1) a lower coarse-grained barren biotite granite system and

(2) mobile apical Li-bearing and topaz–zinnwaldite rare-metal

gra nites associated with greisenized albitites (Fig. 11).

Comparison with rare-metal (element) granites

The rare-metal granites belongs to the S- and A-type gra-

nites and usually form composite bodies. A-type granite

systems are known from Egypt (Gaafar & Ali 2015), and

the Erzgebirge (Breiter 2012) or Slavkovský les (Breiter et al.

1999). The S-type rare-metal systems are more widespread,

including the Gemer granites (see overview Romer & Kroner

2016). The early Permian S-type Cornubian Batholith is

a composite pluton formed from 5 pulses, including granites

rich-in-tourmaline (Simons et al. 2017). The western Erz-

gebirge rare-metal granites show S-type characteristics (e.g.,

Podlesí), where the eastern part is an A-type (Breiter 2012).

The eastern Erzgebirge locality at Cínovec is formed of two

different geochemical and mineralogical granites — the rare-

metal Sn–W–Nb–Ta–Li-bearing granite intruded after

emplacement of deeper seated barren biotite granite and fluid

escape from the rare-metal phase causing explosive breccia-

tion of the country rocks (Breter et al. 2017). The rare-metal

granites in Cínovec were emplaced into a subvolcanic level

(Müller et al. 2005). Breiter et al. (2017) suggested hydrofrac-

turing in the cupola of the rare-metal granite and F and Li par-

titioning to the fluids, which caused greisenization followed

by albitization. The residual melt represents a dry and mica-

poor por tion. Mineralization in the cupo las of the Gemeric

S-type granites is also connected with

partitioning of F, Li, and high field

strength elements to fluids, although

the Cíno vec granite is without signi-

ficant B content. The S-type Geme ric

granites reached the upper crustal

level, forming a contact aureola of

biotite + andaluzite ± cordierite ±

corundum at 450–560 °C and P

100–150 MPa (Faryad in Krist et al.

1992), and cannot trigger the breccia-

tion of country rock in such condi-

tions. The comparison of thickness of

rare-metal granites in the Gemeric

cupolas, which reached less than

several hundred m from the surface,

with other rare-metal granite systems

in the Varis can orogeny in Europe is

Fig. 10. Tetrad effect in chondrite normalized granites indicates the high flux of volatiles in

the rare-metal granite system. The pattern from albitite is for comparison.

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EVOLUTION OF TIN-BEARING S-TYPE GRANITES OF THE GEMERIC UNIT (WESTERN CARPATHIANS)

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, 2018, 69, 5, 483–497

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Sample

Rock type, location

Longitude (°E)

Latitude (°N)

Altitude (m)

GK-6

porphyritic biotite granite, natural outcrop, Betliar

48°43’55.62”

20°31’47.71”

525

GK-7

rare metal granite, natural outcrop, Betliar

48°44’17.55”

20°31’48.89”

609

GK-8

medium grained, tourmaline granite, ore dump, Hnilec

48°49’35.11”

20°29’15.24”

720

GK-9

fine to medium grained muscovite granite, ore dump, Hnilec

48°49’35.11”

20°29’15.24”

720

GK-10

greisen, ore dump, Hnilec

48°49’35.11”

20°29’15.24”

720

GK-17

rare metal granite, natural outcrop, Betliar

48°44’18.87”

20°31’46.86”

640

GZ-1

medium grained, tourmaline granite, natural outcrop, Hnilec

48°48’54.88”

20°30’46.54”

726

GZ-12

aplite, natural outcrop, Poproč

48°43’26.01”

21°02’54.96”

489

ZK-31

muscovite granite, ore dump, Čučma

48°42’57.89”

20°33’27.24”

556

DD3-577

rare metal granite, drill core DD-3; depth 577 m, Dlhá dolina

48°45’56.63”

20°32’07.49”

801

DD3-594

rare metal granite, drill core DD-3; depth 594 m, Dlhá dolina

48°45’56.63”

20°32’07.49”

801

DD3-908

porphyritic biotite granite, drill core DD-3; depth 908 m, Dlhá dolina

48°45’56.63”

20°32’07.49”

801

LIG-17

topaz–Li mica microgranite, taken from trench, Surovec (see Petrík et al. 2011)

48°47’33.04”

20°33’40.69”

766

Appendix

Sample description and GPS location