GeolCarp_Vol70_No6_449

GEOLOGICA CARPATHICA

, DECEMBER 2019, 70, 6, 449–470

doi: 10.2478/geoca-2019-0026

www.geologicacarpathica.com

Titanite composition and SHRIMP U–Pb dating

as indicators of post-magmatic tectono-thermal activity:

Variscan I-type tonalites to granodiorites,

the Western Carpathians

PAVEL UHER



, IGOR BROSKA

, EWA KRZEMIŃSKA

, MARTIN ONDREJKA

TOMÁŠ MIKUŠ

and TOMÁŠ VACULOVIČ

Department of Mineralogy and Petrology, Faculty of Natural Sciences, Comenius University, Ilkovičova 6, 842 15 Bratislava, Slovakia;



pavel.uher@uniba.sk

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

Polish Geological Institute – National Research Institute, Rakowiecka Street 4, 00-975 Warszawa, Poland

Earth Science Institute, Slovak Academy of Sciences, Banská Bystrica branch, Ďumbierska 1, 974 01 Banská Bystrica, Slovakia

Department of Chemistry, Faculty of Science, Masaryk University, Kamenice 5, 625 00 Brno, Czech Republic

(Manuscript received December 3, 2018; accepted in revised form November 11, 2019)

Abstract: Titanite belongs to the common accessory minerals in Variscan (~ 360–350 Ma) metaluminous to slightly

peraluminous tonalites to granodiorites of I-type affinity in the Tatric and Veporic Units, the Western Carpathians,

Slovakia. It forms brown tabular prismatic-dipyramidal crystals (~ 0.5 to 10 mm in size) in association with quartz,

plagioclase, and biotite. Titanite crystals commonly shows oscillatory, sector and convolute irregular zonal textures,

reflecting mainly variations in Ca and Ti versus Al (1–2 wt. % Al

, 0.04–0.08 Al apfu), Fe (0.6–1.6 wt. % Fe

0.02–0.04 Fe apfu), REE (La to Lu + Y; ≤ 4.8 wt. % REE

, ≤ 0.06 REE apfu), and Nb (up to 0.5 wt. % Nb

, ≤ 0.01 Nb

apfu). Fluorine content is up to 0.5 wt. % (0.06 F apfu). The compositional variations indicate the following principal

substitutions in titanite: REE

+ Fe

= Ca

+ Ti

, 2REE

+ Fe

= 2Ca

+ Ti

, and (Al, Fe)

+ (OH, F)

−

= Ti

+ O

2−

The U–Pb SHRIMP dating of titanite reveal their Variscan ages in an interval of 351.0 ± 6.5 to 337.9 ± 6.1 Ma

(Tournaisian to Visean); titanite U–Pb ages are thus ~ 5 to 19 Ma younger than the primary magmatic zircon of the host

rocks. The Zr-in-titanite thermometry indicates a relatively high temperature range of titanite precipitation (~ 650–750 °C),

calculated for assumed pressures of 0.2 to 0.4 GPa and a(TiO

) = 0.6–1.0. Consequently, the textural, geochronological

and compositional data indicate relatively high-temperature, most probably early post-magmatic (subsolidus) precipitation

of titanite. Such titanite origin could be connected with a subsequent Variscan tectono-thermal event (~ 340 ± 10 Ma),

probably related with younger small granite intrusions and/or increased fluid activity. Moreover, some titanite crystals

show partial alteration and formation of secondary titanite (depleted in Fe and REE) + allanite-(Ce) veinlets (Sihla

tonalite, Veporic Unit), which probably reflects younger Alpine (Cretaceous) tectono-thermal overprint of the Variscan

basement of the Western Carpathians.

Keywords: titanite, I-type granites, Zr-in-titanite thermometry, LA–ICP–MS analyses, SHRIMP U–Pb dating, Western

Carpathians.

Introduction

Titanite [previously sphene, CaTi(SiO

)O] together with rutile

and ilmenite belongs to the most widespread titanium minerals

of the Earth. There is a large variability of titanite presence in

various lithologies from early Archean to recent, including

(ultra)basic, intermediate, acid and alkaline magmatic suites

including pegmatites, low-grade to UHP metamorphic rocks,

as well as in some hydrothermal and sedimentary environ-

ments (e.g., Paul et al. 1981; Bernau & Franz 1987; Nakada

1991; Gieré 1992; Russell et al. 1994; Černý et al. 1995;

Bea 1996; Carswell et al. 1996; Bouch et al. 1997; Uher et al.

1998; Castelli & Rubatto 2002; Chakhmouradian et al. 2003;

Broska et al. 2007; Cempírek et al. 2008; Xie et al. 2010; Gao

et al. 2011; McLeod et al. 2011; Chen et al. 2016). The titanite

structure (Speer & Gibbs 1976; Liferovich & Mitchell 2005,

2006) comprises three different cation sites plus five anion

sites, and the general formula of the titanite-group minerals

can be written as XYZO

W. The sites are inhabited by follo-

wing cations: the tetrahedral Z site hosts Si

(and possibly small

amounts of Al

, Ti

, P

, As

, S

, and vacancy), the octa-

hedral Y site occupies Ti

and various small to medium-sized

cations (Mg

, Fe

, Al

, Sc

, Cr

, Mn

, As

, Sb

, V

, Sn

, Zr

, Hf

, Si

, V

, Nb

, Ta

, As

, Sb

, W

the 7-coordinated X site polyhedra contain Ca

and other

mainly medium- to large-sized cations: Na

, K

, Fe

, Mn

, Ba

, Pb

, REE

(La

to Lu

and Y

), Th

, and U

whereas the anionic W site is occupied dominantly by O

−

450

UHER, BROSKA, KRZEMIŃSKA, ONDREJKA, MIKUŠ and VACULOVIČ

GEOLOGICA CARPATHICA

, 2019, 70, 6, 449–470

(OH)

−

, F

−

, and Cl

−

(e.g., Ribbe 1980; Bernau & Franz 1987;

Gieré 1992; Russel et al. 1994; Černý et al. 1995; Perseil &

Smith 1995; Knoche et al. 1998; Brugger & Gieré 1999;

Della Ventura & Bellatreccia 1999; Markl & Piazolo 1999;

Chakhmouradian 2004; Cempírek et al. 2008; Xie et al. 2010;

Stepanov et al. 2012; Pieczka et al. 2017).

The wide compositional variability of titanite reflects diffe-

rent conditions of the host-rock formation and the mineral is

widely used in genetic interpretations. Especially, the content

of Zr in titanite, proportional to temperature and pressure of

its precipitation is successfully used in the application of

the Zr-in-titanite thermobarometer (Hayden et al. 2008).

Moreover, admixtures of radioactive actinides (U and Th iso-

topes) and their decay products (Pb isotopes) in titanite struc-

ture enable to measure the radiometric age of titanite formation

(e.g., Burger et al. 1965; Tilton & Grunenfelder 1968; Resor et

al. 1996; Kennedy et al. 2010; Sun et al. 2012; Gasser et al.

2015; Kohn 2017), recently also combined with oxygen iso-

tope distribution across titanite crystals (Bonamici et al. 2015).

Consequently, titanite composition and isotope characteristics

represent valuable tools for the understanding of the host-rock

origin and tracers of various geological processes, widely

used by petrochronology as well as P–T–t path reconstructions

(e.g., Rubatto & Hermann 2001; Castelli & Rubatto 2002; Gao

et al. 2011; Kohn & Corrie 2011; Stearns et al. 2015; Kirkland

et al. 2016, 2018; Kohn 2017).

Titanite is a characteristic accessory mineral of granitic

rocks, from metaluminous to slightly peraluminous biotite-

± hornblende-bearing tonalites and granodiorites of calc-alka-

line, orogenic-related suites (e.g., Lyakhovich 1968; Wones

1989; Bea 1996; Hoskin et al. 2000; McLeod et al. 2011).

Titanite is also a typical accessory mineral in Variscan granitic

rocks of I-type affinity in the Western Carpathians, Slovakia

(e.g., Schafarzik 1898; Radziszewski 1924; Hovorka 1960;

Hovorka & Hvožďara 1964; Jacko & Petrík 1987; Broska &

Uher 1988; Petrík & Broska 1989, 1994; Broska et al. 1997).

Recently, the West-Carpathian granitic titanite has been inves-

tigated in detail, including its electron-microprobe chemical

composition,

Fe Mössbauer spectroscopy, associated mine-

rals, and alteration products (Broska et al. 2004, 2007; Broska

& Petrík 2015).

Despite above-mentioned results, some aspects of titanite

chemical composition are still not resolved. Moreover, age

and origin of titanite from the West-Carpathian Variscan

granitic rocks have been interpreted controversially: as a pro-

duct of Alpine (Cretaceous) post-magmatic, syn- to post-

tectonic recrystallization of parental granodiorite/tonalite

(Zoubek 1936) or as a result of Variscan (Carboniferous) pri-

mary magmatic (Hovorka 1960; Hovorka & Hvožďara 1964)

to late-magmatic precipitation (Broska et al. 2004, 2007). This

paper presents a detailed study of titanite in the Variscan I-type

granites of the Western Carpathians, including their composi-

tional variations (main and trace element chemistry) with

main substitution mechanisms, as well as in-situ U–Pb dating

and possible genetic scenario based on titanite thermobaro-

metry and chronometry. Such research is a contribution to

our understanding of titanite origin and evolution of the host

granitic rocks.

Regional geology

The Western Carpathians form a part of the Alpine

orogenic

belt, divided into the Inner and Outer Western Carpathians

(Bezák et al. 2011). The Paleozoic basement rocks of the Inner

Western Carpathians occur in three Alpine tectonic units:

Tatric, Veporic, and Gemeric. The Variscan (Devonian to

Carboniferous) calc-alkaline granitic plutons of I- and S-type

affinity (e.g., Petrík & Kohút 1997; Kohút et al. 1999; Broska

& Uher 2001; Kohút & Nabelek 2008; Broska et al. 2013)

occur in the Tatric and Veporic units, they intruded high- to

medium-grade Paleozoic metamorphic rocks (mainly meta-

pelites to metapsammites) of the Variscan nappes, which show

a pre-Alpine, generally south vergency (e.g., Putiš 1992;

Bezák et al. 1997; Bielik et al. 2004). Moreover, small bodies

of Permian post-orogenic to anorogenic S- and A-type granitic

rocks are also present in various tectonic units of the Inner

Western Carpathians, mainly in the Gemeric Unit (e.g., Uher

& Broska 1996; Broska & Uher 2001).

The West-Carpathian Variscan I-type granitic rocks are

represented by coarse- to medium-grained, usually equigra-

nular to slightly porphyric, biotite, locally hornblende-bearing

(leuco)tonalites to granodiorites, rarely more evolved two-mica

granites. Fluorapatite, zircon, allanite-(Ce), epidote, magne-

tite, pyrite and titanite belong to widespread accessory mineral

of these granitic rocks. Moreover, the tonalites to granodio-

rites sporadically contain small bodies of mafic microgranular

enclaves of diorite to melatonalite composition (Petrík &

Broska 1989) and rare dykes of granitic pegmatites (Uher &

Broska 1995). In contrast to the undeformed I-type granitic

rocks of the Tatric Unit, those of the Veporic Unit commonly

show Paleo-Alpine (Cretaceous) metamorphic overprint

mani fested by mildly to strong post-magmatic alteration of

primary magmatic minerals, especially plagioclase, biotite

and allanite-(Ce).

These granitic rocks reveal calc-alkaline, metaluminous to

the slightly peraluminous character with slightly elevated con-

tents of Ca, Mg, Sr, Ba, Ti, Zr and P, and low K, Rb, Li, B, Sn

and F concentrations (Broska & Uher 2001). The whole-rock

REE patterns are relatively steep (La

/Lu

= 10–40), usually

with slightly negative Eu anomaly (Eu

/Eu

* = 0.7–0.9).

The chemical composition, Sr and Nd isotopes (I

= 0.705 ±

0.001, εNd

350

= −0.6 to −4) suggest subduction-related, I-type

character of these granitic rocks, originated by

mixing of

a deeper-seated mafic melt with mantle signature into the fel-

sic crustal magmatic reservoir

(Kohút et al. 1999; Poller et al.

2001; Broska & Petrík 2011; Broska et al. 2013). The zircon

in-situ U–Pb isotope dating indicates an Upper Devonian to

Lower Carboniferous (Mississippian) crystallization age inter-

val (~ 350 to 370 Ma) for the I-type granitic suite in the

Western Carpathians (e.g., Kohút et al. 2009; Broska et al.

2013; Gawęda et al. 2016).

451

TITANITE FROM VARISCAN I-TYPE TONALITES TO GRANODIORITES, WESTERN CARPATHIANS

GEOLOGICA CARPATHICA

, 2019, 70, 6, 449–470

Methods

Accessory titanite and their host rocks were studied in

polished thin sections under a polarizing optical microscope.

Moreover, separates of titanite and other accessory minerals

were obtained by common procedure: crushing of ~ 15 kg rock

sample, sieving (≤ 0.5 mm size was used) and then by using

the Wilfley vibrating table, heavy liquids (bromoform, methy-

lene iodide) and finally by the Cook electromagnetic separa-

tor. Titanite crystals were concentrated mainly in the slightly

paramagnetic fraction of heavy mineral separates. Larger

titanite crystals (~ 3–10 mm) were manually separated from

the host rock (Sih-1 sample). These separated titanite crystals

were fixed and polished in sections of 2.54 cm diameter.

The in situ chemical composition of titanite was analyzed

by the JEOL JXA 8530FE electron-probe microanalyser

(EPMA) at the Earth Sciences Institute of the Slovak Academy

of Sciences in Banská Bystrica at the following conditions:

WDS mode, accelerating voltage 15 kV, probe current 20 nA,

beam diameter 3 µm, counting time 10–30 s on peak, 5–15 s

on background, the ZAF correction. The X-ray lines and used

standards are following: Nb (Lα, LiNbO

), Si (Kα, albite),

Ti (Kα, rutile), Al (Kα, albite), Y (Lα, YPO

), La (Lα, LaPO

Ce (Lα, CePO

), Pr (Lß, PrPO

), Nd (Lα, NdPO

), Sm (Lß,

SmPO

), Gd (Lß, GdPO

), Fe (Kα, hematite), Mn (Kα, rhodo-

nite), Mg (Kα, diopside), Ca (Kα, diopside), Na (Kα, albite),

K (Kα, orthoclase), and F (Kα, fluorite). The chemical compo-

sitional zoning of titanite crystals was studied using the back-

scattered electron imaging (BSE) by the EPMA.

The content of trace elements was measured

using a Laser

Ablation –

Inductively Coupled Plasma

–

Mass Spectrometry

(

LA–ICP–MS) at the Department of Chemistry, Masaryk

University, Brno, which consists of a laser ablation system

UP 213 (New Wave Research, Inc., Fremont, U.S.A.) and

an ICP–MS spectrometer Agilent 7500 CE (Agilent Techno-

logies, Santa Clara, U.S.A.). The laser-ablation system is

equipped with a programmable XYZ-stage to move the sam-

ple along a programmed trajectory during ablation. Visual

target inspection, as well as the photographic documentation,

is accomplished using a built-in microscope/CCD-camera sys-

tem. The ablation cell was flushed with helium (carrier gas),

which transported the laser-induced aerosol to the inductively

coupled argon plasma (1 l.min

-1

). A sample gas flow of argon

was admixed to helium carrier gas flow after the laser ablation

cell. Therefore, the total gas flow was 1.6 l.min

-1

. Laser abla-

tion was performed with a laser spot diameter of 40 μm,

laser pulse fluence of 7 J.cm

-2

, and 10 Hz repetition rate for

60 seconds each. The Si was used as an internal standard and

the NIST SRM 610 silicate glass calibration standard was

applicated.

The U–Th–Pb isotope composition used for dating of tita-

nite was analysed by SIMS using the Sensitive High Resolution

Ion Microprobe (SHRIMP) technique by the SHRIMP IIe/MC

at the Polish Geological Institute – National Research Institute

(PGI–NRI), Warszawa. The fragments of selected titanite

crystals were mounted on adhesive tape together with chips of

reference Khan titanite (e.g., Heaman 2009) and embedded by

epoxy resin (Struers Epofix). After that, the epoxy disc was

polished to reveal cross-sections through the grains, cleaned

and dried. Finally, the polished titanite crystals were imaged

on the Nikon Eclipse LV100NPol optical microscope in trans-

mitted and reflected light mode using the NIS-Elements BR

software and on HITACHI SU3500 EPMA using a back-scat-

tered (BSE) detector to check the homogeneity of titanite frag-

ments and to select proper domains for analyses without the

presence of different mineral inclusions. The sample mount

was then cleaned and coated with gold to yield a conductivity

resistance of 10–20 Ω for the SHRIMP analysis. The basic

analytical procedure for titanite on SHRIMP instrument

described by Sato et al. (2016) has been slightly modified.

The run table for titanite included 6 mass scans of the follo-

wing 10 peaks:

204

Pb (a background measured at 0.045 mass

units above the

204

Pb peak),

200

TiCa

(guide peak),

206

Pb,

207

Pb,

208

Pb,

238

232

Th, ThO, UO, and UO

The primary ion beam was rastered over a 25–30 µm rectan-

gle for 2.0 minutes prior to each single spot collection, to

reduce a surface contributions by common Pb. After that each

measurement has six cycles through the data acquisition of

10 peaks, but a total analytical time for one spot is not extended

18 min. The focusing of an O

2−

primary ion beam on sectioned

titanite grains typically produces a spot with an elliptical size

of about 20–23 μm and depth of 3–4 μm.

The Khan

titanite was used as the principal reference mate-

rial for Pb*/U and Th*/Pb. The counts were acquired on both

the sample and titanite standard along whole analytical ses-

sion. The uranium content of 584 ± 95 ppm, according to

ID–TIMS characteristics provided by Heaman (2009), and

206

Pb/

238

U age

518

± 2 Ma (Kinny et al. 1994)

were taken as

reference values. During about 24 hours of the analytical

session on SHRIMP, twenty Khan analyses yielded a weight

average

207

Pb/

206

Pb age of 518 ± 13 Ma (MSWD = 1.4) and weight

average

238

206

Pb age of 516.6 ± 7.0 Ma (MSWD = 1.4). These

data set (n = 20) gave a lower intercept of age of 517 ± 7 Ma

(MSWD = 0.96) on the W concordia plot (the diagram not

shown). All these calculated Khan datings are within uncer-

tainty of its reference value,

showing similarity to other results

determined for the Khan titanite by the LA–ICP–MS, ID–

TIMS or SHRIMP methods (Kinny et al. 1994; Simonetti et al.

2006; Heaman 2009; Chew et al. 2014; Sato et al. 2016; Ma et

al. 2019).

The SQUID2.50.11.01.03 software (Ludwig 2009) and

attached the Isoplot/Ex version 3.00 Macro program (Ludwig

2003) were used for data processing. The SQUID2 calculates

a ‘calibration constant’, for each analysis of the reference

material (RM) and an error-weighted mean and standard error

for all of these analyses, plus the error on the calibration, and

the external error from the standard dataset. For each analysis

of an unknown, a value for blank and its uncertainty is calcu-

lated. The ratio

204

Pb*/

206

Pb, and the estimated

207

Pb*/

206

Pb age

of the titanite, are used to correct for a common Pb composi-

tion calculated from the Stacey and Kramers (1975) model

of bulk-crustal Pb isotope composition. The spot values for

453

TITANITE FROM VARISCAN I-TYPE TONALITES TO GRANODIORITES, WESTERN CARPATHIANS

GEOLOGICA CARPATHICA

, 2019, 70, 6, 449–470

described from analogous I-type granitic rocks of the Tribeč

Mountains (Broska et al. 2004, 2007). Therefore, their detailed

characterization is beyond the scope of this paper.

Titanite crystal chemistry

The zoning in BSE reflects variations in the chemical com-

position of titanite, lighter zones illustrate elevated contents of

Fe and REE`s whereas darker zones show higher Ca, Al and/

or Ti contents. Aluminium, Fe, REE`s (La to Lu + Y) and Nb

are the most characteristic isomorphic admixtures of investi-

gated titanite, detected by EPMA (Table 2). Their contents are

in the range of 1.0 –2.2 wt. % Al

(0.04– 0.08 Al atoms per

formula unit, apfu), 0.6 –1.6 wt. % Fe

(0.02–0.04 Fe apfu),

up to 4.8 wt. % REE

(≤ 0.06 REE apfu), and up to 0.5 wt. %

(≤ 0.01 Nb apfu). Fluorine content is up to 0.5 wt. %

(0.06 F apfu). Moreover, slightly decreased analytical totals

of measured titanite (usually 97 to 98 wt. %) together with

the high contents of Al, Fe, and F indirectly indicate a presence

of (OH)

−

anion. The irregular late veinlets and patchy zones of

the secondary titanite generally reveal lower contents of Fe

(≤ 1 wt. % Fe

), REE (≤ 2.5 wt. % REE

), Nb (≤ 0.2 wt. %

), and atomic Fe/Al ratio (0.2– 0.4) (Table 2, anal. 39,

58, 74, and 45) with comparison to the primary zones where

the Fe/Al ratio attains 0.4 to 0.8.

The trace-element analyses of titanite by the LA–ICP–MS

method reveal a dominancy of REE`s, especially Y, Ce, and

Nd (average contents attain ~1000 to 7500 ppm; ∑REE = 6300

to 21200 ppm) over Mg, Mn, Nb, V, Zr, Sn, Th, U (elements

with average contents of ~100 to 1300 ppm), and other trace

elements with average contents under 100 ppm (Table 3).

The REE show a distinct dominance of LREE (La to Sm)

over HREE (Gd to Lu, without Y), the average Ce/Yb weight

ratio varies between 15 and 51. Chondrite-normalized titanite

Table 1: Chemical analyses of studied titanite-bearing granitic rocks

from the Western Carpathians. Oxides in wt. %, trace elements in ppm.

Analytical techniques see Broska & Uher (2001). T

Zrn

(°C): zircon

saturation temperature in °C (Watson & Harrison 1983).

Sample

T-63

ZK-120

VG-14

Sih-1

ZK-12

(≈ ZK-79)

(≈ ZK-83)

Rock

tonalite

granodiorite

tonalite

Massif

Tribeč

Prašivá

Vepor

Čierna

Hora

SiO

64.45

67.79

63.18

64.57

64.34

TiO

0.76

0.46

1.04

0.80

0.93

16.38

16.12

16.24

16.34

16.18

4.45

2.95

4.75

4.29

4.68

MnO

0.08

0.05

0.07

0.08

MgO

1.86

1.29

1.62

1.81

CaO

3.46

1.52

3.27

3.59

3.18

4.15

3.92

4.00

4.36

4.14

2.59

3.88

2.13

2.54

2.47

0.26

0.11

0.43

0.29

0.40

Total

98.44

98.09

96.73

98.47

98.21

139

848

403

798

860

829

1237

805

1108

1263

1505

15.24

10.00

37.02

23.01

16.54

43.5

29.24

59.43

52.52

59.26

91.64

60.16

134.06

116.75

118.13

10.68

6.99

17.05

14.12

13.34

40.84

26.46

70.44

55.61

49.82

7.18

4.66

13.56

10.27

8.5

1.69

1.01

3.19

2.38

2.18

4.81

3.08

10.36

7.27

6.19

0.62

0.39

1.42

0.92

0.77

3.25

2.02

7.57

4.71

3.80

0.58

0.36

1.40

0.84

0.66

1.54

0.96

3.81

2.42

1.58

0.21

0.13

0.55

0.36

0.21

1.34

0.86

3.51

2.19

1.12

0.19

0.12

0.48

0.32

0.17

214

136

313

254

290

4.99

3.21

7.05

5.77

6.41

10.87

11.95

25.4

19.23

13.16

0.60

0.82

1.35

0.99

9.45

10.18

10.39

10.28

9.39

Zr/Hf

42.8

42.4

44.4

44.1

45.3

Ce/Yb

68.4

70.0

38.2

53.3

105.5

∑REE

223

146

364

294

282

Zrn

(°C)

797

779

840

808

829

Fig. 2. Photography of titanite crystals (pale brown, 7 and 5 mm

across) in biotite tonalite, Sihla (Sih-1 sample, Vepor Mts.).

455

TITANITE FROM VARISCAN I-TYPE TONALITES TO GRANODIORITES, WESTERN CARPATHIANS

GEOLOGICA CARPATHICA

, 2019, 70, 6, 449–470

Table

Representative

chemical

compositions and

mineral

formulae

studied

titanite

from

the

est-Carpathian

granitic

rocks.

Oxides

and

wt.

%, mineral

formulae in

atoms

per

formula unit (

apfu

Sample

T-63

T-70

ZK-79

ZK-83

Sih-1

ZK-12

Analyse

0.13

0.14

0.35

0.24

0.1

0.07

0.00

0.32

0.21

0.19

0.05

0.44

0.19

0.31

0.20

0.44

0.02

0.66

SiO

30.29

29.81

29.43

29.93

30.26

30.69

30.59

29.75

30.36

30.1

30.32

29.74

30.23

30.01

30.44

29.93

30.40

29.91

37.31

35.74

34.75

36.43

36.72

36.92

36.36

36.51

36.50

35.98

37.22

36.12

36.08

35.32

38.09

36.42

35.42

36.03

1.25

1.27

1.30

1.18

1.25

1.36

1.53

1.20

1.50

1.55

1.37

1.44

1.51

1.27

1.46

2.16

1.36

1.24

1.63

1.54

0.99

1.22

0.61

0.67

0.90

1.25

1.29

0.90

1.39

1.46

1.33

0.84

1.16

0.83

1.15

0.20

0.66

0.82

0.53

0.14

0.04

0.02

0.43

0.57

0.23

0.04

1.14

0.42

0.91

0.77

0.95

0.00

0.62

0.15

0.13

0.27

0.10

0.16

0.00

0.15

0.00

0.10

0.03

0.07

0.20

0.14

0.00

0.05

0.03

0.07

0.64

0.96

1.46

0.69

0.71

0.05

0.03

0.80

0.32

0.47

0.22

0.69

0.86

1.1

0.06

0.44

0.06

0.45

0.05

0.17

0.23

0.15

0.02

0.00

0.14

0.09

0.05

0.01

0.20

0.1

0.27

0.00

0.10

0.00

0.07

0.47

0.97

1.38

0.93

0.37

0.02

0.03

0.67

0.38

0.41

0.08

0.98

0.68

1.23

0.34

0.74

0.00

0.50

0.00

0.23

0.35

0.19

0.12

0.03

0.06

0.17

0.21

0.06

0.05

0.35

0.12

0.38

0.16

0.31

0.05

0.13

0.04

0.24

0.23

0.00

0.08

0.02

0.14

0.34

0.03

0.34

0.21

0.27

0.03

0.16

MnO

0.10

0.06

0.13

0.12

0.17

0.05

0.15

0.12

0.09

0.10

0.13

0.17

0.28

0.08

0.18

0.05

0.16

CaO

27.89

26.64

26.12

26.90

27.71

28.85

28.97

26.93

27.97

27.76

28.71

26.45

27.26

26.49

28.07

27.00

28.92

27.76

0.00

0.03

0.00

0.02

0.00

0.23

0.19

0.1

0.13

0.09

0.43

0.29

0.13

0.37

0.30

0.37

0.06

0.22

0.00

0.20

0.1

0.56

0.05

Sum (-F=O)

99.87

98.74

98.43

98.68

99.00

99.1

98.70

98.24

99.68

98.47

99.48

99.51

99.38

99.61

100.63

99.50

98.28

99.04

REE

1.54

3.36

4.75

2.82

1.51

0.13

0.14

2.44

1.59

1.34

0.58

3.76

2.41

4.37

1.53

2.85

0.16

1.99

Mineral formulae based on 3 (X+Y+ Si) cations

0.994

1.001

0.999

1.002

1.001

1.006

1.003

0.999

0.997

0.999

0.992

0.993

1.001

1.002

0.991

0.994

0.999

0.992

0.002

0.005

0.004

0.002

0.001

0.000

0.005

0.003

0.001

0.007

0.003

0.005

0.003

0.007

0.000

0.010

0.921

0.902

0.887

0.917

0.913

0.910

0.897

0.922

0.902

0.898

0.915

0.907

0.899

0.887

0.933

0.909

0.875

0.898

0.049

0.050

0.052

0.047

0.049

0.052

0.059

0.048

0.058

0.060

0.053

0.057

0.056

0.060

0.049

0.057

0.084

0.053

0.031

0.041

0.039

0.025

0.030

0.015

0.017

0.023

0.031

0.032

0.022

0.035

0.036

0.033

0.021

0.029

0.020

0.029

Sum Y

1.002

0.996

0.984

0.993

0.994

0.978

0.973

0.997

0.994

0.991

1.005

0.994

0.985

1.005

1.002

0.980

0.990

0.003

0.012

0.015

0.009

0.002

0.001

0.000

0.008

0.010

0.004

0.001

0.020

0.007

0.016

0.013

0.017

0.000

0.01

0.002

0.003

0.001

0.002

0.000

0.002

0.000

0.001

0.000

0.001

0.002

0.000

0.001

0.000

0.001

0.008

0.012

0.018

0.008

0.009

0.001

0.000

0.010

0.004

0.006

0.003

0.008

0.010

0.014

0.001

0.005

0.001

0.005

0.001

0.002

0.003

0.002

0.000

0.002

0.001

0.000

0.002

0.001

0.003

0.000

0.001

0.000

0.001

0.006

0.012

0.017

0.01

0.004

0.000

0.008

0.005

0.001

0.012

0.008

0.015

0.004

0.009

0.000

0.006

0.000

0.003

0.004

0.002

0.001

0.000

0.001

0.002

0.001

0.004

0.001

0.004

0.002

0.004

0.001

0.000

0.003

0.000

0.001

0.000

0.002

0.004

0.000

0.004

0.002

0.003

0.000

0.002

0.003

0.002

0.004

0.003

0.005

0.001

0.004

0.003

0.002

0.003

0.004

0.005

0.008

0.002

0.005

0.001

0.005

0.981

0.958

0.950

0.965

0.982

1.013

1.018

0.969

0.984

0.987

1.006

0.946

0.968

0.948

0.979

0.960

1.018

0.986

0.000

0.002

0.000

0.001

0.000

Sum X

1.003

1.004

1.017

1.005

1.016

1.024

1.004

1.009

1.007

1.017

1.001

1.005

1.013

1.004

1.005

1.021

1.018

Sum REE

0.019

0.044

0.063

0.037

0.019

0.002

0.032

0.022

0.017

0.007

0.051

0.031

0.057

0.022

0.039

0.002

0.027

0.023

0.020

0.012

0.013

0.010

0.045

0.030

0.013

0.038

0.031

0.038

0.006

0.023

0.000

0.020

0.01

0.058

0.005

Fe/Al

0.63

0.82

0.76

0.54

0.63

0.29

0.28

0.48

0.53

0.42

0.62

0.65

0.56

0.42

0.51

0.24

0.54

Contents of Mg and K were under detection limits.

456

UHER, BROSKA, KRZEMIŃSKA, ONDREJKA, MIKUŠ and VACULOVIČ

GEOLOGICA CARPATHICA

, 2019, 70, 6, 449–470

patterns of REE show convex shapes from La to Sm with

almost regularly gradual decreasing of HREE`s from Gd to

Lu, and slightly negative Eu anomalies: Eu

/Eu*

attains 0.6

to 0.95, with the exception of ZK-12 sample (Čierna Hora)

where the value attains 1.2 (Fig. 4). The highest positive cor-

relations between the trace elements of titanite (r ≥ 0.7) have

been observed between Zr vs. Hf , ∑REE vs. Zr (Hf), Th vs.

Hf (Zr), and Nb vs. Ta (Fig. 5).

Titanite U–Pb dating

The BSE imaging shows that investigated titanite crystals

are not homogeneous (Fig. 3) and they are locally slightly

porous, but in general, they show sufficiently large unzonal

domains for successful in-situ dating (Fig. 6).

The accuracy of the SHRIMP results is strongly influenced

by content of uranium in titanite and low U grains usually pro-

vide non-accurate results. In consequence, both titanite sam-

ples from the Tribeč Mts. (T-63 and T-70) were excluded from

the dating, because of their relatively low U contents checked

by a single scan of grains on SHRIMP. Finally, only four sam-

ples (ZK-79, ZK-83, Sih-1, ZK-12) were analysed. The titanite

single spot analyses show compositional variability of U (~ 40

to ~ 660 ppm) and Th (~10 to ~ 680 ppm) in these four samples,

used for the dating (Table 4). Contents of Th attain commonly

>200 ppm and variable U/Th weight ratio (~1 to 9) appears

here. However, in a case of ZK-12 and occasionally also in

ZK-79 and ZK-83 samples, a clearly lower Th contents

(usually <100 ppm) and corresponding Th/U ratio (~0.1 to 0.6)

has been obtained, that may suggest a more complex origin of

the parts of crystals.

In the investigated titanite samples, the content of common

Pb is moderate to high, ranging from 1.85 % to 29.52 %

(Table 4);

his table shows also a correlation between common

Pb content and discordance. Thus the final age calculations

were made for all analyzes as well as after rejection the few

highest common Pb results. There are several analyses on

titanite crystals in each sample that have concordant or nearly

concordant U–Pb ages (+3, −4, −6, +11 % of discordance;

Table 4). All from 50 single spot measurements yielded

238

206

Pb age results between 364 ± 14 Ma and 317 ± 12 Ma,

but most of them are grouped at 334 Ma with minor peaks at

341 Ma and 349 Ma (based on a histogram plot, not shown).

The age calculations for each sample were conducted for

(1) all analysed and then for (2) selected titanite grains, where

the lowest common Pb values are <10 % (except Sih-1 sam-

ple) were acquired. All calculated values including concordia

ages from both Tera–Wasserburg and Wetherill diagrams as

well as weighted average

238

206

Pb ages are shown in Table 5

and compared with corresponding zircon ages (Broska et al.

2013). The distribution of data on concordia plots are rela-

tively consistent; results with the lowest MSWD are preferred

yielding the following ages (Table 5, Fig. 7): 343.1 ± 8.2 Ma,

MSWD = 0.47 (Nízke Tatry Mts., ZK-79 sample), 351.0 ± 6.5 Ma,

MSWD = 0.0047 (Vepor Mts., ZK-83 sample), 344 ± 12 Ma,

MSWD = 5.9 (Vepor Mts., Sih-1 sample), and 337.9 ± 6.1 Ma,

Table 3: Average concentrations of trace elements in titanite from the

West-Carpathian granitic rocks (in ppm).

Massif

Tribeč

Nízke

Tatry

Vepor

Čierna

Hora

Det.

lim.

Sample

T-63

T-70

ZK-79 ZK-83

Sih-1

ZK-12

1.8

2.7

174

130

124

239

200

2.2

106

121

2.4

862

705

649

698

704

890

1.7

1342

1131

998

1061

1244

991

5.0

0.4

8.9

7.2

8.2

5.0

3.6

2.8

2.5

2.4

3.6

0.7

1.6

0.3

1678

1942

2050

1526

2682

1222

0.2

406

285

234

273

357

155

0.1

1019

850

866

850

1037

932

0.1

1.5

7.8

6.5

1.2

111

110

118

125

3.9

2.2

0.7

4.3

2.3

2029

1319

705

894

1436

259

0.1

7479

5594

3370

3918

6570

1393

0.1

1065

831

628

652

1176

281

0.3

4822

3779

3343

3333

5580

1468

2.6

984

713

777

797

1266

423

1.5

202

158

202

162

208

154

0.9

597

444

529

519

848

366

3.4

115

0.5

396

398

406

390

592

296

1.5

116

0.2

183

204

218

170

277

151

0.6

0.2

146

173

189

128

243

1.1

0.2

1.4

102

0.1

2.2

1.8

2.1

2.8

1.7

5.7

1.0

102

8.7

3.8

3.4

6.6

0.9

0.8

2.6

1.3

2.4

0.6

5.1

0.4

580

284

292

298

401

0.1

118

154

169

204

0.5

∑REE

19779

15756

12628

12673

21178

6257

Ce/Yb

51.2

32.3

17.9

30.6

27.1

14.7

Y/Ho

22.4

24.3

25.3

21.8

23.0

20.3

Eu*

0.80

0.85

0.95

0.76

0.61

1.19

Zr/Hf

11.6

12.1

11.2

13.5

12.6

10.3

Nb/Ta

11.6

10.9

13.3

11.9

10.2

19.8

Notes: Det. lim. = lower detection limit (ppm); < = value under the lower

detection limit.

/Eu*

= Eu

/√(Sm

*Gd

), where Eu

, Sm

and Gd

are concentrations

of Eu, Sm and Gd normalized to chondrite concentrations (after Barrat et al.

2012).

459

TITANITE FROM VARISCAN I-TYPE TONALITES TO GRANODIORITES, WESTERN CARPATHIANS

GEOLOGICA CARPATHICA

, 2019, 70, 6, 449–470

rocks, especially in allanite-bearing metaluminous to slightly

peraluminous I-type suites, where 80 to 95 wt. % of ∑REE

reside in allanite + titanite (Gromet & Silver 1983), and up to

7 wt. % of LREE occupies titanite (Bea 1996). Contents of

REE in titanite attain usually up to 5 wt. % REE

(e.g.,

Lyakhovich 1968; Higgins & Ribbe 1976; Gromet & Silver

1983; Nakada 1991; Paterson & Stephens 1992; Bea 1996;

Della Ventura & Bellatreccia 1999; Hoskin et al. 2000;

Chakhmouradian 2004; Vuorinen & Hålenius 2005; Xie et al.

2010). Higher REE

contents are relatively rare, for exam-

ple in some titanite crystals in the Ross Mull granite, Scotland,

United Kingdom (≤ 6.1 wt. %; McLeod et al. 2011), rhyolitic

rocks from Colorado and Nevada, USA (≤ 7.4 wt. %; Ackerson

2011; Colombini et al. 2011), metagranite from the Sulu

UHP complex, China (≤ 7.6 wt. %; Chen & Zheng 2015),

the Willow Spring Draw rhyolite, New Mexico, USA (8.2 wt. %

REE

: 2.7 wt. % Y

and 5.5 wt. % of other REE

;

Foord et al. 1993). The highest known contents of REE in

natural titanite-group minerals are Y-rich titanite (yttrotitanite

or keilhauite variety) with 12.1 wt. % REE

, 6.2 wt. % Al

and 5.9 wt. % Fe

from Buöe (Boie) granitic pegmatite

near Arendal, Norway (Vlasov et al. 1964) and natrotitanite

[(Na

0.5

)Ti(SiO

)O], a member of titanite group with

18.5 wt. % of REE

from the Verkhnee Espe rare-element

deposit, Kazakhstan, related to alkaline granites (Stepanov et

al. 2012).

The REE`s together with Al and Fe are dominant cation

isomorphic admixtures in the studied titanite (≤ 4.8 wt. %

REE

1.0–2.2 wt. % Al

, 0.6–1.6 wt. % Fe

; Table 1).

Following principal coupled substitution mechanisms drive

entry of REE`s, Al and Fe into titanite structure:
REE

+ (Fe,Al)

= Ca

+ Ti

(1),

in REE-(Fe,Al)-rich and Na-poor titanite, typical mainly for

granitic rocks (e.g., Zabavnikova 1957; Vlasov et al. 1964;

Lyakhovich 1968; Ribbe 1980; Green & Pearson 1986;

Broska et al. 2004), rarely in alkaline pegmatites (Russell et al.

1994);

2REE

+ Fe

= 2Ca

+ Ti

(2) (Ribbe 1980; Gieré 1992);

+ (Y, HREE)

= 2Ca

(3), found in natrotitanite (Stepanov

et al. 2012);
(Al,Fe)

+ (OH,F)

−

= Ti

+ O

2−

(4), substitution typical mainly

for metamorphic titanite (e.g., Zabavnikova 1957; Ribbe

1980; Green & Pearson 1986; Gieré 1992; Chen & Zheng

2015);
Fe

+ 2(OH, F)

−

= Ti

+ 2O

2−

(5) (Zabavnikova 1957; Gieré

1992), and
Fe

+ vacancy = Ti

+ O

2−

(6)

substitution (Gieré 1992).

The

Fe Mössbauer spectroscopy indicates a general domi-

nance of Fe

over Fe

in titanite from the West-Carpathian

granitic rocks with 13.5 to 22.0 % Fe

[100*Fe

/(Fe

+ Fe

)];

however some titanite samples (Nitra and Sihla) show 43.6

and 58.3 % Fe

, respectively (Broska et al. 2004). Therefore,

the entry of REE into the titanite structure is compensated by

both Fe

and Fe

cations along the (1) and (2) substitution

mechanisms in the studied samples. The REE versus Fe

total

(Fe

+ Fe

) diagram shows positive correlation trend with

atomic REE : Fe ratio between 2:1 and 1:1, which also support

the presence of both iron valence states in titanite (Fig. 8A).

Moreover, some compositions reveal the REE:Fe ratio below

1:1, indicating a presence of other substitution mechanisms

including Fe without REE, mainly (4) exchange (Fig. 8A–B).

Entry of Nb

cation into the structure of investigated titanite

(up to 0.5 wt. % Nb

) could be compensated by trivalent

cations along the Nb

+ (Al, Fe)

= 2Ti

substitution vector (7),

to żabińskiite end-member, Ca(Al

0.5

)(SiO

)O (Pieczka et

al. 2017). However, measured contents of Nb and Ta in

the studied West-Carpathian titanites are too low for unambi-

guous evidence of such a mechanism.

The major and trace element composition of titanite can

discriminates their magmatic versus metamorphic or hydro-

thermal origin. Generally, the Fe/Al atomic ratio over 0.5 cor-

responds to titanite from igneous rocks, conversely values

<0.5 are characteristic for metamorphic titanite (Nakada 1991;

Kowallis et al. 1997, 2018; Aleinikoff et al. 2002). The Fe/Al

ratio of investigated titanite attains 0.4–0.8 for primary REE-

and Fe-enriched domains in contrast to 0.2–0.4 in the secon-

dary REE- and Fe-poor titanite. Therefore, the Fe/Al value is

not unambiguous for primary titanite but it indicates metamor-

phic (non-igneous) origin of secondary titanite zones. Higher

Th/U weight ratio (~1 to 9) in majority of measured titanite

crystals reveals rather a magmatic origin of titanite in contrast

to distinctly lower Th/U ratio (~0.1 to 0.6) in some domains

(especially in ZK-12 sample), probably of secondary titanite

which indicate metamorphic or hydrothermal origin (cf.

Aleinikoff et al. 2002; Li et al. 2010; Gao et al. 2012).

However, the Th/U ratio cannot effectively discriminates

igneous vs. hydrothermal or metamorphic source for high-

temperature titanite (Liu et al. 2018).

The chondrite-normalized pattern of studied titanite, con-

sisting convex shape of LREE, insignificant to absent Eu

anomaly and gradual decreasing of HREE (Fig. 4) also is not

an efficient discriminator for igneous vs. metamorphic or

hydrothermal origin. Analogous REE-normalized patterns

display titanite from granitic rocks (Bea 1996; Bauer 2015;

Kohn 2017) as well as from metamorphic rocks (eclogites;

Gao et al. 2011; Skublov et al. 2014). Consequently, the shape

of the chondrite-normalized REE patterns of titanite is rather

a result of different REE partitioning between the host-rock

minerals.

Titanite age and origin

Titanite is a relatively common accessory mineral and

a principal carrier of titanium in the West-Carpathian Variscan

I-type tonalites to granodiorites; it fixes ≤ 80 wt. % Ti of

the bulk rock (Broska et al. 2004). Titanite is here present

in the association of magnetite + quartz, which indicates

a relatively increased oxygen fugacity (log f O

≈ −12).

460

UHER, BROSKA, KRZEMIŃSKA, ONDREJKA, MIKUŠ and VACULOVIČ

GEOLOGICA CARPATHICA

, 2019, 70, 6, 449–470

Table 4: Isotope U, Th, and Pb data of studied titanite from the West-Carpathian granitic rocks.

spot

204

Pb/

206

Pb ± %

207

Pb/

206

Pb ± %

208

Pb/

206

Pb ± %

206

Pb/

238

U ± %

206

Pb/

254

UO ± % corrected

204

Pb/

206

% U ppm Th ppm Th/U corrected

206

ppm

ZK-79: granodiorite, Brusno, Nízke Tatry Mountains
ZK-79.1.1

0.00823 5.3

0.181 2.5

0.944 1.1

1.612 4.7

0.1040 2.1

0.0087

15.98

231

2.96

3.4

ZK-79.2.1

0.00924 6.7

0.190 7.7

1.306 1.8

1.559 5.6

0.1078 4.0

0.0093

17.07

304

4.68

3.1

ZK-79.3.1

0.00479 9.6

0.129 1.7

1.052 0.6

1.849 2.5

0.1107 0.9

0.0052

9.42

222

4.19

2.4

ZK-79.4.1

0.00435 8.4

0.116 1.0

0.914 0.6

1.521 3.4

0.1009 1.5

0.0043

7.81

276

3.41

3.9

ZK-79.5.1

0.00530 8.1

0.135 2.8

1.049 0.6

1.703 2.8

0.1059 1.1

0.0056

10.21

256

4.00

2.9

ZK-79.6.1

0.01240 4.4

0.222 5.4

1.288 3.8

1.890 6.2

0.1203 5.2

0.0115

21.11

291

4.77

2.9

ZK-79.7.1

0.00457 8.0

0.115 1.0

0.887 0.6

1.530 2.8

0.1017 1.4

0.0042

7.71

277

3.30

4.0

ZK-79.8.1

0.00317 5.5

0.101 1.5

0.181 3.0

1.652 3.2

0.1023 1.4

0.0032

5.94

163

0.24

7.5

ZK-79.9.1

0.00277 10.0

0.101 0.9

0.433 0.6

1.561 2.4

0.1008 1.1

0.0032

5.93

108

151

1.40

5.1

ZK-79.10.1

0.00830 7.9

0.177 1.1

0.442 1.1

1.684 4.8

0.1120 2.4

0.0085

15.47

0.59

2.0

ZK-79.11.1

0.00495 8.9

0.129 1.0

1.154 0.6

1.718 1.9

0.1065 1.2

0.0052

9.51

265

4.49

2.7

ZK-79.12.1

0.00762 6.5

0.169 2.7

1.829 0.5

1.708 3.2

0.1129 1.7

0.0079

14.47

477

7.34

3.2

ZK-79.13.1

0.00450 8.5

0.117 1.0

0.903 0.6

1.628 2.1

0.1026 1.1

0.0044

7.98

250

3.38

3.4

ZK-79.14.1

0.00537 9.2

0.134 1.0

1.041 0.6

1.829 2.3

0.1127 1.7

0.0055

10.06

205

3.87

2.5

ZK-79.15.1

0.00512 8.0

0.132 0.9

1.004 0.6

1.774 3.0

0.1098 1.3

0.0053

9.78

239

3.73

3.0

ZK-83: tonalite, Hriňová, Slovenské Rudohorie Mountains
ZK-83.1.1

0.00190 7.9

0.082 0.7

0.336 0.5

1.488 1.9

0.0976 0.9

0.0020

3.62

204

231

1.13

9.7

ZK-83.2.1

0.00304 7.9

0.096 0.8

0.632 0.5

1.643 2.3

0.1034 0.4

0.0029

5.28

107

244

2.28

5.1

ZK-83.3.1

0.00642 4.5

0.142 5.6

0.584 3.7

1.660 3.8

0.1068 1.2

0.0061

11.08

115

187

1.63

5.4

ZK-83.4.1

0.00092 7.5

0.069 1.2

0.086 2.6

1.496 3.2

0.0973 1.3

0.0010

1.88

398

0.19

19.1

ZK-83.5.1

0.00528 7.5

0.129 0.9

0.960 0.6

1.821 3.2

0.1126 1.4

0.0051

9.40

210

3.62

2.8

ZK-83.6.1

0.00630 6.4

0.145 1.8

0.942 0.6

1.633 3.8

0.1087 1.6

0.0062

11.42

253

3.29

3.8

ZK-83.7.1

0.00099 7.4

0.068 0.5

0.070 0.8

1.603 2.9

0.0998 1.3

0.0010

1.85

338

0.13

15.9

ZK-83.8.1

0.00741 6.5

0.156 4.7

0.899 2.4

1.881 3.0

0.1124 1.5

0.0071

12.91

174

3.11

2.5

ZK-83.9.1

0.00467 5.9

0.124 8.2

0.622 2.5

1.584 3.9

0.1025 1.9

0.0048

8.82

113

223

1.97

5.2

ZK-83.10.1

0.00826 7.2

0.196 3.8

0.428 4.0

1.886 3.5

0.1182 1.7

0.0097

17.78

0.26

1.8

ZK-83.11.1

0.00643 4.4

0.137 5.7

0.640 2.1

1.737 4.0

0.1093 2.3

0.0057

10.51

109

215

1.97

5.1

ZK-83.12.1

0.00752 7.0

0.169 2.6

0.981 0.6

1.831 3.6

0.1159 1.6

0.0079

14.42

216

3.43

3.0

ZK-83.13.1

0.00514 8.5

0.125 1.0

1.050 0.6

1.692 2.5

0.1076 1.4

0.0049

8.90

255

3.92

3.1

ZK-83.14.1

0.00134 7.7

0.073 1.5

0.084 1.3

1.455 3.5

0.0974 1.4

0.0013

2.37

305

0.14

14.9

ZK-83.15.1

0.00694 6.6

0.156 4.6

1.114 0.6

1.935 2.4

0.1174 1.1

0.0070

12.85

229

4.24

2.6

Sih-1: tonalite, Sihla, Slovenské Rudohorie Mountains
Sih-1.1.1

0.00704 6.4

0.165 2.5

1.326 0.5

1.643 4.4

0.1080 2.6

0.0076

13.98

381

5.29

3.4

Sih-1.1.2

0.00518 8.7

0.141 0.9

1.237 0.6

1.833 2.7

0.1104 1.6

0.0060

11.03

272

4.86

2.6

Sih-1.2.1

0.00532 8.7

0.135 1.0

1.350 0.6

1.667 3.2

0.1045 1.4

0.0056

10.27

338

5.54

2.8

Sih-1.3.1

0.01585 4.1

0.289 3.1

1.387 0.6

1.623 3.8

0.1064 1.7

0.0161

29.52

261

4.08

2.4

Sih-1.4.1

0.01314 4.6

0.244 1.4

2.176 0.5

1.539 2.8

0.1070 1.1

0.0130

23.83

678

9.42

3.1

Sih-1.5.1

0.00534 8.2

0.143 0.9

1.308 0.5

1.803 2.8

0.1097 1.6

0.0061

11.19

305

5.26

2.7

ZK-12 tonalite, Kysak, Čierna Hora Mountains
ZK-12.1.1

0.00142 7.3

0.075 0.6

0.102 0.8

1.524 2.5

0.0967 0.9

0.0015

2.72

341

0.22

15.7

ZK-12.2.1

0.00910 3.9

0.176 2.9

0.642 0.6

1.652 2.7

0.1061 1.5

0.0084

15.43

119

209

1.76

5.3

ZK-12.3.1

0.01265 5.7

0.234 1.0

0.521 2.3

1.466 3.6

0.1108 1.5

0.0123

22.58

0.16

2.9

ZK-12.4.1

0.00105 8.5

0.070 1.1

0.077 0.8

1.443 3.4

0.0937 1.1

0.0011

2.05

347

0.15

15.9

ZK-12.5.1

0.00131 4.8

0.074 0.4

0.088 1.2

1.385 4.2

0.0923 1.7

0.0014

2.56

658

0.15

30.4

ZK-12.6.1

0.00271 6.2

0.090 0.7

0.292 0.5

1.655 2.0

0.0994 0.9

0.0026

4.70

178

156

0.88

7.8

ZK-12.7.1

0.00369 5.8

0.103 0.7

0.209 0.7

1.532 4.0

0.0972 2.0

0.0034

6.24

144

0.36

6.4

ZK-12.8.1

0.00150 4.8

0.075 1.1

0.069 1.9

1.420 4.3

0.0935 1.8

0.0015

2.69

558

0.05

25.7

ZK-12.9.1

0.00143 6.9

0.075 1.4

0.087 2.7

1.517 3.3

0.0972 1.3

0.0015

2.75

310

0.13

14.5

ZK-12.10.1

0.00143 9.4

0.077 0.7

0.301 0.5

1.494 2.9

0.0957 1.2

0.0016

2.92

249

255

1.02

11.4

ZK-12.11.1

0.00177 5.8

0.081 4.2

0.160 6.5

1.379 3.7

0.0919 1.6

0.0019

3.45

408

154

0.38

18.6

ZK-12.12.1

0.00524 7.4

0.139 0.9

0.268 1.0

1.696 3.1

0.1053 1.5

0.0058

10.69

0.22

2.8

ZK-12.13.1

0.00423 4.8

0.115 2.0

0.210 2.5

1.432 3.9

0.0955 1.7

0.0042

7.72

190

0.21

8.6

ZK-12.14.1

0.00348 7.5

0.101 0.8

0.391 1.4

1.622 2.2

0.1017 1.4

0.0033

6.02

107

129

1.21

5.0

ZK-12.15.1

0.00487 6.2

0.129 0.7

0.458 0.6

1.701 2.1

0.1050 0.8

0.0052

9.46

110

138

1.25

5.0

Errors are 1-sigma; Pb

and Pb

indicate the common and radiogenic portions, respectively.

Error in standard calibration was 0.81 % (not included in above errors but required when comparing data from different mounts).

isotopic ratio selected to concordia calculation

461

TITANITE FROM VARISCAN I-TYPE TONALITES TO GRANODIORITES, WESTERN CARPATHIANS

GEOLOGICA CARPATHICA

, 2019, 70, 6, 449–470

Table 4 (continued): Isotope U, Th, and Pb data of studied titanite from the West-Carpathian granitic rocks.

spot

corrected

208

ppm

232

Th/

238

U ± %

206

Pb/

238

U age

(Ma)

207

Pb/

206

Pb age

(Ma)

discordant

238

206

± %

207

206

± %

207

235

U ± %

206

238

U ± % error

corr.

ZK-79: granodiorite, Brusno, Nízke Tatry Mountains
ZK-79.1.1

2.5

3.1 1.2

317 ± 12

653 ± 322

19.61 4.0

0.0614 15.0

0.432 15.5

0.0510 4.0 0.3

ZK-79.2.1

3.6

4.8 1.6

347 ± 17

411 ± 844

18.05 4.6

0.0550 37.7

0.420 38.0

0.0554 4.6 0.1

ZK-79.3.1

2.3

4.3 0.7

338 ± 12

564 ± 285

18.46 3.8

0.0589 13.1

0.440 13.6

0.0542 3.8 0.3

ZK-79.4.1

3.2

3.5 1.1

347 ± 13

291 ± 261

−19

18.12 3.8

0.0521 11.4

0.397 12.0

0.0552 3.8 0.3

ZK-79.5.1

2.8

4.1 0.7

334 ± 12

518 ± 305

18.70 3.8

0.0577 13.9

0.425 14.4

0.0535 3.8 0.3

ZK-79.6.1

3.1

4.9 1.2

343 ± 23

−556 ± 1371

165

18.65 6.7

0.0370 50.9

0.274 51.4

0.0536 6.7 0.1

ZK-79.7.1

3.2

3.4 1.0

350 ± 13

90 ± 296

−295

18.03 3.8

0.0478 12.5

0.366 13.0

0.0555 3.8 0.3

ZK-79.8.1

0.5

0.2 1.5

335 ± 12

387 ± 131

18.69 3.6

0.0544 5.9

0.401 6.9

0.0535 3.6 0.5

ZK-79.9.1

1.7

1.5 0.8

345 ± 12

627 ± 154

18.03 3.7

0.0607 7.1

0.464 8.0

0.0554 3.7 0.5

ZK-79.10.1

0.3

0.6 1.6

354 ± 13

466 ± 451

17.68 4.1

0.0563 20.4

0.439 20.8

0.0566 4.1 0.2

ZK-79.11.1

2.9

4.6 0.6

337 ± 12

498 ± 278

18.53 3.8

0.0572 12.6

0.425 13.2

0.0540 3.8 0.3

ZK-79.12.1

5.7

7.6 1.0

359 ± 13

550 ± 369

17.35 3.9

0.0585 16.9

0.465 17.3

0.0576 3.9 0.2

ZK-79.13.1

2.7

3.5 0.2

335 ± 12

238 ± 284

−42

18.83 3.8

0.0509 12.3

0.373 12.9

0.0531 3.8 0.3

ZK-79.14.1

2.4

4.0 1.2

351 ± 13

434 ± 325

17.83 3.9

0.0555 14.6

0.429 15.1

0.0561 3.9 0.3

ZK-79.15.1

2.7

3.9 1.0

345 ± 13

491 ± 259

18.10 3.8

0.0570 11.7

0.434 12.3

0.0553 3.8 0.3

ZK-83: tonalite, Hriňová, Slovenské Rudohorie Mountains
ZK-83.1.1

2.7

1.2 0.5

347 ± 12

398 ± 97

18.03 3.6

0.0547 4.3

0.418 5.6

0.0555 3.6 0.6

ZK-83.2.1

2.9

2.3 3.0

350 ± 14

248 ± 172

−42

17.95 4.0

0.0512 7.5

0.393 8.5

0.0557 4.0 0.5

ZK-83.3.1

2.2

1.7 1.6

343 ± 14

67 ± 518

−419

18.43 4.1

0.0474 21.7

0.354 22.1

0.0542 4.1 0.2

ZK-83.4.1

0.9

0.2 1.7

350 ± 12

414 ± 55

17.90 3.6

0.0550 2.4

0.424 4.4

0.0559 3.6 0.8

ZK-83.5.1

2.4

3.8 0.8

354 ± 13

252 ± 295

−41

17.77 3.8

0.0512 12.8

0.398 13.4

0.0563 3.8 0.3

ZK-83.6.1

3.0

3.4 1.7

360 ± 13

319 ± 314

−9

17.42 3.8

0.0528 13.8

0.418 14.3

0.0574 3.8 0.3

ZK-83.7.1

0.5

0.1 0.9

344 ± 12

355 ± 49

18.22 3.6

0.0536 2.2

0.406 4.2

0.0549 3.6 0.9

ZK-83.8.1

1.8

3.2 0.8

328 ± 13

48 ± 600

−594

19.27 4.1

0.0470 25.1

0.336 25.4

0.0519 4.1 0.2

ZK-83.9.1

2.5

2.0 1.1

340 ± 13

440 ± 475

18.42 3.7

0.0557 21.4

0.417 21.7

0.0543 3.7 0.2

ZK-83.10.1

0.1

0.3 0.7

343 ± 13

1159 ± 334

17.70 4.0

0.0785 16.9

0.611 17.3

0.0565 4.0 0.2

ZK-83.11.1

2.4

2.0 0.8

345 ± 13

−232 ± 604

253

18.44 3.7

0.0419 24.0

0.313 24.2

0.0542 3.7 0.2

ZK-83.12.1

2.4

3.6 1.2

353 ± 13

592 ± 372

17.64 3.9

0.0597 17.2

0.467 17.6

0.0567 3.9 0.2

ZK-83.13.1

3.0

4.1 1.1

351 ± 13

151 ± 347

−135

17.98 3.8

0.0491 14.8

0.376 15.3

0.0556 3.8 0.2

ZK-83.14.1

0.5

0.1 0.4

357 ± 13

326 ± 82

−10

17.56 3.6

0.0529 3.6

0.416 5.1

0.0569 3.6 0.7

ZK-83.15.1

2.5

4.4 0.8

350 ± 13

402 ± 461

17.91 3.9

0.0548 20.6

0.421 20.9

0.0558 3.9 0.2

Sih-1: tonalite, Sihla, Slovenské Rudohorie Mountains
Sih-1.1.1

4.1

5.4 3.3

344 ± 14

723 ± 298

18.03 4.1

0.0634 14.0

0.485 14.6

0.0555 4.1 0.3

Sih-1.1.2

2.9

5.0 1.2

334 ± 12

834 ± 229

18.47 3.8

0.0669 11.0

0.499 11.6

0.0541 3.8 0.3

Sih-1.2.1

3.6

5.7 2.4

333 ± 12

522 ± 288

18.78 3.8

0.0578 13.1

0.424 13.7

0.0533 3.8 0.3

Sih-1.3.1

2.7

4.2 1.6

278 ± 11

520 ± 697

22.56 4.1

0.0578 31.8

0.353 32.0

0.0443 4.1 0.1

Sih-1.4.1

7.0

9.7 0.2

319 ± 12

220 ± 577

−46

19.77 4.0

0.0505 24.9

0.353 25.3

0.0506 4.0 0.2

Sih-1.5.1

3.2

5.4 1.1

334 ± 12

798 ± 227

18.51 3.8

0.0658 10.8

0.490 11.5

0.0540 3.8 0.3

ZK-12 tonalite, Kysak, Čierna Hora Mountains
ZK-12.1.1

0.7

0.2 3.6

336 ± 12

379 ± 68

18.65 3.7

0.0542 3.0

0.401 4.7

0.0536 3.7 0.8

ZK-12.2.1

2.0

1.8 1.0

324 ± 12

−283 ± 549

219

19.67 3.7

0.0411 21.6

0.288 21.9

0.0508 3.7 0.2

ZK-12.3.1

0.2

0.2 0.9

364 ± 14

93 ± 697

−295

17.34 4.1

0.0479 29.4

0.381 29.7

0.0577 4.1 0.1

ZK-12.4.1

0.6

0.2 1.2

335 ± 12

379 ± 64

18.71 3.7

0.0542 2.8

0.399 4.7

0.0534 3.7 0.8

ZK-12.5.1

1.1

0.2 1.6

337 ± 12

393 ± 41

18.59 3.7

0.0545 1.8

0.404 4.1

0.0538 3.7 0.9

ZK-12.6.1

1.6

0.9 0.6

321 ± 11

227 ± 121

−42

19.64 3.6

0.0507 5.3

0.356 6.4

0.0509 3.6 0.6

ZK-12.7.1

0.5

0.4 1.0

326 ± 12

129 ± 168

−156

19.38 3.7

0.0486 7.1

0.346 8.0

0.0516 3.7 0.5

ZK-12.8.1

0.3

0.1 1.7

337 ± 12

317 ± 60

−6

18.65 3.6

0.0527 2.6

0.390 4.5

0.0536 3.6 0.8

ZK-12.9.1

0.4

0.1 0.8

341 ± 12

385 ± 75

18.38 3.6

0.0543 3.4

0.408 4.9

0.0544 3.6 0.7

ZK-12.10.1

2.9

1.1 1.3

336 ± 12

436 ± 83

18.66 3.6

0.0556 3.7

0.411 5.2

0.0536 3.6 0.7

ZK-12.11.1

1.7

0.4 0.7

333 ± 12

402 ± 158

18.84 3.6

0.0548 7.1

0.401 7.9

0.0531 3.6 0.5

ZK-12.12.1

0.1

0.2 0.6

329 ± 12

700 ± 217

18.89 3.8

0.0628 10.2

0.458 10.9

0.0530 3.8 0.3

ZK-12.13.1

0.5

0.2 0.9

331 ± 12

319 ± 176

−4

18.99 3.6

0.0528 7.8

0.383 8.6

0.0527 3.6 0.4

ZK-12.14.1

1.4

1.2 0.4

338 ± 12

207 ± 194

−65

18.64 3.7

0.0503 8.4

0.372 9.2

0.0536 3.7 0.4

ZK-12.15.1

1.4

1.3 0.5

331 ± 12

524 ± 186

18.87 3.7

0.0578 8.5

0.423 9.3

0.0530 3.7 0.4

462

UHER, BROSKA, KRZEMIŃSKA, ONDREJKA, MIKUŠ and VACULOVIČ

GEOLOGICA CARPATHICA

, 2019, 70, 6, 449–470

Table 5: The U–Pb age results of titanite (this study) and zircon

(Broska et al. 2013) calculated by Tera–Wasserburg (T–W),

Wetherill (W) and Mean U–Pb methods. Preferred results are written

in bold font.

Sample

age (Ma) ± (Ma)

MSWD N

calculation

Titanite (this study)
ZK-79

343.7 6.8

1.4 15

T–W

(Nízke Tatry Mts.)

343.1 8.2

0.47 8

341.8 5.8

0.60 15

Mean U–Pb

ZK-83

348.5 6.6

0.31 15

T–W

(Vepor Mts.)

351.0 6.5

0.0047 12

347.8 6.5

0.42 15

Mean U–Pb

Sih-1

336 11

6.5 5

T–W

(Vepor Mts.)

344 12

5.9 4

340 13

0.18 4

Mean U–Pb

ZK-12

334.9 6.2

1.7 15

T–W

(Čierna Hora Mts.)

337.9 6.1

0.85 10

334.0 6.1

0.59 15

Mean U–Pb

Zircon (Broska et al. 2013; *recalculated)
NTBS-2

353 3

1.6 11

T–W

(Nízke Tatry Mts.)

353 2.2

0.00 11

W (*)

Sihla-1

357 2

1.8 16

T–W

(Vepor Mts.)

356.1 2

0.99 16

W (*)

CH SK-1

357 3

1.9 8

T–W

(Čierna Hora Mts.)

356.4 2.4

0.58 8

W (*)

Therefore it precipitated from a relatively oxidizing and water

enriched environment, exclusively in the granitic rocks with

higher CaO/Al

(wt. %) bulk rock ratio (0.15–0.25) and

≥ 0.4 wt. % TiO

(Broska et al. 2004).

Variscan calc-alkaline granitic rocks of I- and S-type affi-

nity belong to the most voluminous lithologies within Paleo-

zoic crystalline basement of the West-Carpathian Tatric and

Veporic units. Their age of magmatic crystallization has been

determined recently by single-grain and in situ U–Pb dating of

zircon and monazite. The dating ages are usually between

~ 360 and 340 Ma (Upper Devonian to Carboniferous); they

indicate a main interval of Variscan plutonic activity in

the West-Carpathian Tatric and Veporic crystalline basement

(e.g., Poller et al. 2000; Gaab et al. 2005; Burda & Gawęda

2009; Kohút et al. 2009; Broska et al. 2013; Burda et al.

2013a, b; Gawęda et al. 2016). This age interval is also corro-

borated by chemical U–Th–Pb dating of monazite (e.g., Finger

et al. 2003; Uher et al. 2014) and some older Rb–Sr whole-

rock isochron data (Cambel et al. 1990 and references therein).

Such Upper Devonian to early Carboniferous granitic mag-

matism belongs to older phase of plutonic activity, located

within internal parts of the Variscan orogen for example in

the Hintertal Plutonic Suite (mainly the Pletzen Pluton) of

the Seckau Complex, Austroalpine basement of the Eastern

Alps (Mandl et al. 2018), in part of the Moldanubian plutonic

complex (Weinsberg granite) and the Central Bohemian

Batholith (Sázava granodiorite; Cháb et al. 2008; Žák et al.

2014 and references therein), in southern Schwarzwald and

NW part of the French Massif Central, e.g. Guéret batholith

(Kroner & Romer 2013 and references therein).

Our SHRIMP U–Pb titanite results also reveal Variscan age

interval between 351 ± 6.5 and 338 ± 6 Ma, which corresponds

to early Carboniferous, Tournaisian to Visean stage (Table 5,

Fig. 7). However, they are systematically lower (~5 to 19 Ma)

in comparison with zircon U–Pb ages of 353–356 ± 2 Ma

achieved

by in-situ SIMS method from the same titanite-

bearing granitic rocks from the Western Carpathians (Broska

et al. 2013; Table 5).

Here we suggest the following two most plausible interpre-

tations of this age discrepancy: (1) the titanite ages indicate

their younger, late-magmatic crystallization in contrast to

the early-magmatic age of zircon precipitation; or (2) post-

magmatic (subsolidus) origin of titanite due to younger event

connected with subsequent overprint of the parental granitic

rocks (discussed below).

For estimating of titanite crystallization temperature

(Ttn)], we applicate the Zr-in-titanite thermobarometry

(Hayden et al. 2008). This geothermobarometer is dependent

on Zr content in titanite as well as activity of coexisting quartz

[a(SiO

)] and rutile [a(TiO

)] in the investigating rock, where

a(SiO

) = a(TiO

) = 1.0 for quartz-and rutile-bearing rocks.

How ever, rutile does not identify in our tonalites to granodio-

rites; instead of ilmenite, Ti-bearing magnetite, biotite and

allanite-(Ce) represent principal carriers of Ti here. In such

rutile-absent magmatic rocks, a(TiO

) attains values ≥ 0.6 but

most of the ilmenite- and biotite-bearing rocks are nearly rutile

saturated (Hayden & Watson 2007; Ferry & Watson 2007;

Chambers & Kohn 2012). We calculate a(TiO

) = 0.6 to 1.0

for estimating of possible interval of T

(Ttn). The maximum

(Ttn) was achieved at a(TiO

) = 1.0; the activity below 1.0

produced slightly decreasing of this temperature. For example,

for a(TiO

) = 0.9 and 0.6, the T

(Ttn) were 5–6 °C and 24

to 28 °C lower, respectively (Table 6). Pressure represents

the other important parameter, influencing the T

(Ttn). We

applicate pressures of 0.2 to 0.4 GPa as the most realistic

values for magmatic emplacement, initial cooling and uplift of

common orogen-related granitic intrusions. The emplacement/

solidification pressure of the West-Carpathian titanite-bearing

I-type granitic rocks, calculated based on Al-in-hornblende

geobarometry attains ~ 0.35 to 0.4 GPa (Petrík & Broska 1994;

Broska et al. 1997). The pressure (P) positively correlates

with T

(Ttn); the values are 22–24 °C higher at P = 0.4 GPa

with a comparison of 0.2 GPa, using the same a(TiO

) value.

Con sequently, the Zr-in-titanite thermobarometry reveal

(Ttn) = 650–750 °C for a(TiO

) = 0.6–1.0 and P = 0.2–0.4 GPa

for the investigated granitic rocks (Table 6).

Interpretation of such temperature is also dependent on

the diffusion rate and corresponding Zr closure temperature in

titanite [T

Zr(Ttn)]. This parameter is further a function of

titanite crystal size and cooling rate. Our titanite crystals are

relatively large, ~ 0.5 to 10 mm across (Figs. 2–3, 6). Such

large crystal size secured retention (negligible Zr diffusion) of

titanite at the temperature ≥ 750 °C during 10

–10

years at

common cooling rate of ~10–100 °C/Ma (Cherniak 2006;

Hayden et al. 2008; Kirkland et al. 2016, 2018; Kohn 2017).

However, the measured U–Pb ages are additionally influenced

464

UHER, BROSKA, KRZEMIŃSKA, ONDREJKA, MIKUŠ and VACULOVIČ

GEOLOGICA CARPATHICA

, 2019, 70, 6, 449–470

by possible partial loss of Pb from titanite lattice expressed as

Pb closing temperature in titanite [T

Pb(Ttn)]. The T

Pb(Ttn)

is generally lower than T

Zr(Ttn), due to the higher mobility

of Pb with comparison to Zr (Cherniak 2006; Kirkland et al.

2016, 2018). Nevertheless, T

Pb(Ttn) is also relatively high

(≥ 700–800 °C) for large titanite crystals (≥ 0.5 mm) at cooling

rate of ~10–100 °C/Ma (Gao et al. 2012; Sun et al. 2012;

Spencer et al. 2013; Kohn 2017). Based on above calculations

and assumptions, we can conclude T

Zr(Ttn) > T

Pb(Ttn) >

(Ttn) for our granitic rocks and therefore the calculated

(Ttn) are not influenced by Zr and Pb mobility in the studied

titanite crystals. Consequently, our data represent rather true

precipitation temperatures at the measured age than the age of

titanite closure temperature.

If we consider the late-magmatic origin of titanite, a time of

magmatic evolution, including pluton accretion and mineral

crystallization from the solidified melt of the parental granite

is necessary to take into consideration. Recent growing dataset

of evidence suggests that granitic pluton emplacement and

assembly occurs by incremental accretion of numerous suc-

cessive and relatively small pulses of magma with little liquid

that accumulates by dyke-like propagation over variable time

periods, generally from 10

to 10

years, depending of geody-

namic setting and source fertility (e.g., Coleman et al. 2004;

Glazner et al. 2004; Michel et al. 2008; Schaltegger et al.

2009; Barboni et al. 2013). Sensitive in-situ zircon U–Pb geo-

chronological data indicate amalgamation of large granitic

batholiths (~10

to 10

in their maximum extent) during

approximately 5 to 10 Ma, in contrast to emplacement time of

smaller composite plutons (<10

; ~1.5 Ma), and espe-

cially to one distinct magmatic pulse or small single plutons

which create only during 10

to 10

years (e.g., Matzel et

al. 2006; Michel et al. 2008; Carichi et al. 2012). Complete

amalgamation time of the West-Carpathian I-type granite plu-

tons (~10

to 10

in order of magnitude) could be esti-

mated over ~10 Ma, including numerous magmatic pulses.

The model of long-lasting incremental growing of granitic

pluton formed by repeated magma injections into an active

shear zone during over ~30 Ma period has been recently

applied for Variscan composite polygenetic intrusion of

the Tatra granitoid pluton (Gawęda et al. 2016). On the other

hand, the age difference between zircon and titanite U–Pb

ages for the same granitic rocks in our case (~5 to 19 Ma;

Table 5) is generally too large. For example, the Re di Castello

pluton in Adamello granite batholith, Italy represents comag-

matic crystallization of zircon and titanite during one or seve-

ral closely subsequent magmatic pulses, where U–Pb dating of

Fig. 8. Substitution diagrams and vectors of titanite from the West-

Carpathian granitic rocks.

Table 6: Calculated titanite saturation temperature [T

(Ttn)] at various assumed pressure (0.2 to 0.4 GPa) based on average Zr concentration

in titanite (Table 3) at a(TiO

) = 0.6 and 1.0 (Hayden et al. 2008) and corresponding zircon saturation temperature [T

(Zrn)] (Watson & Harrison

1983).

Sample

Area

Zr (ppm)

(Ttn) (°C) at 0.2 GPa

(Ttn) (°C) at 0.3 GPa

(Ttn) (°C) at 0.4 GPa

(Zrn) (°C)

a(TiO

) 0.6

a(TiO

) 1.0

a(TiO

) 0.6

a(TiO

) 1.0

a(TiO

) 0.6

a(TiO

) 1.0

T-63

Tribeč Mts.

406

698

726

710

738

722

750

797

T-70

Tribeč Mts.

285

680

707

692

718

703

730

ZK-79

Nízke Tatry Mts.

234

671

696

682

708

693

720

779

ZK-83

Vepor Mts.

273

678

704

690

716

701

728

840

Sih-1

Vepor Mts.

357

692

719

703

731

715

743

808

ZK-12

Čierna Hora Mts.

155

651

675

662

687

673

698

829

0.04

0.06

0.08

0.10

0.12

0.84

0.86

0.88

0.90

0.92

0.94

Ti (apfu)

Tribeč T-63
Tribeč T-70
N. Tatry ZK-79
Vepor. ZK-83
Vepor. Sih-1
Č. Hora ZK-12

(Al,Fe)

(OH,F)Ti

-1

0.00

0.01

0.02

0.03

0.04

0.05

0.06

0.07

0.08

0.00

0.01

0.02

0.03

0.04

0.05

pfu)

total

(apfu)

Tribeč T-63
Tribeč T-70
N. Tatry ZK-79
Vepor. ZK-83
Vepor. Sih-1
Č. Hora ZK-12

2:1

1:1

1:2

REE

-2

-1

REEFe

-1

REEFe

(OH)Ca

-1

-2

-1

465

TITANITE FROM VARISCAN I-TYPE TONALITES TO GRANODIORITES, WESTERN CARPATHIANS

GEOLOGICA CARPATHICA

, 2019, 70, 6, 449–470

titanite reveal only 130 to 700 ka younger ages than zircon

(Schaltegger et al. 2009).

Textural patterns indicate titanite crystallization at the ex pense

of magmatic Ti-rich magnetite, magnesian biotite and Ca-rich

plagioclase which can be observed as armoured inclusions

in titanite, where re-equilibration involved oxidation of

the ulvöspinel (Fe

TiO

) component in Ti-rich magnetite

produced titanite and Ti-poor magnetite in the Tribeč I-type

granites (Broska et al. 2007). Titanite and epidote partly

replace magmatic biotite and late-magmatic, Ti-poor magne-

tite is commonly overgrown by titanite in the Čierna Hora

granitic rocks (Bónová et al. 2010).

The calculation of a model

mineral equilibrium in the K

O–CaO–FeO–Al

–TiO

–

SiO

–H

O–O

(KCFATSHO) system indicates that pure mag-

netite + titanite forms in granites as a product of the reaction

between the early magmatic Ti-rich magnetite, Mg-rich biotite

(phlogopite), and anorthite-rich plagioclase in a fluid-rich

environment derived from a melt under relatively oxidizing

conditions (Broska et al

. 2007

; Broska & Petrík 2011).

he above- mentioned authors suggest a late-magmatic origin

of titanite; assuming equilibrium among biotite, K-feldspar

and magnetite, where the intersection of the calculated biotite

stability curves with the curve of minimum water content in

the haplogranite system (after Johannes & Holtz 1996) gives

4.8 wt.% H

O at 744 °C and 0.4 GPa for the titanite-bearing

tonalite of the Čierna Hora Mts. (Bónová et al. 2010). Appli-

cation of the Fe–Ti oxide geothermometry (Sauerzapf et al.

2008; Ghiorso & Evans 2008) show ~630 to 780 °C interval

for the equilibrium of magnetite–ilmenite pair for the titanite-

bearing granitic rocks (Tribeč, Čierna Hora; Broska & Petrík

2011). Moreover, this titanite producing reaction indicates

the temperature of ~710 °C at 0.4 GPa pressure and aH

O = 0.5,

calculated using the Thermocalc 3.31 (Holland & Powell 2011)

and the AX software for end-member activities (Broska &

Petrík 2015). These calculated temperatures are in accordance

with our results based on Zr-in-titanite thermometry (Table 6).

However, such temperatures (~ 650 to 750 °C) are near but

mostly under tonalite solidus at ~ 0.3–0.4 GPa (e.g., Singh &

Johannes 1996). Experiments indicate a beginning of dehydra-

tion melting in biotite–plagioclase–quartz assemblage of tona-

lite composition at 760 °C and 0.5 GPa, using biotite chemistry

close to ~50 mol. % annite, 0.5 apfu Al and 0.3 apfu Ti in

octahedral site (Singh & Johannes 1996) which is similar to

the biotite composition of investigated West-Carpathian gra-

nitic rocks (Petrík 1980; Petrík & Broska 1989, 1994; Bónová

et al. 2010).

After the formation of subduction-related I-type granites,

subsequent Variscan crustal shortening during younger col-

lisional event might have trigger partial melting and intrusion

of limited amounts of leucogranitic melts and/or related

high-temperature fluids into I-type tonalites to granodiorites,

dated at ~ 340 Ma by chemical U–Th–Pb monazite method in

the Tribeč Mts. (Broska & Petrík 2015) and Branisko near

Čierna Hora (Bónová et al. 2005). Almandine garnet from

granitic pegmatite near Rimavská Baňa (Veporic Unit) also

reveals a Visean Sm–Nd isotopic age of 339.0 ± 7.7 Ma (Thöni

et al. 2003). Another example of two magmatic pulses has

been documented by LA–MC–ICP–MS U–Pb zircon dating

form granitic rocks of the Tatry Mts., where the high lumines-

cence zircon cores record age of 350 ± 3 Ma, and younger,

low luminescence zircon rims gives 337 ± 6 Ma (Burda et al.

2013b).

Optical and BSE photomicrographs of the West-Carpathian

granitic titanite and associated minerals (Broska et al. 2004,

2007; Broska & Petrík 2011, 2015) together with our results

(Fig. 3) clearly document its complex evolution including

growth and superimposed partial dissolution–reprecipitation

and alteration phenomena. In some cases, primary titanite was

partly to almost completely replaced by secondary ilmenite ±

epidote pseudomorphs with many pores (Broska et al. 2007).

Complex textural patterns are characteristic feature of acces-

sory titanite of various origin; they commonly occur in titanite

crystals of volcanic (Nakada 1991; Colombini et al. 2011),

plutonic (Paterson et al. 1989; Paterson & Stephens 1992;

McLeod et al. 2011; Middleton et al. 2013) as well as post-

magmatic and metamorphic origin (Černý et al. 1995; Cempírek

et al. 2008). In our samples, we interpret such textures as

a result of subsolidus, fluid-induced high-temperature precipi-

tation of titanite during a Variscan post-magmatic event.

Moreover, the late irregular veinlets and irregular patchy

zones of younger, secondary titanite occur along cleavage

planes, fissures and crystal rims of primary titanite (Fig. 3G–H),

commonly with secondary allanite-(Ce), epidote, quartz,

albite, K-feldspar, chlorite, ilmenite, TiO

phase (rutile and/or

anatase), and hematite. This late mineral association could be

connected with Alpine metamorphic overprint of the Variscan

basement of the Western Carpathians, especially in the Veporic

Unit, where Cretaceous (~100 to 70 Ma) metamorphic condi-

tions of the Kráľova Hoľa Complex attained 430–530 °C and

550–850 MPa (Janák et al. 2001; Jeřábek et al. 2008).

Summary

The study of large titanite crystals (~0.5 to 10 mm) from

Variscan I-type granitic rocks of the Western Carpathians

allows the following main conclusions:

• Titanite, as a characteristic accessory mineral of Variscan

I-type granitic rocks, commonly shows complex composi-

tional oscillatory, sector and convolute zonal textures,

reflecting mainly variations in Ca and Ti versus Al, Fe, REE

(≤ 4.8 wt. % REE

), and Nb (≤ 0.5 wt. % Nb

• Following principal substitutions controlling the crystal

chemistry were detected in the studied titanite:

REE

+ Fe

= Ca

+ Ti

, 2REE

+ Fe

= 2Ca

+ Ti

, and

(Al, Fe)

+ (OH, F)

−

= Ti

+ O

2−

• Chondrite-normalized REE patterns of titanite show convex

shapes from La to Sm, usually slightly negative Eu anoma-

lies and almost regularly gradual decreasing of HREE`s

from Gd to Lu.

• U–Pb SHRIMP dating of titanite yield the Variscan ages of

351.0 ± 6.5 to 337.9 ± 6.1 Ma interval (Carboniferous, late

466

UHER, BROSKA, KRZEMIŃSKA, ONDREJKA, MIKUŠ and VACULOVIČ

GEOLOGICA CARPATHICA

, 2019, 70, 6, 449–470

Tournaisian to Visean). These ages are ~ 5 to 19 Ma younger

than the primary magmatic U–Pb ages of zircon in corre-

sponding rocks (Broska et al. 2013).

• Application of Zr-in-titanite geothermometry implies

a possibly fluid-driven relatively high-temperature titanite

precipitation, ~ 650 to 750 °C at inferred pressure of 0.2 to

0.4 GPa and a(TiO

) = 0.6–1.0.

• Mineral assemblage, U–Pb age dating and geothermometry

indicate possible late-magmatic but rather early post-

magmatic (subsolidus) origin of investigated titanite.

The post- magmatic precipitation of titanite was probably

connected with a subsequent Variscan tectono-thermal event

(~ 340 ± 10 Ma), probably related with younger small granite

intrusions and increased fluid activity.

• Veinlets and replacement zones of secondary titanite in

the association of other late minerals (epidote, quartz, albite,

K-feldspar, chlorite, ilmenite, rutile and/or anatase, and

hematite) are probably products of Alpine (Cretaceous)

metamorphic overprint.

Acknowledgements:

This research was supported by

the Slovak Research and Development Agency under con-

tracts APVV-14-0278, APVV-15-0050, VEGA Agency Nos.

1/0257/13 and 1/0499/15.

Analytical assistance with the

SHRIMP IIe/MC calibration was provided by Zbigniew

Czupyt. We are grateful to Daniel Dunkley for his assistance

on the beginning analytical works on titanite and to Anna

Pietranik for procurement of the Khan titanite reference mate-

rial.

We also thank Igor Petrík (handling editor), Jolanta Burda

and Adam Pieczka (both reviewers) for their critical and con-

structive suggestions.

References

Ackerson M.R. 2011: Trace element partitioning between titanite and

groundmass in silicic volcanic systems. MSc. Thesis, University

of North Carolina, Chapel Hill, U.S.A., 1–69.

Aleinikoff J.N., Wintsch R.P., Fanning C.M. & Dorais M.J. 2002:

U–Pb geochronology of zircon and polygenetic titanite from the

Glastonbury Complex, Connecticut, USA: an integrated SEM,

EMPA, TIMS, and SHRIMP study. Chem. Geol. 188, 125–147.

Barboni M., Schoene B., Ovtchanova M., Bussy F., Schaltegger U. &

Gerdes A. 2013: Timing of incremental pluton construction and

magmatic activity in a back-arc setting revealed by ID-TIMS

U/Pb and Hf isotopes on complex zircon grains. Chem. Geol.

340, 76–83.

Barrat J.A., Zanda B., Moynier F., Bollinger C., Liorzou C. & Bayon G.

2012: Geochemistry of CI chondrites: Major and trace elements,

and Cu and Zn isotopes. Geochim. Cosmochim. Acta 83, 79–92.

Bauer J.E. 2015: Complex zoning patterns and rare earth element

varitions across titanite crystals from the Half Dome Granodio-

rite, central Sierra Nevada, California. MSc. Thesis, University

of North Carolina, Chapel Hill, 1–76.

Bea F. 1996: Residence of REE, Y, Th and U in granites and crustal

protoliths; implications for the chemistry of crustal melts.

J. Petrol. 37, 521–552.

Bernau R. & Franz G. 1987: Crystal chemistry and genesis of Nb-, V-,

and Al-rich metamorphic titanite from Egypt and Greece. Can.

Mineral. 25, 695–705.

Bezák V., Jacko S., Janák M., Ledru P., Petrík I. & Vozárová A. 1997:

Main Hercynian lithotectonic units of the Western Carpathians.

In: Grecula P., Hovorka D. & Putiš M. (Eds.): Geological evolu-

tion of the Western Carpathians. Mineralia Slovaca Monographs,

Bratislava, 261–268.

Bezák V., Biely A., Elečko M., Konečný V., Mello J., Polák M. &

Potfaj M. 2011: A new synthesis of the geological structure of

Slovakia – the general geological map at 1:200000 scale. Geol.

Quarterly 55, 1–8.

Bielik M., Šefara J., Kováč M., Bezák V. & Plašienka D. 2004:

The Western Carpathians – interaction of Hercynian and Alpine

processes. Tectonophysics 393, 63–86.

Bonamici C.E, Fanning C.M., Kozdon R., Fournelle J.H. & Walley

J.W. 2015: Combined oxygen-isotope and U–Pb zoning studies

of titanite: New criteria for age preservation. Chem. Geol. 398,

70–84.

Bónová K., Jacko S., Broska I. & Siman P. 2005: Contribution to

geochemistry and geochronology of leucogranites from Branisko

Mts. Miner. Slov. 37, 349–350 (in Slovak).

Bónová K., Broska I. & Petrík I. 2010: Biotite from Čierna Hora

Mountains granitoids (Western Carpathians, Slovakia) and esti-

mation of water contents in granitoid melts. Geol. Carpath. 61,

3–17.

Bouch J.E., Hole M.J. & Trewin N.H. 1997: Rare earth and high

strength element partitioning behaviour in diagenetically preci-

pitated titanites. Neues Jahrb. Mineral. Abh. 172, 3–21.

Broska I. & Petrík I. 2011: Accessory Fe–Ti oxides in the West-Car-

pathian I-type granitoids: witnesses of the granite mixing and

late oxidation processes. Mineral. Petrol. 102, 87–97.

Broska I. & Petrík I. 2015: Variscan thrusting in I- and S-type granitic

rocks of the Tribeč Mountains, Western Carpathians (Slovakia):

evidence from mineral compositions and monazite dating. Geol.

Carpath. 66, 455–471.

Broska I.

Uher P. 1988: Accessory minerals of granitoid rocks of

Bojná and Hlohovec blocks, the Považský Inovec Mts. Geol.

Carpath. 39, 505–520.

Broska I.

Uher P.., 2001: Whole-rock chemistry and genetic typo-

logy of the West-Carpathian Variscan granites. Geol. Carpath.

52, 79–90.

Broska I., Petrík I.

Benko P. 1997: Petrology of the Malá Fatra

granitoid rocks (Western Carpathians, Slovakia). Geol. Carpath.

48, 27–37.

Broska I., Vdovcová K., Konečný P., Siman P.

Lipka J. 2004:

Accessory titanite in the granitoids of the Western Carpathians:

distribution and composition. Miner. Slov. 36, 237–246 (in

Slovak).

Broska I., Harlov D., Tropper P.

Siman P. 2007: Formation of mag-

matic titanite–ilmenite phase relations during granite alteration

in the Tribeč Mountains, Western Carpathians, Slovakia. Lithos

95, 58–71.

Broska I., Petrík I., Be′eri-Shlevin Y., Majka J.

Bezák V. 2013:

Devonian/Mississippian I-type granitoids in the Western Car-

pathians: A subduction-related hybrid magmatism. Lithos

162–163, 27–36.

Brugger J.

Gieré R. 1999: As, Sb, Be and Ce enrichment in mine-

rals from a metamorphosed Fe–Mn deposit, Val Ferrera, Eastern

Swiss Alps. Can. Mineral. 37, 37–52.

Burda J.

Gawęda A. 2009: Shear-influenced partial melting in the

Western Tatra metamorphic complex: Geochemistry and geo-

chronology. Lithos 110, 373–385.

Burda J., Gawęda A.

Klötzli U. 2013a: Geochronology and petroge-

nesis of granitoid rocks from the Goryczkowa Unit, Tatra Moun-

tains (Central Western Carpathians). Geol. Carpath. 64, 419–435.

Burda J., Gawęda A. & Klötzli U. 2013b: U–Pb zircon age of the

youngest magmatic activity in the High Tatra granites (Central

Western Carpathians). Geochronometria 40, 134–144.

467

TITANITE FROM VARISCAN I-TYPE TONALITES TO GRANODIORITES, WESTERN CARPATHIANS

GEOLOGICA CARPATHICA

, 2019, 70, 6, 449–470

Burger A.J., von Knorring O. & Clifford T.N. 1965: Mineralogical and

radiometric studies of monazite and sphene occurrences in the

Namib Desert, South-West Africa. Mineral. Mag. 35, 519–528.

Cambel B., Kráľ J. & Burchart J. 1990: Isotopic geochronology of the

Western Carpathian crystalline complex with catalogue of data.

Veda, Bratislava, 1–184 (in Slovak with English summary).

Carichi L., Annen C., Rust A. & Blundy J. 2012: Insights into the

mechanisms and timescales of pluton assembly from deforma-

tion patterns of mafic enclaves. J. Geophys. Res. 117, B11206,

1–18.

Carswell D.A., Wilson R.N. & Zhai M. 1996: Ultra-high pressure alu-

minous titanite in carbonate-bearing eclogites at Shuanghe in

Dabieshan, central China. Mineral. Mag. 60, 461–471.

Castelli D. & Rubatto D. 2002: Stability of Al- and F-rich titanite in

metacarbonate: petrologic and isotopic constraints from a poly-

metamorphic eclogitic marble of the internal Sesia Zone (Wes-

tern Alps). Contrib. Mineral. Petrol. 142, 627–639.

Cempírek J., Houzar S. & Novák M. 2008: Complexly zoned niobian

titanite from hedenbergite skarn at Písek, Czech Republic, con-

strained by substitutions Al(Nb,Ta)Ti

-2

, Al(F,OH)(TiO)

-1

and

SnTi

-1

. Mineral. Mag. 72, 1293–1305.

Černý P., Novák M. & Chapman R. 1995: The Al(Nb,Ta)Ti

-2

substitu-

tion in titanite: the emergence of a new species? Mineral. Petrol.

52, 61–73.

Cháb J., Breiter K., Fatka O., Hladil J., Kalvoda J., Šimůnek Z.,

Štorch P., Vašíček Z., Zajíc J. & Zapletal J. 2008: Short geology

of the Bohemian Massif basement and their Carboniferous and

Permian cover. Czech Geological Survey Press, Prague, 1–284

(in Czech).

Chakhmouradian A.R. 2004: Crystal chemistry and paragenesis of

compositionally unique (Al-, Fe-, Nb-, and Zr-rich) titanite from

Afrikanda, Russia. Am. Mineral. 89, 1752–1762.

Chakhmouradian A.R., Reguir E.P. & Mitchell R.H. 2003: Titanite in

carbonatitic rocks: Genetic dualism and geochemical signifi-

cance. Period. Mineral. 72, Special Issue 1, Eurocarb workshop

Italy, 107–113.

Chambers J.A. & Kohn M.J. 2012: Titanium in muscovite, biotite,

and hornblende: Modelling, thermometry and rutile activities in

metapelites and amphibolites. Am. Mineral. 97, 543–555.

Chen Y.-X. & Zheng Y.-F. 2015: Extreme Nb/Ta fractionaction in

metamorphic titanite from ultrahigh-pressure metagranite.

Geochim.

Cosmochim. Acta 150, 53–73.

Chen Y.-X., Zhou K., Zheng Y.-F., Gao X.-Y. & Yang Y.-H. 2016:

Polygenetic titanite records the composition of metamorphic

fluids during the exhumation of ultrahigh-pressure metagranite

in the Sulu orogen. J. Metamorph. Geol. 34, 573–594.

Cherniak D.J. 2006: Zr diffusion in titanite. Contrib. Mineral. Petrol.

152, 639–647.

Chew D.M., Petrus J.A. & Kamber B.S. 2014: U–Pb LA–ICP–MS

dating using accessory mineral standards with variable common

Pb. Chem. Geol. 363, 185–199.

Coleman D.S., Gray W. & Glazner A.F. 2004: Rethinking the empla-

cement and evolution of zoned plutons: geochronologic evi-

dence for incremental assembly of the Tuolumne Intrusive Suite,

California. Geology 32, 433–436.

Colombini L.L., Miller C.F., Gualda G.A.R., Wooden J.L. &

Miller J.S. 2011: Sphene and zircon in the Highland Range vol-

canic sequence (Miocene, southern Nevada, USA): elemental

partitioning, phase relations, and influence on evolution of silic-

ic magma. Mineral. Petrol. 102, 29–50.

Della Ventura G. & Bellatreccia F. 1999: Zr- and LREE-rich titanite

from Tre Croci, Vico Volcanic complex (Latium, Italy). Mineral.

Mag. 63, 123–130.

Ferry J.M. & Watson E.B. 2007: New thermodynamic models and

revised calibrations for the Ti-in-zircon and Zr-in-rutile ther-

mometers. Contrib. Mineral. Petrol. 154, 429–437.

Finger F., Broska I., Haunschmidt B., Hraško Ľ., Kohút M., Krenn E.,

Petrík I., Riegler G. & Uher P. 2003: Electron-microprobe dating

of monazites from Western Carpathian basement granitoids: plu-

tonic evidence for an important Permian rifting event subsequent

to Variscan crustal anatexis. Int. J. Earth Sci. 92, 86–98.

Foord E.E., Hlava P.F., Erd R.C. & Lichte F.E. 1993: Rhyolite-hosted

REE–Fe–Nb-bearing titanite from Willow Spring Draw, Sierra

County, New Mexico, U.S.A. In: Rare earth minerals: chemistry,

origin and ore deposits. 1 and 2 April 1993. Abstracts. The Natu-

ral History Museum London, United Kingdom, 39–41.

Gaab A.S., Poller U., Janák M., Kohút M. & Todt W. 2005: Zircon

U–Pb geochronology and isotopic characterization for the

pre-Mesozoic basement of the Northern Veporic Unit (Central

Western Carpathians, Slovakia). Schweiz. Mineral. Petrogr. Mitt.

85, 69–88.

Gao X.-Y., Zheng Y.-F. & Chen Y.-X. 2011: U–Pb ages and trace ele-

ments in metamorphic zircon and titanite from UHP eclogite in

the Dabie orogen: constraints on P–T–t path. J. Metamorph.

Geol. 29, 721–740.

Gao X.-Y., Zheng Y.-F., Chen Y.-X. & Guo J. 2012: Geochemical and

U–Pb age constraints on the occurrence of polygenetic titanites

in UHP metagranite in the Dabie orogen. Lithos 136–139,

93–108.

Gasser D., Jeřábek P., Faber C., Stünitz, H., Menegon L., Corfu F.,

Erambert M. & Whitehouse M.J. 2015: Behaviour of geochro-

nometers and timing of metamorphic reactions during deforma-

tion at lower crustal conditions: phase equilibrium modeling and

U–Pb dating of zircon, monazite, rutile and titanite from the

Kalak Nappe Complex, northern Norway. J. Metamorph. Geol.

33, 513–534.

Gawęda A., Burda J., Klötzli U., Golonka J. & Szopa K. 2016:

Episodic construction of the Tatra granitoid intrusion (Central

Western Carpathians, Poland/Slovakia): consequences for the

geodynamics of Variscan collision and Rheic Ocean closure. Int.

J. Earth Sci. 105, 1153–1174.

Ghiorso M.S. & Evans B.W. 2008: Thermodynamics of rhombo-

hedral oxide solid solutions and a revision of the Fe–Ti two-

oxide geothermometer and oxygen-barometer. Am. J. Sci. 308,

957–1039.

Gieré R. 1992: Compositional variation of metasomatic titanite from

Adamello (Italy). Schweiz. Mineral. Petrogr. Mitt. 72, 167–177.

Glazner A.F., Bartley J.M., Coleman D.S., Gray W. & Taylor R.Z.

2004: Are plutons assembled over millions of years by amalga-

mation from small magma chambers? GSA Today 14, 4–11.

Green T.H. & Pearson N.J. 1986: Rare-earth element partitioning be-

tween sphene and coexisting silicate liquid at high pressure and

temperature. Chem. Geol. 55, 105–119.

Gromet L.P. & Silver L.T. 1983: Rare earth element distribution

among minerals in a granodiorite and their petrogenetic implica-

tions. Geochim. Cosmochim. Acta 47, 925–939.

Hayden L.A., Watson E.B. & Wark D.A. 2008: A thermometer for

sphene (titanite). Contrib. Mineral. Petrol. 155, 529–540.

Heaman L.M. 2009: The application of U–Pb geochronology to

mafic, ultramafic and alkaline rocks: an evolution of the three

mineral standards. Chem. Geol. 261, 43–52.

Higgins J.B. & Ribbe P.H. 1976: The crystal chemistry and space

groups of natural and synthetic titanites. Am. Mineral. 61,

878–888.

Holland T.J.B. & Powell R. 2011: An improved and extended inter-

nally consistent thermodynamic dataset for phases of petro-

logical interest, involving a new equation of state for solids.

J. Metamorph. Geol. 29, 333–383.

Hoskin P.W.O., Kinny P.D., Wyborn D. & Chappell B.W. 2000: Iden-

tifying accessory mineral saturation during differentiation in

granitoid magmas: an integrated approach. J. Petrol. 41,

1365–1396.

468

UHER, BROSKA, KRZEMIŃSKA, ONDREJKA, MIKUŠ and VACULOVIČ

GEOLOGICA CARPATHICA

, 2019, 70, 6, 449–470

Hovorka D. 1960: Contribution to petrography of Veporide grani-

toids. Acta Geol. Geogr. Univ. Comen. Geol. 4, 255–262

(in Slovak).

Hovorka D. & Hvožďara P. 1964: Accessory minerals of the Veporide

granitoid rocks. Acta Geol. Geogr. Univ. Comen. Geol. 9,

145–179 (in Slovak).

Jacko S. & Petrík I. 1987: Petrology of the Čierna hora Mts. granitoid

rocks. Geol. Carpath. 38, 515–544.

Janák M., Plašienka D., Frey M., Cosca M., Schmidt S.Th., Lupták B.

& Méres Š. 2001: Cretaceous evolution of a metamorphic core

complex, the Veporic unit, Western Carpathians (Slovakia): P–T

conditions and in situ

Ar/

Ar UV laser probe dating of

metapelites. J. Metamorph. Geol. 19, 197–216.

Jeřábek P., Janák M., Faryad S.W., Finger F. & Konečný P. 2008:

Polymetamorphic evolution of pelitic schists and evidence for

Permian low-pressure metamorphism in the Vepor Unit, West

Carpathians. J. Metamorph. Geol. 26, 465–485.

Johannes W. & Holtz F. 1996: Petrogenesis and experimental petrolo-

gy of granitic rocks. Springer, Berlin – Heidelberg – New York,

1–335.

Kennedy A.K., Kamo S.L., Nasdala L. & Timms N.E. 2010: Grenville

skarn titanite: potential reference material for SIMS U–Th–Pb

analysis. Can. Mineral. 48, 1423–1443.

Kinny P.D., McNaughton N.J., Fanning C.M.

Maas R. 1994:

518 Ma sphene (titanite) from the Khan pegmatite, Namibia,

southwest Africa: a potential ion-microprobe standard. Abstract,

8th International Conference on Geochronology, Cosmochrono-

logy and Isotope Geology. U.S. Geological Survey, 171. Circular

1107.

Kirkland C.L., Spaggiari C.V., Johnson T.E., Smithies R.H., Danišík

M., Evans N., Wintage M.T.D., Clark C., Spencer C., Mikucki E.

& McDonald B.J. 2016: Grain size matters: Implications for

element and isotopic mobility in titanite. Precambrian Res. 278,

283–302.

Kirkland C.L., Hollis J., Danišík M., Petersen J., Evans N.J. &

McDonald B.J. 2018: Apatite and titanite from the Karrat Group,

Greenland; implications for charting the thermal evolution of

crust from the U-Pb geochronology of common Pb bearing

phases. Precambrian Res. 300, 107–120.

Knoche R., Angel R.J, Seifert F. & Fliervoet T.F. 1998: Complete

substitution of Si for Ti in titanite Ca(Ti

1-x

)

Am. Mineral. 83, 1168–1175.

Kohn M.J. 2017: Titanite petrochronology. Rev. Mineral. Geochem.

83, 419–441.

Kohn M.J. & Corrie S.L. 2011: Preserved Zr-temperatures and U–Pb

ages of high-grade metamorphic titanite: Evidence for a static

hot channel in the Himalayan orogen. Earth. Planet. Sci. Lett.

311, 136–143.

Kohút M. & Nabelek P.I. 2008: Geochemical and isotopic (Sr, Nd

and O) constraints on sources of Variscan granites in theWestern

Carpathians. J. Geosci. 53, 307–322.

Kohút M., Kovach V.P., Kotov A.B., Salnikova E.B. & Savatenkov

V.M. 1999: Sr and Nd isotope geochemistry of Variscan

granitic rocks from the Western Carpathians – implications

for granite genesis and crustal evolution. Geol. Carpath. 50,

477–487.

Kohút M., Uher P., Putiš M., Ondrejka M., Sergeev S., Larionov N. &

Paderin I. 2009: SHRIMP U–Th–Pb zircon dating of the grani-

toid massifs in the Malé Karpaty Mountains (Western Carpa-

thians): evidence of Meso-Variscan successive S- to I-type

granitic magmatism. Geol. Carpath. 60, 345–350.

Kowallis B.J., Christiansen E.H. & Griffen D.T. 1997: Compositional

variations in titanite. Geological Society of America Abstracts

with Programs 29, A-402.

Kowallis B.J., Christiansen E.H., Dorais M., Winkel A., Henze P.,

Franzen L. & Webb H. 2018: Compositional variations of Fe, Al,

and F in titanite (sphene). Geological Society of America Annual

Meeting, Indianapolis, Indiana, USA, 2018, Paper No. 137-11.

Kroner U. & Romer R.L. 2013: Two plates – many subduction

zones: the Variscan orogeny reconsidered. Gondwana Res. 24,

298–329.

Li J.-W., Deng X.-D., Zhou M.F., Liu Y.-S., Zhao X.-F.

Guo J.-L.

2010: Laser ablation ICP-MS titanite U–Th–Pb dating of hydro-

thermal ore deposits: A case study of the Tonglushan Cu–Fe–Au

skarn deposit, SE Hubei Province, China. Chem. Geol. 270,

56–67.

Liferovich R.P. & Mitchell R.H. 2005: Solid solution of rare earth

elements in synthetic titanite: a reconnaissance study. Mineral.

Petrol. 83, 271–282.

Liferovich R.P. & Mitchell R.H. 2006: Solid solutions of niobium in

synthetic titanite. Can. Mineral. 44, 1089–1097.

Liu Y., Fan Y., Zhou T., Zhang L., Noel C., White N.C., Hong H. &

Zhang W. 2018: LA–ICP–MS titanite U–Pb dating and mineral

chemistry of the Luohe magnetite-apatite (MA)-type deposit in

the Lu-Zong volcanic basin, Eastern China. Ore Geol. Rev. 92,

284–296.

Ludwig K.R. 2003: User`s Manual for Isoplot 3.00: A Geochronolo-

gical toolkit for Microsoft Excel. Berkeley Geochron. Center

Spec. Publ. 4, Berkeley, 1–70.

Ludwig K.R. 2009: SQUID 2: A User’s Manual, rev.12 April 2009.

Berkeley Geochronology Center Special Publication 5, 1–110.

Lyakhovich V.V. 1968: Accessory minerals. Nauka, Moscow, 1–276

(in Russian).

Ma Q., Evans N.J., Ling X-X., Yang J-H., Wu F-W., Zhao Z-D. &

Yang Y-H. 2019: Natural Titanite reference materials for in

situ U–Pb and Sm–Nd isotopic measurements by LA–(MC)–

ICP–MS. Geostand. Geoanal. Res. 43, 355–384.

Mandl M., Kurz W., Hauzenberger C., Fritz H., Klötzli U. & Schuster

R. 2018: Pre-Alpine evolution of the Seckau Complex

(Austro alpine basement/Eastern Alps): Constraints from in-situ

LA-ICP-MS U–Pb zircon geochronology. Lithos 296–299,

412–430.

Markl G. & Piazolo S. 1999: Stability of high-Al titanite from low-

pressure calcsilicates in light of fluid and host-rock composition.

Am. Mineral. 84, 37–47.

Matzel J.E.P., Bowring S.A. & Miller R.B. 2006: Time scales of plu-

ton construction at differing crustal levels: Examples from the

Mount Stuart and Tenpeak intrusions, North Cascades, Washing-

ton. Geol. Soc. Am. Bull. 118, 1412–1430.

McLeod G.W., Dempster T.J. & Faithfull J.W. 2011: Deciphering

magma-mixing processes using zoned titanite from the Ross of

Mull Granite, Scotland. J. Petrol. 52, 55–82.

Michel J., Baumgartner L., Putlitz B., Schaltegger U. & Ovtcharova M.

2008: Incremental growth of the Patagonian Torres del Paine

laccolith over 90 k.y. Geology 36, 459–562.

Middleton A.W., Förster H.-J., Uysal I.T., Golding S.D. & Rhede D.

2013: Accessory phases from the Soulz monzogranite, Soultz-

sous-Forêts, France: Implications for titanite destabilisation and

differential REE, Y and Th mobility in hydrothermal systems.

Chem. Geol. 335, 105–117.

Nakada S. 1991: Magmatic processes in titanite-bearing dacites, cen-

tral Andes of Chile and Bolivia. Am. Mineral.76, 548–560.

Paterson B.A. & Stephens W.E. 1992: Kinetically induced composi-

tional zoning in titanite: implications for accessory-phase/melt

partitioning of trace elements. Contrib. Mineral. Petrol. 109,

373–385.

Paterson B.A., Stephens W.E. & Herd D.A. 1989: Zoning in granitoid

accessory minerals as revealed by backscattered electron ima-

gery. Mineral. Mag. 53, 55–61.

Paul B.J., Černý P., Chapman R. & Hinthorne J.R. 1981: Niobian

titanite from the Huron Claim pegmatite, Southeastern Manitoba.

Can. Mineral. 19, 549–552.

469

TITANITE FROM VARISCAN I-TYPE TONALITES TO GRANODIORITES, WESTERN CARPATHIANS

GEOLOGICA CARPATHICA

, 2019, 70, 6, 449–470

Perseil E.-A. & Smith D.C. 1995: Sb-rich titanite in the manganese

concentrations at St. Marcel-Praborna, Aosta Valley, Italy:

petrography and crystal-chemistry. Mineral. Mag. 59, 717–734.

Petrík I. 1980: Biotites from granitoid rocks of the West Carpathians

and their petrogenetic importance. Geol. Carpath. 31, 215–230.

Petrík I. & Broska I. 1989: Mafic enclaves in granitoid rocks of the

Tribeč Mts., Western Carpathians: geochemistry and petrology.

Geol. Carpath. 40, 667–696.

Petrík I. & Broska I. 1994: Petrology of two granite types from the

Tribeč Mountains, Western Carpathians: an example of allanite

(+ magnetite) versus monazite dichotomy. Geol. J. 29, 59–78.

Petrík I. & Kohút M. 1997: The evolution of granitoid magmatism

during the Variscan orogen in the Western Carpathians. In:

Grecula P., Hovorka D., Putiš M. (Eds.): Geological evolution

of the Western Carpathians. Miner. Slov., Monograph,

235–252.

Pieczka A., Hawthorne F.C., Ma C., Rossman G.R., Szełeg E., Szusz-

kiewicz A., Turniak K., Nejbert K., Ilnicki S.S, Buffat P. &

Rutkowski B. 2017: Żabińskiite, ideally Ca(Al

0.5

)(SiO

)O,

a new mineral of the titanite group from the Piława Górna peg-

matite, the Góry Sowie Block, southwestern Poland. Mineral.

Mag. 81, 591–610.

Poller U., Janák M., Kohút M. & Todt W. 2000: Early Variscan mag-

matism in the Western Carpathians: U–Pb zircon data from

grani toids and orthogneisses of the Tatra Mountains (Slovakia).

Int. J. Earth Sci. 89, 336–349.

Poller U., Todt W., Kohút M. & Janák M. 2001: Nd, Sr, Pb isotope

study of the Western Carpathians: implication for Palaeozoic

evolution. Schweiz. Mineral. Petrogr. Mitt. 81, 159–174.

Putiš M. 1992: Variscan and Alpidic nappe structures of the Western

Carpathian crystalline basement. Geol. Carpath. 43, 369–380.

Radziszewski P. 1924: About the Carpathian granites. Prace Polsk.

Inst. Geol. 1 (1921–1924), 97–154 (in Polish with French

summary).

Resor P.G., Chamberlain K.R., Frost C.D., Snoke A.W. & Frost B.R.

1996: Direct dating of deformation: U–Pb age of syndeforma-

tional sphene growth in the Proterozoic Laramie Peak shear

zone. Geology 24, 623–626.

Ribbe P.H. 1980: Titanite. In: Ribbe P.H. (Ed.): Orthosilicates.

Rev. Mineral. 5, 137–154.

Rubatto D. & Hermann J. 2001: Exhumation as fast as subduction?

Geology 29, 3–6.

Russell J.K., Groat L.A. & Halleran A.A.D. 1994: LREE-rich niobian

titanite from Mount Bisson, British Columbia: Chemistry and

exchange mechanisms. Can. Mineral. 32, 575–587.

Sato K., Siga O.Jr., Basel M.A.S., Tassinari C.C.G. & Onoe A.T.

2016: SHRIMP U–Th–Pb analyses of titanites: analytical tech-

niques and examples of terranes of the South-Southeast of Brazil

– Geoscience Institute of the University of São Paulo. Geol. Sér.

Cient. Univ. São Paulo 16, 3–18.

Sauerzapf U., Lattard D., Burchard M. & Engelmann R. 2008:

The tita nomagnetite–ilmenite equilibrium: new experimental data

and thermooxybarometric application to the crystallization of

basic to intermediate rocks. J. Petrol. 49, 1161–1185.

Schafarzik F. 1898: Industrial rocks of the Nitra Comitate. Földt.

Kozl. 28, 369–399 (in Hungarian).

Schaltegger U., Brack P., Ovtcharova M., Peytcheva I., Schoene B.,

Stracke A., Marocchi M. & Bargossi G.M. 2009: Zircon and

titanite recording 1.5 million years of magma accretion, crystal-

lization and initial cooling in a composite pluton (southern

Adamello batholith, northern Italy). Earth Planet. Sci. Lett. 286,

208–218.

Simonetti A., Heaman L.M., Chacko T. & Banerjee N.R. 2006: In situ

petrographic thin section U–Pb dating of zircon, monazite, and

titanite using laser ablation–MC–ICP–MS. Int. J. Mass Spectr.

253, 87–97.

Singh J. & Johannes W. 1996: Dehydration melting of tonalites.

Part I. Beginning of melting. Contrib. Mineral. Petrol. 125,

16–25.

Skublov S.G., Berezin A.V., Rizvanova N.G., Meľnik A.E. &

Myskova T.A. 2014: Multistage Svecofennian metamorphism:

Evidence from the composition and U–Pb age of titanite

from eclogites of the Belomorian mobile belt. Petrology 22,

381–388.

Speer J.A. & Gibbs G.V. 1976: The crystal structure of synthetic ti-

tanite, CaTiOSiO

, and the domain textures of natural titanites.

Am. Mineral. 61, 238–247.

Spencer K.J., Hacker B.R., Kylander-Clark A.R.C., Andersen T.B.,

Cottle J.M., Stearns M.A., Poletti J.E. & Seward G.G.E. 2013:

Campaign-style titanite U–Pb dating by laser-ablation ICP:

Implications for crustal flow, phase transformations and titanite

closure. Chem. Geol. 341, 84–101.

Stacey J.S. & Kramers J.D. 1975: Approximation of ter restrial lead

isotope evolution by a two-stage model. Earth Planet. Sci. Lett.

26, 207–221.

Stearns M.A., Hacker B.R., Ratschbacher L., Rutte D. & Kylander-

Clark A.R.C. 2015: Titanite petrochronology of the Pamir

gneiss domes: Implications for middle to deep crust exhuma-

tion and titanite closure to Pb and Zr diffusion. Tectonics 34,

784–802.

Stepanov A.V., Bekenova G.K., Levin V.L. & Hawthorne F.C. 2012:

Natrotitanite, ideally (Na

0.5

)Ti(SiO

)O, a new mineral from

the Verkhnee Espe deposit, Akjailyautas Mountains, Eastern

Kazakhstan district, Kazakhstan: description and crystal struc-

ture. Mineral. Mag. 76, 37–44.

Sun J.F., Yang J.H., Wu F.Y., Xie L.W., Yang Y.H., Liu Z.C. & Li X.H.

2012: In situ U–Pb dating of titanite by LA-ICPMS. Chin. Sci.

Bull. 57, 2506–2516.

Thöni M., Petrík I., Janák M. & Lupták B. 2003: Preservation of

Variscan garnet in Alpine metamorphosed pegmatite from

the Veporic Unit, Western Carpathians: Evidence from Sm–Nd

isotope data. J. Czech Geol. Soc. 48, 123–124.

Tilton G.R. & Grünenfelder M.C. 1968: Sphene: Uranium-lead ages.

Science 159, 1458–1461.

Uher P. & Broska I. 1995: Pegmatites in two suites of Variscan oro-

genic rocks (Western Carpathians, Slovakia). Mineral. Petrol.

55, 27–36.

Uher P. & Broska I. 1996: Post-orogenic Permian granitic rocks in the

Western Carpathian-Pannonian area: Geochemistry, mineralogy

and evolution. Geol. Carpath. 47, 311–321.

Uher P., Černý P., Chapman R., Határ J. & Miko O. 1998: Evolution

of Nb-Ta minerals in the Prašivá granitic pegmatites, Slovakia:

II. External hydrothermal Pb, Sb overprint. Can. Mineral. 36,

535–545.

Uher P., Kohút M., Ondrejka M., Konečný P. & Siman P. 2014:

Monazite-(Ce) in Hercynian granites and pegmatites of the

Bratislava Massif, Western Carpathians: Compositional varia-

tions and Th–U–Pb electron-microprobe dating. Acta Geol. Slov.

6, 215–231.

Vlasov K.A., Sindeyeva N.D., Serdyuchenko D.P., Eshkova Je. M.,

Kuzmenko M.V. & Pyatenko Ju.A. 1964: Geochemistry,

mine ralogy and genetic types of rare-element deposits. Part II.

Mine

ralogy of rare elements. Nauka, Moscow, 1–832 (in

Russian).

Vuorinen J.H. & Hålenius U. 2005: Nb-, Zr- and REE-rich titanite

from the Alnö alkaline complex: Crystal chemistry and its

impor tance as a petrogenetic indicator. Lithos 83, 128–142.

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.

Wones D.R. 1989: Significance of the assemblage titanite + magne-

tite + quartz in granitic rocks. Am. Mineral. 74, 744–749.