GeolCarp_Vol66_No2_83

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Introduction

With the advent of sophisticated microanalytical techniques in
the last decades, many heavy mineral provenance studies be-
came geochemically oriented. A large range of detrital heavy
mineral  species,  including  garnets,  chromian  spinel,  tourma-
lines,  amphiboles,  pyroxenes,  zircon,  apatites,  ilmenite  and
rutile, has been subjected to geochemical analyses (for review,
see Mange & Morton 2007). Among them, garnet geochemis-
try  has  turned  to  be  the  most  widely  used  mineral-chemical
tool for determination and discrimination of sediment prove-
nance  because  garnet  is  a common  member  of  many  heavy
mineral  assemblages  and  is  a relatively  stable  mineral  under
both  weathering  and  burial  diagenetic  conditions  (Morton  &
Hallsworth  1999,  2007).  Moreover,  the  garnets  show  a wide
range in major element compositions depending on the litho-
logy of the parent rocks. Likewise, chemical compositions of
tourmaline-supergroup  minerals  vary  in  a  wide  range,  which
also  makes  them  ideal  minerals  for  geochemical  discrimina-
tion  of  provenance.  Henry  &  Guidotti  (1985)  and  Henry  &
Dutrow  (1992)  demonstrated  that  tourmaline  geochemistry
reflects very well the local environment in which the mineral
developed.  Specifically,  they  showed  that  the  Al—Fe

total

—Mg

and the Ca—Fe

total

—Mg ternary diagram enable us to distinguish

tourmalines from a variety of rock types. This important find-
ing enhanced the application of tourmaline geochemistry in
provenance studies (e.g. von Eynatten & Gaupp 1999; Nasci-
mento et al. 2007; Morton et al. 2011, 2013; Jian et al. 2013).

The provenance of the Permian sandstones from the

Malužiná Formation in the Malé Karpaty Mts (Hronicum

Provenance of the Permian Malužiná Formation sandstones

(Malé Karpaty Mountains, Western Carpathians): evidence

of garnet and tourmaline mineral chemistry

MAREK VĎAČNÝ

and PETER BAČÍK

Geological Institute, Slovak Academy of Sciences, Branch: Ďumbierska 1, 974 01 Banská Bystrica, Slovak Republic; vdacny@savbb.sk

Comenius University in Bratislava, Faculty of Natural Sciences, Department of Mineralogy and Petrology, Mlynská dolina G,

842 15 Bratislava, Slovak Republic; bacikp@fns.uniba.sk

(Manuscript received September 9, 2014; accepted in revised form March 12, 2015)

Abstract: The chemistry of detrital garnets (almandine; spessartine-, grossular-, and pyrope-rich almandine; andradite)
and mostly dravitic tourmalines from three sandstone samples of the Permian Malužiná Formation in the northern part of
the Malé Karpaty Mts (Western Carpathians, SW Slovakia) reveals a great variability of potential source rocks. They
comprise (1) low-grade regionally metamorphosed rocks (metacherts, blue schists, metapelites and metapsammites),
(2) contact-thermal metamorphic calcareous rocks (skarns or rodingites), (3) garnet-bearing mica schists and gneisses
resulting from the regional metamorphism of argillaceous sediments, (4) amphibolites and metabasic sub-ophiolitic rocks,
(5) granulites, (6) Li-poor granites and their associated pegmatites and aplites as well as (7) rhyolites. Consequently, the
post-Variscan, rift-related sedimentary basin of the Malužiná Formation originated in the vicinity of a low- to high-grade
crystalline basement with granitic rocks. Such lithological types of metamorphic and magmatic rocks are characteristic for
the Variscan terranes of the Central Western Carpathians (Tatricum and Veporicum Superunits).

Key words:

Permian, Western Carpathians, detrital heavy minerals, Hronicum Unit.

Unit, Western Carpathians, Slovakia) has already been inves-
tigated several times. However, previous provenance studies
on  the  Malužiná  Formation  sandstones  concentrated  mainly
on either petrography of major framework grains and modal
analysis of detrital framework components (Vnačný 2013) or
on bulk rock geochemistry (Vnačný et al. 2013). Both modal
and  bulk  rock  analyses,  however,  produce  only  an  overall
composition  of  the  source  rocks  and  cannot  determine  if
within-sample  provenance  mixing  took  place  (c.f.  Cawood
1991).  On  the  other  hand,  the  mineral  chemistry  of  detrital
heavy  minerals  documents  not  only  within-sample  prove-
nance mixing but also provides more detailed information on
source rock characteristics (Asiedu et al. 2000). In addition,
data obtained from mineral chemistry of derived detrital con-
stituents can be directly compared with those from potential
source terranes.

Accordingly, the main objective of this study was to ob-

tain  more  specific  information  on  the  lithology  of  potential
parent  source  rocks  for  the  Malužiná  Formation  sandstones
from the Malé Karpaty Mts by examining the chemical com-
position  of  the  detrital  garnets  and  tourmalines.  Moreover,
this study brings a more detailed picture about the paleogeo-
graphical setting of the Malužiná Formation sandstones.

General geology

For the present study, we collected sandstone samples

from the Malužiná Formation of the Ipoltica Group, situated
in the Hronicum Unit in the northern part of the Malé Kar-

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paty  Mts  (Fig. 1).  The  type  profile  of  the  Malužiná  Forma-
tion is located in the Ipoltica valley and is completed by data
from the Malužiná valley in the Nízke Tatry Mts (Vozárová
& Vozár 1981). The Malužiná Formation attains regional ex-
tent in the basal part of the Hronicum Unit; its thickness at-
tains up to 2200 m, as calculated from some outcrops in the
Nízke Tatry Mts and from borehole data in the basement of
the  Middle  Slovakian  neovolcanic  area  (Vozárová  &  Vozár
1981,  1988).  The  lower  boundary  towards  the  lower  Nižná
Boca Formation (a part of the Ipoltica Group) is lithological.
The  upper  boundary  is  again lithological  towards  the  sedi-
ments of the Lower Triassic age situated above the Malužiná
Formation concordantly without sedimentary interruption.

As concerns the lithology (Fig. 2), the main features of the

Malužiná Formation include: (1) an internal arrangement into
three megacycles; (2) presence of synchronous volcanite lay-
ers and bodies of basic to intermediate composition and of
slight to pronounced tholeiitic chemistry (Vozár 1977, 1997;
Dostal et al. 2003) in the first and third megacycles; and (3) a
variegated colour of sediments ranging from red, brown, vio-
let, grey to whitish-grey (Vozárová & Vozár 1981, 1988).

In the Malužiná Formation, the amount of coarse detrital

constituents is higher when compared with the Nižná Boca
Formation (Fig. 2). Coarse sandstone to conglomerate layers

constitute the basal parts of all three megacycles. Single beds
are well developed with graded bedding at the base, but pla-
nar to laminar bedding in the upper parts.

The middle portions of single megacycles reveal a cyclical

internal structure in which medium- to coarse-grained clas-
tics predominate. Commonly, single cycles are asymmetrical
and composed of sandstone, aleurolite to aleuropelite. Shale
to aleurolite intraclasts occur here frequently (Vozárová &
Vozár 1981).

The upper portions of megacycles have again cyclical in-

ternal structures mainly made of fine sediments. Laminar to
horizontal  stratification  prevails  in  aleurite  to  aleuropelite
rocks. Layers with carbonate concretions together with gyp-
sum  to  anhydrite  lenses  (Drnzík  1969;  Novotný  &  Badár
1971) occur mostly in the upper parts of the first and second
megacycles  (Fig. 2).  Organic  hieroglyphs  were  observed
there as well.

The Malužiná Formation ranges from the Early to the Late

Permian age (Planderová 1973; Planderová & Vozárová
1982). This was also corroborated by the

206

Pb/

238

U and

207

Pb/

235

U dating. An age of 263 ± 11 Ma was documented

from  uranium-rich  layers  of  the  upper  part  of  the  second
megacycle  (Rojkovič  1997).  Clastic  micas  from  sandstones
of  the  second  megacycle,  which  were  analysed  by  the

Fig. 1. Schematic geological map of the Upper Paleozoic rocks of the Hronicum Unit in the Malé Karpaty Mts (after Vozárová & Vozár 1988).
Sampling localities of sandstone samples collected south-west of Smolenice are indicated. Explanations: 1 – Quaternary sediments, 2 – Ter-
tiary sediments. Hronicum Unit—Šturec Nappe: 3 – Middle and Upper Triassic – carbonates, undivided, 4 – Lower Triassic – quartz
sandstones, shales, 5 – Late Paleozoic—Permian – andesites, basalts, and volcanoclastics (Malužiná Formation), 6 – Late Paleozoic—
Permian – conglomerates, sandstones, shales with volcanigenic material admixture (Malužiná Formation), 7 – Late Paleozoic—
Stephanian – grey conglomerates, sandstones, shales (Nižná Boca Formation). Krížna Nappe: 8 – Mesozoic, undivided. Others: 9 – foliation
cleavage, 10 – faults, 11 – overthrusts, 12 – overthrust line of nappes.

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Ar/

Ar method, revealed 342 ± 3 Ma as the age of cooling

of the source area (Vozárová et al. 2005).

The sedimentary environment was of a deltaic to lacustrine

character  (Vozárová  &  Vozár  1981,  1988;  Vozárová  et  al.
2009). Considerable size of the water reservoir with higher sa-
linity  is  indicated  by  the  preserved  sedimentary  structures,
overwhelming turbidite sandstone layers, organic hieroglyphs
and chemogenous layers. Synsedimentary tectonic activity con-
centrated  to  movements  along  the  subvertical  faults  confining
the sedimentary domains. Further, this activity was connected
with rifting movements in the basinal centers, which is reflected
by  the  megacyclic  internal  structure  of  the  Malužiná  Forma-
tion with mostly coarse detrital sediments in the basal portions
of single megacycles as well as by the repeated extrusions that
produced volcanic layers (Vozárová & Vozár 1981, 1988). In
the palinspastic picture of Variscan basins of the Western Car-
pathians, the Upper Paleozoic sediments of the Hronicum Unit
reveal typical features of basins created by the rifting tectonic
regime along the southern periphery of the Variscan orogenic
belt (Vozárová & Vozár 1981, 1988).

Petrographic composition of the sampled

sandstones

Detrital garnets and tourmalines were studied in three

sandstone samples. All came from the third megacycle of the
Malužiná Formation (Fig. 2). These three sandstone samples
have  a low  primary  matrix  content,  spanning  the range  of
0.4—5.6 %.  The  dominant  detrital  components  are  quartz
grains,  whereby  monocrystalline  (29.8—53.2 %)  prevails
over  polycrystalline  (8.6—13.6 %)  quartz.  Thus,  the  ratio  of
monocrystalline to polycrystalline quartz varies from 2.2 to
6.2.  The  fragments  of  potassium  feldspars  (K)  and  plagio-
clases (P) are in similar amounts, causing the K/P ratio to os-
cillate around 1 (K/P = 0.8—1.3). The content of clastic mica
in  the  sandstones  is  negligible,  ranging  from  0  to  0.8 %.
Likewise, the content of metamorphic rock fragments is com-
paratively  uniform,  varying  only  slightly  from  2.6  to  3.2 %.
On  the  other  hand,  the  content  of  volcanic  (0.2—16.2 %)
and  sedimentary  (0.4—5.0 %)  lithic  fragments  varies  more
distinctly.

The composition of heavy mineral assemblages is as fol-

lows:  apatite  (2.5—25.0 %),  biotite  (3.2—17.5 %),  garnet
(13.7—15.9 %),  hematite,  ilmenite  and  magnetite  (4.4—
67.3 %), titanite (5.3—26.3 %), tourmaline (3.2—24.8 %), and
zircon  (2.8—8.0 %).  The  zircon-tourmaline-rutile  (ZTR)  in-
dex  (Hubert  1962)  varies  from  20.2  to  42.1 %.  These  com-
paratively  low  ZTR  index  values  indicate  mineralogical
immaturity of the sampled sandstones.

Analytical techniques

In three sandstone samples 10-VD, 12-VD, and 17-VD,

detrital  garnet  and  tourmaline  crystals  were  separated  from
heavy  mineral  concentrates  obtained  from  crushed  rock  us-
ing  standard  procedures  described  by  Mange  &  Maurer
(1992).  These  procedures  included  sieving  to  obtain  the

Fig. 2. Schematic lithostratigraphical subdivision of the Ipoltica
Group (Vozárová & Vozár 1981) with approximate indication of the
places of sampling (marked by an arrow).

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0.063—0.250 mm fraction, separation in heavy liquid (bro-
moform of D = 2.8 g/cm

) and finally hand picking of indi-

vidual grains. Acquired garnets and tourmalines were then
mounted in epoxy resin, polished and coated with carbon for
electron microprobe analysis (EMPA).

The EMPA was carried out using a Cameca SX-100 elec-

tron microprobe at the Department of Electron Microanalysis
at the State Geological Institute of Dionýz Štúr in Bratislava
(Slovak Republic). The apparatus is equipped with four wave-
length-dispersive mode spectrometers. During the procedure
an accelerating voltage of 15 kV, a beam current of 20 nA and
a beam focussed to 5 µm were used. The following standards
and measured lines were used: orthoclase (Si K

α, K Kα),

TiO

(Ti K

α), Al

(Al K

α), metallic Cr (Cr Kα), fayalite

(Fe K

α), rhodonite (Mn Kα), metallic Ni (Ni Kα), forsterite

Fig. 3. Representative back-scattered electron (BSE) images of garnets (Grt) from the sandstone samples 12-VD and 17-VD. a – A grain
with inclusion of rutile (Rt), b – A grain with thin regular dark zones, c – A split grain filled with chlorite (Chl), d – A grain with dark
inclusions of quartz (Qz).

(Mg K

α), wollastonite (Ca Kα), albite (Na Kα), LiF (F Kα),

and NaCl (Cl K

α). Raw data were processed using the Quan-

tiview  software  provided  by  Cameca  and  the  PAP  routine
was  used  for  data  correction.  A total  of  45  garnets  in  three
samples (10-VD, 12-VD, and 17-VD) and 29 tourmalines in
two samples (10-VD and 12-VD) were analysed in this study
using  single-spots.  One  to  three  spots  per  grain  were  ran-
domly placed in the grain core parts.

The garnet crystal-chemical formula calculation was based

on 8 cations. The Fe

/Fe

proportion was calculated from

the charge-balanced formula. The tourmaline crystal-chemi-
cal formulae were calculated on the basis of 15Y + Z + T cat-
ions, Fe

/Fe

proportion and

2—

were obtained from the

charge-balanced formula, OH was calculated as OH = 4—F—
Cl—

O apfu (atoms per formula unit), B = 3 apfu.

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Results

Chemical composition and features of garnets

Garnets in the sandstone samples studied are subhedral to an-

hedral, up to 200 µm in size (Fig. 3). They do not display any
inherited cores or overgrowth marginal zones. However, some of
them contain inclusions of quartz, rutile, apatite, and muscovite.

The majority of garnets have almandine composition, with a

predominance  of  the  spessartine  component  only  in  a  single
garnet  grain  in  the  12-VD  sample  and  two  crystals  in  the
17-VD showing andradite composition (Table 1, Fig. 4). The
dominant  almandine  component  varies  between  62  and
68 mol % in the 10-VD sample, 37 and 80 mol % in the 12-VD
sample and attains 52 to 74 mol % in the 17-VD sample. If we
exclude rare andradite compositions, spessartine is usually the
second most abundant component in the majority of the stud-
ied garnet grains. It achieves 22 mol % in 10-VD, 39 mol % in
12-VD, and 30 mol % in 17-VD. The grossular component is
relatively  abundant  in  12-VD  (up  to  26 mol %)  and  17-VD
(

≤32 mol %), while it is very low in 10-VD (≤1.9 mol %).

The pyrope component is mostly enriched in the 12-VD sam-

Fig. 4. Classification diagram of garnets (n = 45) from the sand-
stones studied based on the end-member component proportions.

Table 1: Representative electron microprobe analyses of detrital garnets from the Malužiná Formation sandstones.

Sample

10-VD 10-VD 12-VD 12-VD 12-VD 17-VD 17-VD 17-VD

Analysis

no. 7 9 6 19

29 5 6 14

SiO

36.38

36.72

37.48

38.92

37.09

36.10

37.43

34.14

TiO

0.03 0.03 0.02 0.08 0.11 0.03 0.19 0.00

21.08 21.02 21.42 22.50 20.97 20.97 21.33 0.00

0.00 0.03 0.03 0.17 0.03 0.00 0.01 0.00

2.50 2.24 0.91 1.63 1.26 2.41 0.76

32.08

FeO

26.93

29.58

35.21

20.39

27.48

26.75

32.99

0.00

MnO

9.63 5.04 0.74 0.56

10.75

11.19 1.78 0.44

MgO

3.19 3.69 3.73 8.68 2.40 1.93 3.18 0.00

NiO

0.00 0.02 0.00 0.00 0.00 0.00 0.00 0.00

CaO

0.91 1.97 1.55 7.95 1.33 1.12 3.31

32.75

0.00

0.03

0.05

0.00

0.02

0.05

0.03

Total

100.68 100.36 101.14 100.89 101.43 100.55 101.04 99.44

2.923 2.940 2.973 2.942 2.968 2.927 2.971 2.911

0.077 0.060 0.027 0.058 0.032 0.073 0.029 0.000

0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.089

ΣZ

3.000 3.000 3.000 3.000 3.000 3.000 3.000 3.000

0.002

0.001

0.005

0.007

0.002

0.011

0.000

1.920 1.924 1.976 1.946 1.945 1.930 1.967 0.000

0.000 0.002 0.002 0.010 0.002 0.000 0.000 0.000

0.078 0.073 0.021 0.039 0.047 0.068 0.021 1.970

0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.030

ΣY

2.000

0.073 0.062 0.033 0.053 0.029 0.079 0.025 0.000

1.810 1.981 2.336 1.289 1.839 1.814 2.190 0.000

0.656 0.342 0.050 0.036 0.729 0.768 0.119 0.001

0.382 0.441 0.441 0.978 0.286 0.234 0.376 0.001

0.000

0.001

0.000

0.079 0.169 0.132 0.644 0.114 0.098 0.282 2.993

0.000 0.004 0.008 0.000 0.003 0.007 0.008 0.005

ΣX

3.000 3.000 3.000 3.000 3.000 3.000 3.000 3.000

Pyrope

12.57 14.71 14.74 32.62 9.55 7.80 12.57 0.02

Spessartine

21.59

11.42

1.66

1.19

24.31

25.65

3.99

0.05

Almandine

61.85 68.10 79.12 44.38 61.83 63.02 73.34 0.00

Andradite

3.83 3.63 1.04 1.97 2.36 3.39 1.05

98.66

Uvarovite

0.00 0.08 0.08 0.52 0.08 0.00 0.02 0.00

Schorlomite

0.16 0.12 0.07 0.35 0.50 0.15 0.69 0.00

Grossular

0.00 1.93 3.29

18.97 1.37 0.00 8.34 1.27

100.00

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ple in which it exhibits a range of 5.8 to 33 mol %. Garnets in
the 10-VD sample have a medium content of pyrope compo-
nent  between  9.4  and  15 mol %,  whereas  in  almandine  crys-
tals  of  the  17-VD  sample,  the  pyrope  constituent  ranges
between  3.6  and  13 mol %.  The  content  of  andradite  end-
member is typically low (

≤4 mol %) with an exception of an-

dradite-dominant grains in the 17-VD sample. Moreover, it
reaches up to 6.2 mol % in 10-VD and 12-VD and is enriched
only in a single almandine grain in the 17-VD sample having
19 mol %, although it usually does not exceed 4 mol % in this
sample. The proportion of other components, such as uvaro-
vite and schorlomite, is lower than 0.5 mol %.

The chemical composition of garnets is controlled by sub-

stitutions of cations in the X site. The most abundant Fe

cation is substituted mostly by Mn

but also by Ca

and

. However, there is no general substitution trend present

for all the analysed garnets. Aluminium is the vastly domi-
nant cation in the Y site and is substituted by Fe

only insig-

nificantly with an exception of andradite-enriched garnets.
The andradite-dominant composition is the result of
CaFe

(Fe

, Mn, Mg)

—1

substitution.

To summarize, three major garnet groups and two minor

garnet groups can be recognized from the chemical composi-
tion of the studied garnet grains. The major groups are al-

Table 2: Representative electron microprobe analyses of detrital tourmalines from the Malužiná Formation sandstones.

*OH = 4—F—Cl—

O apfu, B = 3 apfu.

Sample

10-VD 10-VD 10-VD 10-VD 12-VD 12-VD 12-VD 12-VD

Analysis

no.

1 2 5 13 4 18 33 37

SiO

36.15

36.63

35.97

35.78

36.87

37.02

37.26

36.52

TiO

0.83 0.53 0.75 0.45 0.47 0.70 0.69 0.14

10.57 10.55 10.47 10.27 10.55 10.69 10.67 10.61

32.86 32.09 33.47 29.02 32.24 32.51 32.31 32.12

0.08 0.00 0.02 0.01 0.02 0.02 0.09 0.00

0.00 0.00 0.00 0.31 0.00 0.00 0.00 0.00

FeO

4.22 5.96 6.77

12.67 8.89 6.20 4.49 7.61

MnO

0.01

0.00

0.03

0.00

0.07

0.00

MgO

8.13 7.51 5.79 4.99 5.56 7.49 8.30 7.20

NiO

0.00 0.01 0.00 0.00 0.02 0.01 0.03 0.00

CaO

1.00 0.47 0.47 0.22 0.26 0.64 1.31 0.12

1.98 2.25 1.86 2.62 2.02 2.19 2.00 2.62

0.02 0.02 0.02 0.02 0.02 0.01 0.02 0.02

3.22 3.35 3.19 3.54 3.39 3.35 3.11 3.58

0.00

0.01 0.00 0.01 0.01 0.01 0.01 0.00 0.02

O=F

0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00

O=Cl

0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00

Total

99.08 99.35 98.83 99.91 100.38

100.84

100.29

100.57

5.944 6.036 5.974 6.057 6.075 6.021 6.069 5.982

0.056 0.000 0.026 0.000 0.000 0.000 0.000 0.018

ΣT

6.000 6.036 6.000 6.057 6.075 6.021 6.069 6.000

3.000 3.000 3.000 3.000 3.000 3.000 3.000 3.000

5.990 6.000 5.997 5.790 5.998 5.997 5.989 6.000

0.010 0.000 0.003 0.001 0.002 0.003 0.011 0.000

0.000 0.000 0.000 0.209 0.000 0.000 0.000 0.000

ΣZ

6.000 6.000 6.000 6.000 6.000 6.000 6.000 6.000

0.102

0.066

0.094

0.057

0.059

0.085

0.017

0.323 0.231 0.529 0.000 0.264 0.234 0.215 0.183

0.000 0.000 0.000 0.040 0.000 0.000 0.000 0.000

0.580 0.821 0.940 1.794 1.225 0.843 0.612 1.042

0.002 0.000 0.005 0.000 0.009 0.001 0.000 0.000

1.992 1.845 1.433 1.051 1.365 1.815 2.016 1.757

0.000 0.001 0.000 0.001 0.003 0.001 0.004 0.000

ΣY

3.000

2.964

3.000

2.943

2.925

2.979

2.931

3.000

0.177 0.083 0.084 0.039 0.046 0.111 0.229 0.022

0.633 0.717 0.600 0.859 0.645 0.691 0.633 0.833

0.004 0.004 0.003 0.004 0.003 0.002 0.004 0.005

ΣX

0.813 0.805 0.688 0.902 0.695 0.804 0.866 0.860

0.187 0.195 0.312 0.098 0.305 0.196 0.134 0.140

0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000

0.002 0.000 0.003 0.002 0.003 0.001 0.000 0.005

0.461 0.323 0.462 0.000 0.272 0.361 0.618 0.081

3.537 3.677 3.535 3.998 3.725 3.638 3.382 3.914

ΣV+W

4.000 4.000 4.000 4.000 4.000 4.000 4.000 4.000

Σcations

18.813 18.805 18.688 18.902 18.695 18.804 18.866 18.860

ΣAl

6.369 6.231 6.552 5.790 6.261 6.231 6.204 6.201

Mg/Fe

3.433

2.248

1.524

0.703

1.114

2.152

3.292

1.686

Na/Ca

3.583 8.626 7.139

21.887 14.033 6.209 2.762

38.056

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mandine, spessartine-rich almandine, and grossular-rich al-
mandine garnets. They may be accompanied by two minor
groups: pyrope-rich almandine and andradite garnets.

Chemical composition and features of tourmalines

Tourmalines in the sandstones form euhedral to subhedral

prismatic crystals up to 200 µm in size (Fig. 5). Similarly to gar-
nets, tourmalines also do not exhibit any inherited cores or
overgrowth marginal zones.

Tourmalines from the 10-VD and 12-VD samples (Table 2)

belong to the alkali group of tourmalines with dravitic compo-
sition (Fig. 6a,b). The atomic Fe

/(Fe

+ Mg) ratio is similar

in  both  samples  (Table 2)  varying  in  the  range  of  0.22—0.34
and 0.23—0.47 in the 10-VD and 12-VD samples, respectively.
Only  one  tourmaline  crystal  in  the  10-VD  sample  shows
schorlitic  composition  attaining  the  Fe

/(Fe

+ Mg) ratio of

0.63 (Fig. 6b). Tourmalines in the 10-VD sample are generally
more  alkali-deficient  with  the  X-site  vacancy  proportion  be-
tween 0.1 and 0.3 than in 12-VD with the X-site vacancy usu-
ally  between  0.1  and  0.2,  except  for  one  analysis  in  a single
tourmaline grain with 0.3 (Table 2, Figs. 6 and 7a). Likewise,
10-VD  is  enriched  in  Al  with  its  content  between  6.2  and
6.6 apfu with an exception of schorlitic tourmaline (5.8 apfu),

Fig. 5. Representative back-scattered electron (BSE) images to doc-
ument the shape and size of two tourmaline grains from the sand-
stone sample 12-VD.

while in 12-VD Al attains only up to 6.3 apfu (Table 2). The
increase in vacancy and Al slightly shifts composition to the
magnesio-foitite end-member (Fig. 7a). The composition of
tourmaline is mainly controlled by the exchange of Fe

for

(Fig. 7b). Moreover, both cations are mutually involved

"AlNa

—1

(Mg, Fe

)

—1

(Fig. 7c) and NaAlCa

—1

(Mg, Fe

)

—1

(Fig. 7d) substitutions. However, the

"AlNa

—1

(Mg, Fe

)

—1

mechanism has a better correlation which suggests that the
change in charge after the substitution of Al for Mg and Fe

is balanced preferentially by an increase in vacancy in the
X-site rather than by the substitution of Na

for Ca

which is

typical for Al enriched compositions.

Fig. 6.  Classification  diagrams  of  tourmalines  (n = 29)  from  the
sandstones.  a  –  Classification  into  mineral  groups  based  on  the
X-site  occupancy (Hawthorne & Henry 1999), b – Classification
into  generalized  mineral  species  based  on  the  X-site  vacancy  and
Fe

/(Fe

+ Mg) proportion (Henry et al. 2011).

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Among minor elements, the tourmalines studied are slightly

enriched in Ti attaining 1.2 wt. %, 0.15 apfu, and Ca (up to
1.3 wt. %, 0.23 apfu) (Table 2). All other minor elements in-
cluding F and Cl are negligible, typically near or below the
detection limit of EMPA.

Discussion

Provenance of garnets

Garnets are common accessory minerals in various source

rocks and their compositions are controlled by P/T condi-

tions  as  well  as  the  lithology  and  chemical  composition  of
the  parent  rock,  although  some  overlaps  among  garnets  oc-
curring in different rocks have been recognized (e.g. Asiedu
et  al.  2000).  The  garnets  are  widespread  in  numerous  types
of metamorphic rocks, but are also found in acid to interme-
diate volcanic rocks, granites and pegmatites, peridotites and
kimberlites  (e.g.  Deer  et  al.  1997  and  references  therein).
Further, they occur in the form of detrital grains in sediments
(Suggate & Hall 2014).

Garnets with the predominant almandine end-member may

crystallize under different conditions, from granitic melts to
metamorphic rocks of amphibolite to granulite facies (Deer et
al. 1997). Therefore, the interpretation of provenance of al-

Fig. 7. Diagrams determining substitution trends in the tourmalines (n = 29) from the sandstones. Solid black lines represent an ideal trend of
substitution, while dashed grey lines represent an actual trend of substitution. a – X-site vacancy vs. octahedral Al diagram with substitution
vectors (Bačík et al. 2008), b – MgFe

—1

substitution, c –

"AlNa

—1

(Mg, Fe

)

—1

substitution, d – NaAlCa

—1

(Mg, Fe

)

—1

substitution.

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Deer  et  al.  1997).  In  metamorphic  rocks,  spessartine-rich
almandine  garnets  are  known  to  originate  from  low-grade
regionally  metamorphosed  rocks  such  as  metapelites,  meta-
cherts, and blue schists (Takeuchi et al. 2008). The spessar-
tine-rich  almandine  garnets  from  the  Malužiná  Formation
sandstones  were  presumably  derived  from  metamorphic
rocks, but eventually also from leucogranites or pegmatites.
The  above-mentioned  metapelites,  metacherts,  and  blue
schists  as  well  as  leucogranites  and  pegmatites  may  be
good candidates for source rocks of these spessartine-rich al-
mandine  garnets.  Consequently,  the  origin  of  detrital  spes-
sartine-rich almandine garnets could be presumably derived
from low-P/T metamorphic rocks such as contact-metamor-
phic rocks and felsic igneous rocks.

Complete grossular-almandine solid solution occurs at

high pressure (Hariya & Nakano 1972; Takeuchi et al.
2008). Grossular-rich almandine garnet actually occurs in
high-P/T crystalline schists (Tsujimori et al. 2000; Takeuchi
et al. 2008). In this regard, the grossular-rich almandine gar-
nets from the Malužiná Formation sandstones are considered
to have been derived from high-P/T metamorphic rocks.

For garnets forming under high-grade metamorphic condi-

tions an increase of the pyrope end-member is characteristic
(Miyashiro 1953, 1973; Sturt 1962; Nandi 1967; Miyashiro
& Shido 1973; Oszczypko & Salata 2005). Therefore, high-
pyrope content almandine garnets occur in epidote-amphibo-
lite to granulite facies gneisses (Miyashiro 1953; Coleman et
al.  1965;  Takeuchi  et  al.  2008).  Hence,  the  detrital  pyrope-
rich  almandine  garnets  of  the  Malužiná  Formation  sand-
stones  may  have  been  derived  from  schists  and  gneisses
resulting  from  the  regional  metamorphism  of  argillaceous
sediments. On the other hand, garnet peridotites and associ-
ated eclogites can be excluded as possible source rocks due
to the low  ( < 50 %) pyrope component in the studied pyrope-
rich  almandine  garnets  (Coleman  et  al.  1965;  Deer  et  al.
1992; von Eynatten & Gaupp 1999).

Andradite garnet typically occurs mainly in contact or ther-

mally metamorphosed impure calcareous sediments. More-
over, the higher oxidation state of skarns, alpine serpentinites,
and some alkaline igneous rocks produces andradite-rich gar-
nets (Deer et al. 1997; Takeuchi et al. 2008). Thus, detrital an-
dradite garnets from the Malužiná Formation sandstones
might have been derived from such thermally metamorphosed
impure calcareous and/or skarn-like rocks.

Suggate & Hall (2014) discussed a large garnet composi-

tional database compiled from the literature and showed how
useful  such  data  could  be  in  identifying  the  provenance  of
detrital  garnets.  These  authors  calculated  the  six  principal
garnet  end-member  compositions  (pyrope,  almandine, spes-
sartine, uvarovite, grossular, and andradite), devised a multi-
stage  methodology  to  match  garnet  compositions  to  source
rocks, and identified a series of garnet provenance fields on
ternary  plots.  Using  Suggate  &  Hall’s  approach,  we  found
out  that  the  detrital  garnets  from  the  Malužiná  Formation
sandstones  were  very  likely  derived  from  amphibolites  and
metabasic  sub-ophiolitic  rocks,  but  derivation  from  granu-
lites, blueschists, and granites cannot be excluded. Two gar-
net  grains  with  andradite  composition  can  be  related  to
calc-silicates, skarns, and rodingites (Fig. 8).

According to the discussion above, the garnets analysed

may have been derived from a variety of rock types. The ad-
ditional petrographic and geochemical information available
for the Malužiná Formation sandstones (Vozárová & Vozár
1988; Vnačný 2013; Vnačný et al. 2013), does not enable us
to unambiguously exclude any of the aforementioned rock
types as sources of the garnets.

Provenance of tourmalines

Tourmalines are the most usual B-bearing minerals in the

Earth’s crust. However, they accumulate in B-enriched rocks
such  as  felsic  intrusive  rocks  with  average  contents  of  10  to
30 ppm  B  but  attaining  over  500 ppm  in  fertile  granites  and
pegmatites (e.g. Černý 1991). The most boron enriched S-type
granites  are  typically  produced  during  anatectic  processes  in
continental collision zones (London et al. 1996). Occurrences
of  B-enriched  peraluminous  magma  derived  from  metasedi-
mentary protolith in the back-arc volcanic environment are far
rarer (Pichavant et al. 1988).

Tourmalines are present in various environments in granitic

bodies  –  from  apical  parts  to  dispersed  tourmaline  inside
the host rock or alternatively in breccias and veins in the gra-
nitic  body  (London  et  al.  1996).  Tourmaline  in  apical  parts
usually  forms  thin  to  skeletal  crystals  and  frequently  inter-
growths with quartz. It displays rapid internal chemical frac-
tionation  from  schorl-dravitic  core  with  fine  oscillatory
zoning  to  Fe-enriched  alkali-deficient  composition  with
lacking chemical zoning in the rim (London et al. 1996). In
contrast,  mixing  processes  during  the  Fe-Mg  infiltration
from the wall rock to the B-enriched magma can also result
in tourmaline crystallization (Taylor et al. 1979). Tourmaline
dispersed  in  the  granitic  body  forms  euhedral  to  anhedral
crystals without chemical zoning and is usually Al-enriched
charge-balanced by increased X-site vacancy or deprotoniza-
tion of OH (London et al. 1996).

Tourmaline is also an abundant mineral of granitic pegma-

tites. These are the dominant genetic environment of Li-bear-
ing  tourmalines  including  elbaite  and  fluor-elbaite  (e.g.
Jolliff  et  al.  1986;  Selway  et  al.  1999;  Tindle  et  al.  2002),
rossmanite (Selway et al. 1999), and liddicoatite (Teerstra et
al.  1999).  However,  granitic  pegmatites  usually  comprise
schorlitic to foititic (Novák et al. 1999; Selway et al. 1999;
Bačík et al. 2011) and more rarely also dravitic tourmalines
(Novák et al. 1999, 2011; Bačík et al. 2012).

Tourmaline is also the most common B-bearing mineral in

metamorphic processes as well. It is a chemically and struc-
turally  resistant  mineral  stable  in  variable  P/T  conditions
from  diagenetic  environment  to  granulite  facies  (Henry  &
Dutrow  1996).  The  lower  limits  of  its  stability  can  be  de-
rived from its presence in the diagenetic zone of sedimentary
basins and in near-surface hydrothermal deposits as low as,
or  lower  than,  150 °C  and  100 MPa  (Henry  et  al.  1999;
Moore et al. 2004). The upper thermal stability of tourmaline
has been studied experimentally and also on natural samples.
It  is  controlled  by  the  incongruent  melting  of  tourmaline,
which  has  been  observed  in  experiments  between  725  and
950 °C depending on pressure and composition (e.g. Morgan
&  London  1989;  Holtz  &  Johannes  1991;  Wolf  &  London

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1997;  von  Goerne  et  al.  1999;  Bačík  et  al.  2011;  London
2011; van Hinsberg 2011). Pressure stability of tourmaline is
also very wide. Experimental data reveal that Mg end-mem-
ber tourmaline is stable up to at least 6 GPa (Krosse 1995).
Further  evidence  for  UHP  tourmalines  comes  from  inclu-
sions  of  coesite  in  tourmaline  grains  from  the  Kokchetav
Massif in northern Kazakhstan, the Erzgebirge in Germany,
and Lago di Cignano and the Dora Maira Massif in the Alps
(Schertl et al. 1991; Marschall et al. 2009; Ertl et al. 2010).

Tourmaline reflects changes in P/T conditions but also in

chemical composition of the host rock and associated miner-
als as well. It is also resistant to re-equilibration and homog-
enization to extreme conditions. Negligible rates of diffusion
for major and trace elements in its structure were indicated
by detrital compositions and sharp compositional and isoto-
pic breaks that have persisted during prolonged periods at el-
evated temperature (e.g. van Hinsberg & Marschall 2007;
van Hinsberg & Schumacher 2007).

Tourmaline extremely fractionates specific chemical ele-

ments (Henry & Dutrow 1996). In the medium grade it has the
highest Mg/Fe and Na/Ca ratio among all phases. Similarly
high Mg/Fe and Na/Ca ratios were documented in high-grade
metamorphic rocks (Henry & Guidotti 1985). These fraction-
ation trends should be considered in determination of tourma-
line host-rock genetic types in metamorphic conditions.

Determination of the chemical composition of detrital

tourmaline allows an estimation of its most possible genetic
environment.  The  proportion  of  major  elements  including
Al, Fe, Mg, and Ca, which are the most influenced by vari-
able  genetic  environment,  can  be  used  for  that  purpose.
Comparing proportions of Al, Fe, and Mg to empirically de-
termined  fields  of  various  genetic  types  (Fig. 9a)  (Henry  &
Guidotti 1985), the tourmalines studied can be ascribed to ori-
gin from metapelites and metapsammites coexisting (10-VD)
or  not  coexisting  (12-VD)  with  an  Al-saturating  phase.

Fig. 9. Diagrams for determination of tourmaline genetic environ-
ment. Tourmalines (n = 29) from the sandstone samples 10-VD and
12-VD are compared with published data (fields). a – Al—Fe

total

—Mg

diagram (in molecular proportions). This diagram is divided into re-
gions that define the compositional range of tourmalines from differ-
ent rock types. The rock types represented are: 1 – Li-rich granitoid
pegmatites and aplites, 2 – Li-poor granitoids and their associated
pegmatites and aplites, 3 – Fe

-rich quartz-tourmaline rocks (hy-

drothermally altered granites), 4 – metapelites and metapsammites
coexisting with an Al-saturating phase, 5 – metapelites and meta-
psammites not coexisting with an Al-saturating phase, 6 – Fe

-rich

quartz-tourmaline rocks, calc-silicate rocks, and metapelites,
7 – low-Ca metaultramafics and Cr, V-rich metasediments,
8 – metacarbonates and meta-pyroxenites (modified after Henry &
Guidotti 1985). b – Ca—Fe

total

—Mg diagram (molecular proportions).

The rock types defined by the fields in this diagram are somewhat
different than those in Al—Fe

total

—Mg diagram. These fields are:

1 – Li-rich granitoid pegmatites and aplites, 2 – Li-poor granitoids
and  associated  pegmatites  and  aplites,  3  –  Ca-rich  metapelites,
metapsammites,  and  calc-silicate  rocks,  4  –  Ca-poor  metapelites,
metapsammites,  and  quartz-tourmaline  rocks,  5  –  metacarbonates,
6 – metaultramafics (Henry & Guidotti 1985). c – Ca vs. X-site va-
cancy  diagram  with  the  fields  for  selected  metamorphic  grades  and
genetic types (Henry & Dutrow 1996).

A  similar  observation  was  made  on  the  comparison  of  the
Ca,  Fe,  and  Mg  proportions  (Fig. 9b)  (Henry  &  Guidotti
1985). The relatively low proportion of Ca and X-site vacancy
in  the  tourmalines  studied  suggests  a  medium  grade  of
metamorphism  according  to  Henry  &  Dutrow  (1996)

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(Fig. 9c). This is also supported by the relatively high Mg/Fe
(1.11—3.43)  and  Na/Ca  (2.76—38.05)  ratio  in  most  of  the
tourmalines  studied,  which  is  typical  for  the  medium  grade
(Henry  &  Guidotti  1985).  The  possibility  of  high-grade
metamorphic origin for the tourmalines studied is limited by
the very low F content (Grew et al. 1990) and the Si content
sufficient  for  full  or  almost  full  T-site  occupancy,  which
eventually  limits  access  of  the  tetrahedral  Al  (Grew  et  al.
1990; Cempírek et al. 2006) or B (Ertl et al. 2008) typical for
high-grade  environments.  Only  one  tourmaline  grain  with
a distinctly lower Mg/Fe ratio of 0.70 could be related to the
Li-poor  granitic  genetic  environment  (Fig. 9a,b)  (Henry  &
Guidotti 1985). We speculate that the subtle difference in the
composition  of  the  10-VD  and  12-VD  sample  could  result
from the slightly higher temperature during crystallization of
12-VD  tourmalines  or  eventually  from  differences  in  the
protolith composition.

Absence of inherited cores and overgrowths in the tourma-

lines studied suggests that these crystallized during only one
genetic event. The possibility of a homogenization process
can be excluded since these tourmalines do not exhibit any
features (increased F,

Al,

B, and Ca content, for example)

typical for high-grade metamorphism with temperatures over
700 °C necessary for initiation of diffusion in tourmalines
(Bačík et al. 2011; Ertl et al. 2012).

Source areas of the Malužiná Formation sandstones and
paleogeography

Previous petrographic, cathodoluminescence, and whole-

rock  geochemical  studies  on  sandstones  from  the  Malužiná
Formation suggested their derivation from multiple source ar-
eas  (Vnačný  2013;  Vnačný  et  al.  2013).  In  these  works,  we
speculated  that  the  source  areas  were  probably  located  quite
close to the site of deposition and had broken high relief. The
detritus of the Malužiná Formation sandstones was very likely
stripped  rapidly  from  the  elevated  areas  and  transported  a
short-distance into the sedimentary basin. Acid (felsic) plu-
tonic rocks and low- to high-grade metamorphic rocks, felsic
and  mafic  volcanic  rocks  were  identified  as  major  source
lithologies. These rather broad compositional types of source
rocks  could  be  refined  here  to  specific  source-rock  types  by
the aid of mineral chemistry of garnets and tourmalines. The
present  evaluation  of  chemical  composition  of  these  two
heavy minerals revealed the following possible parent source
rocks  for  the  Malužiná  Formation  sandstones:  (1)  low-grade
regionally  metamorphosed  rocks  (metacherts,  blue  schists,
metapelites  and  metapsammites  coexisting  or  not  coexisting
with  an  Al-saturating  phase),  (2)  thermally  metamorphosed
impure  calcareous  rocks  with  skarn  deposits  and  rodingites,
(3)  garnet-mica  schists,  gneisses  resulting  from  the  regional
metamorphism  of  argillaceous  sediments,  (4)  amphibolites
and metabasic sub-ophiolitic rocks, (5) granulites, (6) Li-poor
granites and their associated pegmatites and aplites as well as
(7)  rhyolites.  Moreover,  additions  from  the  synsedimentary
andesite-basalt  continental  tholeiites  (Vozár  1997;  Dostal  et
al. 2003) are apparent from the presence of fragments of these
rocks  in  the  particle  composition  of  the  Malužiná  Formation
sandstones (Vnačný 2013; Vnačný et al. 2013).

As mentioned above, it is evident that metamorphosed and

acid volcanic rocks are one of the principal sources. Several
low-grade metamorphosed complexes, that mostly emerge in
the form of tectonically restricted slices on the middle- and
higher  metamorphosed  complexes  or  that  lie  directly  on
granitoids,  occur  in  the  pre-Pennsylvanian  crystalline  base-
ment of the Central Western Carpathians (Biely et al. 1996).
Acid volcanism products were found in the Northern Vepori-
cum  Unit,  namely  in  the  Jánov  Grúň  Complex  in  the
Kráƒovohoƒské  Tatry  Mts  (Bajaník  et  al.  1979;  Miko  1981)
and in the Krakƒová Formation (Korikovskij & Miko 1992).
We  suppose  that  clastic  garnets  and  tourmalines  of  the
Malužiná  Formation  sandstones  could  have  originated  in
these  regions.  Some  of  the  detrital  garnets  and  tourmalines
were  derived  from  the  plutonic  complexes  associated  with
the Variscan subduction processes.

In this manner, the mineral chemistry of detrital garnets

and tourmalines permitted us to more precisely interpret the
character of the original basement rocks. Thus, we can now
infer that the Malužiná rift system originated on a medium-
to high-grade crystalline core complex composed of garnet-
mica schists, gneisses, amphibolites and metabasic sub-ophio-
litic  rocks,  and  granulites  penetrated  with  Li-poor  granites,
pegmatites,  and  aplites.  This  is  characteristic  for  the
Variscan terranes of the Central Western Carpathians (Biely
et al. 1996; Vozárová et al. 2009). The occurrences of conti-
nental  tholeiites  determine  the  axial  part  of  the  former  rift-
trough.  Fragments  from  low-grade  metasediments  such  as
metacherts,  blue  schists,  metapelites  and  metapsammites,
could have come from the Variscan orogenic zone.

Dostal et al. (2003) provided a tectonic reconstruction

concerning  the  Malužiná  Formation.  These  authors  stated
that  the  Malužiná  Formation  represents  a part  of  a post-
Variscan overstep suite that was formed after accretion of the
Gothic terranes to Laurussia. Our previous and present find-
ings about the provenance of the Malužiná Formation sand-
stones  are  in  good  agreement  with  their  paleogeographical
reconstruction  that  came  from  the  studies  of  Tait  et  al.
(2000)  and  Stampfli  et  al.  (2001a,b,  2002).  Specifically,  it
was  assumed  that  the  Gothic  terranes,  which  included  Ar-
morica  and  correlatives,  rifted  off  the  northern  Gondwanan
margin in the Late Silurian, and this led to the development of
the Paleo-Tethys Ocean. Subduction of the Rheic Ocean be-
neath  the  leading  edge  of  the  Gothic  terranes  eventually
caused a collision with the southern margin of Laurussia in
the Late Devonian to Early Carboniferous. Subduction of Pa-
leo-Tethys  beneath  the  southern  margin  of  the  accreted
Gothic terranes and dextral transpressional and transtensional
displacement  of  terranes  followed  in  the  Carboniferous  and
Permian. Some rift basins were converted into oceanic back-
arc basins as a consequence of Triassic roll-back of the trench.

Conclusions

The chemical composition shows that almandine, spessar-

tine-rich almandine, grossular-rich almandine, pyrope-rich
almandine, and andradite garnets occur in the Permian sand-
stones from the Malužiná Formation in the Malé Karpaty

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Mts. Tourmalines from the sandstones studied belong to a
group of alkali tourmalines with dravitic composition, with
the exception of a single tourmaline grain that has schorlitic
composition.

The detrital garnets from the Malužiná Formation sand-

stones  were  very  likely  derived  from  garnet-mica  schists,
gneisses, metapelites, metacherts, amphibolites and metaba-
sic  sub-ophiolitic  rocks.  Derivation  from  granulites,  blue-
schists,  granites  and  volcanic  rocks  cannot  be  excluded.
Some  garnet  grains  with  andradite  composition  can  be
linked with calc-silicates, skarns, and rodingites.

The tourmalines from the Malužiná Formation sandstones

presumably  crystallized  in  Al-poor  as  well  as  in  Al-rich
metasedimentary rocks and a minority of them also in Li-poor
granitic  rocks  or  pegmatites.  Additionally,  the  relatively  low
proportion of Ca and X-site vacancy in the tourmalines studied
suggests  a  medium  grade  of  metamorphism.  Absence  of  in-
herited  cores  and  overgrowths  in  the  tourmalines  examined
suggests crystallization during only one genetic event.

Judging from the chemical composition of the detrital gar-

nets  and  tourmalines,  the  Malužiná  rift  system  very  likely
originated on a medium- to high-grade crystalline core com-
plex  composed  of  garnet-mica  schists,  gneisses,  amphibo-
lites  and  metabasic  sub-ophiolitic  rocks,  and  granulites
penetrated  with  Li-poor  granites,  pegmatites,  and  aplites.
Fragments  from  low-grade  metasediments  such  as  meta-
cherts,  blue  schists,  metapelites  and  metapsammites,  could
have come from the Variscan Orogenic Zone.

Acknowledgments: This work was supported by the Opera-
tional  Programme  Research  and  Development  through  the
project:  Centre  of  Excellence  for  Integrated  Research  into
the  Earth’s  Geosphere  (ITMS: 26220120064),  which  is  co-
financed through the European Regional Development Fund.
This work was also supported by the Slovak Research and De-
velopment Agency under the Contract No. APVV-0546-11.

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