GeolCarp_Vol64_No1_23

www.geologicacarpathica.sk

GEOLOGICA CARPATHICA

, FEBRUARY 2013, 64, 1, 23—38 doi: 10.2478/geoca-2013-0002

Introduction

Sandstone  geochemistry  has  a number  of  important  applica-
tions  (e.g.  Potter  1978;  Bhatia  1983,  1985;  Roser  &  Korsch
1988; Floyd et al. 1991; McLennan et al. 1993; Dinelli et al.
1999; Getaneh 2002; Lacassie et al. 2004; Rahman & Suzuki
2007; Dey et al. 2009). For instance, major-element chemistry
can provide information about the tectonic setting of sedimen-
tary  basins,  allowing  distinction  between  sandstones  derived
from oceanic island arc, continental island arc, active conti-
nental  margin,  and  passive  margin  settings  (Bhatia  1983;
Roser & Korsch 1986; Kroonenberg 1994). Major- and trace-
element  chemistry  have  been  used  to  evaluate  sedimentation
rates and depositional environments in orogenic belts (Sugisaki
1984).  Moreover,  major-element  chemistry  has  been  utilized
to infer the original clastic assemblages in deeply buried and
altered sedimentary rocks and to help clarify the processes that
produced the sediments (Argast & Donnelly 1987). Trace ele-
ments  also  have  value  in  some  kinds  of  provenance  studies.
(See Boggs 2009, Ch. 7, for discussion of this subject.)

Provenance of the Permian sandstones from the Malužiná

Formation in the Malé Karpaty Mts has not as yet been anal-
ysed with the geochemical approach. Forasmuch as the
Malužiná Formation is a part of the rootless nappe Hronic

Unit, we decided to unravel the source-area weathering, prov-
enance, and tectonic setting of the putative source area of the
Malužiná Formation sandstones. To this end, we evaluated the
major- and trace-element geochemistry of these sandstones, in
relation to their mineral composition. The present study sup-
plies new data not only on local geology but also important
material for various comparisons and correlations. Finally, our
detailed analysis may improve our understanding of the Per-
mian paleogeography and tectonic evolution.

Geological setting

The Late Paleozoic of the Hronicum, defined by Vozárová

& Vozár (1981, 1988) as the Ipoltica Group with two litho-
stratigraphic  units  of  a lower  order  –  the  Nižná  Boca  and
the  Malužiná  Formations,  is  variably  preserved  and  occurs
as tectonically  reduced  fragments  in  the  basal  part  of  the
multi-nappe structure in various regions of the Western Car-
pathians (Fig. 1a).

The Permian Malužiná Formation overlies the Pennsylva-

nian Nižná Boca Formation from which it develops gradually
without break of sedimentation. The Malužiná Formation
ranges from the Cisuralian to the Lopingian in age (Autunian—

Geochemistry of the Permian sandstones from the Malužiná

Formation in the Malé Karpaty Mts (Hronic Unit, Western

Carpathians, Slovakia): implications for source-area

weathering, provenance and tectonic setting

MAREK VĎAČNÝ

, ANNA VOZÁROVÁ

and JOZEF VOZÁR

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

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

Geological Institute, Slovak Academy of Sciences, Dúbravská cesta 9, P.O. Box 106, 840 05 Bratislava, Slovak Republic;

jozef.vozar@savba.sk

(Manuscript received January 19, 2012; accepted in revised form June 13, 2012)

Abstract: The Permian sandstones of the Malužiná Formation in the northern part of the Malé Karpaty Mts are domi-
nantly quartzofeldspathic and quartzolithic in composition with abundant feldspars and volcanic, plutonic igneous and
less metasedimentary lithic fragments, indicating the sand grains were derived from a basement uplift and recycled
orogen. The Malužiná Formation sandstones have moderate to high SiO

contents (68—85 wt. %; on average 76 wt. %),

TiO

concentrations averaging 0.3 wt. %, Al

contents of about 12 wt. %, and Fe

(total Fe as Fe

) + MgO

contents of around 2.9 wt. %. The Chemical Index of Alteration (CIA) values for the Permian Malužiná Formation
sandstones vary from 45 to 68 with an average of 55, indicating low to moderate weathering of the source area. The bulk
chemical composition and selected trace elements preserve the signatures of a felsic and intermediate igneous prov-
enance, and suggest mostly an active continental margin tectonic setting of the source area for the Malužiná Formation
sandstones. The Eu/Eu* ( ~ 0.78), La/Sc ( ~ 7.28), Th/Sc ( ~ 2.10), La/Co ( ~ 6.67), Th/Co ( ~ 1.85), and Cr/Th ( ~ 6.57)
ratios as well as the chondrite-normalized REE patterns with flat HREE, LREE enrichment, and negative Eu anomalies
indicate derivation of the Malužiná Formation sandstones from felsic rock sources. The deposition of the Malužiná
Formation sandstones took place in a rifted continental margin environment supplied from collision orogen on a thick
continental crust composed of rocks of older fold belts.

Key words: Permian, Western Carpathians, sandstone geochemistry, provenance, tectonic setting.

VĎAČNÝ, VOZÁROVÁ and VOZÁR

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GEOLOGICA CARPATHICA, 2013, 64, 1, 23—38

Saxonian—Thuringian according to the Central European local
stratigraphic  scale)  (e.g.  Planderová  1973;  Planderová  &
Vozárová 1982; Rojkovič et al. 1992; Vozárová et al. 2005).
Lithologically, the Malužiná Formation is characterized by a
dominance of siliciclastic sedimentary rocks (polymict con-
glomerates,  sandstones,  siltstones,  shales)  with  sporadic
chemogenic sediment interbeds (caliches and evaporites) of
a variable thickness. There is a significant inner cyclic struc-
ture  of  the  sedimentary  sequences  which  are  arranged  into
three regional megacycles. An important phenomenon is the
polyphasic synsedimentary andesite-basalt volcanism, repre-
sented by rift-related continental tholeiites, in the 1st and 3rd
megacycles,  comprising  huge  lava  flows  generated  during

two eruption phases (Vozár 1997; Dostal et al. 2003). As es-
timated from the surface occurrences in the Nízke Tatry Mts
and drilling data, the maximum thickness of the Malužiná
Formation is 2200—2400

m (Vozárová & Vozár 1988). Volca-

nics and sediments in the Malužiná Formation are generally
very low-grade metamorphosed. The grade of metamorphism
did not exceed the diagenesis/anchizone boundary, which is
characterized by the pumpellyite-prehnite-quartz mineral as-
sociation (Vrána & Vozár 1969) and by the illite crystallinity
indices from pelites (Plašienka et al. 1989; Šucha 1989; Šucha
& Eberl 1992). Lithofacies analyses of the Malužiná Forma-
tion sequences, the character of volcanism and the structural
arrangement of sediments in the entire megasequence suggest

Fig. 1. a – Distribution of the Ipoltica Group in the Western Carpathians (after Vozárová & Vozár 1988). Explanations: 1 – surface oc-
currences, 2 – established and inferred distribution of the Hronic nappes, 3 – overthrust lines of the Hronic nappes, significant faults and
boundaries  delimitating  distribution  of  the  Ipoltica  Group,  4  –  significant  lines  in  the  Alpine  structure  of  the  Western  Carpathians:
a –  ubeník-Margecany line, b – Čertovica line, c – Peripieninian lineament. b – Late Paleozoic of the Hronicum in the Malé Karpaty Mts
(after Vozárová & Vozár 1988). Explanations: 1 – Quaternary sediments, 2 – Tertiary sediments. Hronicum—Šturec Nappe: 3 – Mid-
dle and Upper Triassic – carbonates, undivided, 4 – Lower Triassic – quartz sandstones, shales, 5 – Late Paleozoic—Permian – andes-
ites,  basalts  and  volcanoclastics  (Malužiná  Formation),  6  –  Late  Paleozoic—Permian  –  conglomerates,  sandstones,  shales  with
volcanogenic 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 – over-
thrust line of nappes, 13 – sample location.

GEOCHEMISTRY OF THE PERMIAN SANDSTONES FROM THE MALUŽINÁ FORMATION (SLOVAKIA)

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GEOLOGICA CARPATHICA, 2013, 64, 1, 23—38

an  intracontinental,  rift-related  type  of  the  original  deposi-
tional  basin.  Thus,  the  depositional  environment  was  conti-
nental and was characterized by deltaic-lacustrine and alluvial
sub-environments,  including  micro-environments  controlled
by arid to semiarid climate (Vozárová & Vozár 1988).

In the northern part of the Malé Karpaty Mts, the Ipoltica

Group occupies the area to the SW of Smolenice and Lošonec
in a belt 1.5—2.5

km wide, 15

km long, NE—SW-oriented, and

extends to the western margin of the mountain range to the
S of Sološnica (Fig.

1b). The Mesozoic of the Krížna Nappe

is  the  direct  tectonic  basement  of  the  Ipoltica  Group  in  the
whole  area.  From  the  east  and  west  sides  of  the  Malé  Kar-
paty  Mts,  the  geological  units  are  tectonically  bordered  by
the Tertiary faults of NE—SW direction. As a consequence of
this tectonic phenomenon, we can interpret the continuation
of all geological units (including the Ipoltica Group) into the
pre-Neogene  basement  of  the  Vienna  (western  part)  and
Danube (eastern part) Basins.

Sampling and methods

Twenty-five representative samples of sandstones were col-

lected  within  the  Malužiná  Formation  in  the  Malé  Karpaty
Mts.  Sampling  spatially  covered  the  whole  regional  occur-
rence of the studied lithostratigraphic unit, including its lower
and  upper  parts.  The  exact  locations  of  sampling  sites  are
shown in Fig.

1b. Medium-grained sandstones were preferen-

tially selected for petrographic and geochemical analyses.

Thin sections of collected samples were prepared and exam-

ined by a petrographic microscope. The modal composition of
the Malužiná Formation sandstones was reviewed. The petro-
graphic  examination  and  modal  analyses  of  the  sandstone
samples were carried out following the method of Dickinson
(1970).  Modal  analyses  were  performed  on  the  thin  sections
by counting 500 points on each slide using the Gazzi-Dickin-
son point-counting method. Various types of lithic grains were
distinguished on the basis of textural and mineralogical char-
acteristics.  Only  aphanitic  polycrystalline  grains  were  classi-
fied as lithic fragments and quartz/feldspar grains larger than
0.06 mm,  when  occurring  within  lithic  fragments,  were
counted with the discrete quartz or feldspar component.

In all thin sections, the heavy minerals constitute less than

1 %  of  the  total  framework  clasts.  In  order  to  facilitate  the
present  study,  we  conducted  conventional  heavy  mineral
analysis  for  ten  medium-grained  sandstone  samples.  The
0.063—0.250

mm fraction of the dried samples was sieved

out  for  the  heavy  mineral  analysis.  The  heavy  fraction  was
separated from the light fraction with the gravity separation
method  using  a  heavy  liquid  (bromoform  with  a  measured
specific gravity of 2.8). We point-counted 350 grains in each
heavy  mineral  mount.  Problematic  opaque  and  non-opaque
heavy minerals were embedded in polished sections and mi-
croanalytically determined (EDS). The ZTR index, which is
a measure  of  mineralogical  maturity  of  heavy-mineral  as-
semblages  in  sandstones,  was  calculated  as  a  percentage  of
the combined zircon, tourmaline, and rutile grains among the
transparent, non-micaceous, detrital heavy minerals for each
sample (Hubert 1962).

Twenty-five sandstone samples of the Permian Malužiná

Formation  were  analysed  for  major  and  trace  elements  by
Acme Analytical Laboratories (Vancouver) Ltd., Vancouver,
Canada.  Major  elements  were  analysed  by  inductively  cou-
pled plasma emission spectrometry (ICP) and trace and rare
earth  elements  (REE)  by  inductively  coupled  plasma  mass
spectrometry  (ICP-MS).  Loss  on  ignition  (LOI)  was  deter-
mined  by  heating  the  samples  at  1000

°C for two hours.

Sample  digestion  procedures  are  similar  for  both  ICP  and
ICP-MS.  Two  hundred  milligrams  of  pulverized  sample
were  mixed  with  1.5

g of a flux of lithium metaborate and

lithium tetraborate in a graphite crucible. Subsequently, the
crucible was placed in a muffle furnace and heated to
1050

°C for 15

min. The molten mixture was dissolved in

100

ml of 5% HNO

(ACS grade nitric acid diluted in dem-

ineralized water). International reference samples (standards)
and  reagent  blanks  were  added  to  the  sample  sequence.  At
the  second  stage  (sample  analysis),  sample  solutions  were
aspirated  into  an  ICP  emission  spectrometer  (Jarrel  Ash
AtomComb 975) or an ICP mass spectrometer (Perkin-Elmer
Elan 6000) for the determination of element content. Major
elements were determined with accuracy better than 2

% and

trace elements with accuracy better than 10

Results

Petrography and mineral composition

A part of the Malužiná Formation sandstones is coloured

violet or red owing to the presence of finely disseminated he-
matite pigment, which occurs as a very thin coating around
grains or is infiltrated within the matrix; others are light grey
to beige. The sedimentary structure of the Malužiná Forma-
tion sandstones is mostly massive and horizontal current
laminated, occasionally cross-bedded. Destructive activity is
represented by washouts and erosive channel structures asso-
ciated with a swarm of intraformational claystone- and silt-
stone clasts. The deformation structures, such as load casts,
are frequent.

The sandstones of the Malužiná Formation are typically

medium-  to  coarse-grained  and  contain  high  percentages  of
subangular  to  angular  grains.  Sorting  of  the  framework
grains  ranges  from  moderately  well  sorted  to  poorly  sorted
( = 0.50 to 2.00) (after Folk 1974; textural comparison chart
showing  degree  of  sorting  is  after  Jerram  2001).  Thus,  the
Malužiná  Formation  sandstones  are  texturally  immature  or
submature.

The Malužiná Formation sandstones have dominantly

quartzofeldspathic composition with predominance of quartz.
On the quartz-feldspar-rock fragment (QFR) plot of McBride
(1963), these sandstones can be classified as arkose, subar-
kose, lithic subarkose, and feldspathic litharenite (Fig. 2).
Thus, the petrographic classification indicates a group of arko-
sic sediments for the Malužiná Formation sandstones.

Quartz is the dominant framework grain, constituting an

average of 57 % of the rock volume, and occurring as
monocrystalline (mean 39.4 %; range 18—64.2 %) and poly-
crystalline (mean 17.6 %; range 7—29.4 %) grains. Some

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GEOLOGICA CARPATHICA, 2013, 64, 1, 23—38

polycrystalline quartz grains display sutured internal bound-
aries between composite crystals, indicating a probable early
stage in development of metamorphic polycrystalline quartz.

Feldspars (orthoclase, microcline, microperthite, plagio-

clases)  constitute  around  24.5 %  of  the  total  framework
grains  of  the  sandstones.  Both  potassium  feldspar  (mean
13.3 %; range 6—26 %) and plagioclase (mean 11.2 %; range
3.2—24.4 %) are present in almost equal amounts. Microcline
grains have well-developed grid twinning. Many plagioclase
grains  are  characterized  by  distinctive  albite  twinning,  with
twin lamellae that are straight and parallel. The feldspars in
the  studied  sandstones  are  predominantly  fresh  and  unal-
tered, but there are a few grains showing some weak degrees
of alteration to sericite or kaolinite.

Next in abundance to feldspar, lithic grains make up to

14.4 %  of  the  total  framework  constituents.  Specifically,
there are some volcanic (mean 6.8 %; range 0—20.4 %), low-
grade metamorphic (mean 3.8 %; range 0—16.4 %), and sedi-
mentary  (mean  3.8 %;  range  0—16.8 %)  rock  fragments.
Volcanic rock fragments include felsic, intermediate microli-
thic,  basic  lathwork,  and  vitric  to  vitrophyric  grains.  Meta-
morphic  rock  fragments  are  grains  with  tectonite  and
nonfoliated  fabric.  The  grains  with  tectonite  fabric  include
metasedimentary fragments of schist, sericite- and quartzose
phyllite, paragneiss, and mica schist. The grains with nonfo-
liated fabric comprise metaquartzite clasts composed mainly
of  quartz  with  strongly  sutured  contacts.  Sedimentary  rock
fragments involve fine-grained sandstone, siltstone, shale or
mudstone, and chert.

White mica is generally more abundant than biotite, both

constituting on average 1.4 % (range 0—9.6 %) of the total
framework grains in the studied sandstones. Biotite grains
are usually baueritized.

The sandstones of the Malužiná Formation have very low

matrix contents (mean 2.7 %; range 0—10.4 %). These low
contents indicate that it is a primary depositional matrix, and
not a diagenetic clay. The matrix of the sandstones is slightly
recrystallized, changed into a sericite and scarce chlorite ag-
gregate. Quartzose, calcite and ferruginous cements are pre-
served, but only in a negligible content.

The heavy mineral assemblage in the Malužiná Formation

sandstones  is  characterized  by  the  presence  of  opaque  and
non-opaque minerals. The following opaque heavy minerals
occur in the studied sandstones: magnetite, ilmenite and he-
matite (mainly diagenetic in origin). The non-opaque heavy
minerals  are  represented  here  by  three  groups:  ultrastable
(zircon,  tourmaline  and  rutile),  stable  (apatite  and  biotite),
and moderately stable (titanite and garnet). The average pro-
portion of observed heavy minerals in the studied sandstones
is  as  follows  (listed  in  the  decreasing  percentage):  biotite
(29.55 %),  magnetite,  ilmenite  and  hematite  (27.58 %),  ti-
tanite (13.86 %), tourmaline (10.21 %), garnet (8.68 %), ap-
atite (5.78 %), zircon (3.93 %), and rutile (0.39 %). The ZTR
index  varies  widely  (19.57—59.68 %)  among  the  Malužiná
Formation sandstones, but its average value is comparatively
low (33.21 %), showing their mineralogical immaturity.

We found only little petrographic evidence of diagenetic

features, such as dissolution of feldspar and rock fragments,
compaction, reduction of the existing pore space through re-
arrangements,  and  rotation  and  fragmentation  of  grains  re-
sulting in dissolution of quartz grains and cementation. Our
observations  of  only  weak  diagenetic  alterations  of  feld-
spars, for example, inconspicuous albitization and other pro-
cesses,  document  that  the  original  composition  of  the
Malužiná  Formation  sandstones  was  only  insignificantly
modified.  Thus,  we  exclude  considerable  diagenetic  over-
print  which  could  influence  the  mineral  and  chemical  com-
position of the studied sandstones.

Chemical composition

The individual major and trace element analyses of the

sandstones of the Malužiná Formation from the Malé Kar-
paty Mts are presented in Table 1.

Major elements

The Malužiná Formation sandstones have moderate to

high SiO

contents (on average 76 wt. %; range 68—

85 wt. %), TiO

concentrations averaging 0.3 wt. % (range

0.05—0.63 wt. %), Al

contents of about 12 wt. % (range

7.88—14.98 wt. %), and Fe

(total Fe as Fe

) + MgO

contents  of  around  2.9 wt. %  (range  0.69—4.67 wt. %).  The
samples show no marked differences in their major element
chemical  composition  (for  details,  see  Table 1).  Variations
in  the  major  element  geochemistry  of  the  Malužiná  Forma-
tion sandstones are shown on Harker diagrams (Fig. 3). The
linear relationship of TiO

, Al

, Fe

, MnO, CaO, MgO,

O, and K

O with SiO

in the Malužiná Formation sand-

stones is conspicuous in these Harker variation diagrams. In
general, SiO

increases and TiO

, Al

, Fe

, MnO, CaO,

MgO, Na

O, and K

O decrease in the Malužiná Formation

Fig. 2. Classification of the Malužiná Formation sandstones accord-
ing to McBride (1963). Points within the triangle represent relative
proportions of Q (quartz), F (feldspar), and R (rock fragments) end
members.

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Fig. 3. Harker variation diagrams for the Malužiná Formation sandstones. The increase in SiO

re-

flects an increased mineralogical maturity, i.e. a greater quartz content and a smaller proportion of
other detrital grains.

sandstones  due  to  the  increase  in
mineralogical  maturity  (Fig. 3).
This  mineralogical  maturity  is
characterized  by  an  increase  in
the quartz content and a decrease
in  unstable  detrital  grains  (e.g.
feldspar  and  volcanic  rock  frag-
ments)  in  the  Malužiná  Forma-
tion  sandstones,  which  also
reflects  a  stratigraphic  trend.  The
negative correlation of SiO

with

the other major elements is due to
most  of  the  silica  being  seques-
tered  in  quartz,  as  indicated  by
Osman  (1996).  In  the  present
samples,  TiO

concentrations in-

crease with Al

, suggesting

that TiO

is probably associated

with phyllosilicates especially
with

illite

(Dabard

1990);

+ MgO are also well corre-

lated with Al

. The latter corre-

lation implies that these oxides
are associated with phyllosili-
cates, particularly in matrix chlo-
rites (Dabard 1990).

Trace elements

The processes controlling the

trace element composition of sed-
imentary rocks may be investigated
using

normalization

diagrams

(spider  diagrams).  Trace  element
concentrations  of  the  Malužiná
Formation  sandstones  are  in  con-
currence  with  the  average  upper
continental  crust  (UCC)  with  the
exception  of  Ba,  Nb,  Sr  and  Tb
contents  (Fig. 4).  In  the  present
samples,  Ba  (78—3185 ppm)  is
strongly  enriched  in  three  sam-
ples,  slightly  depleted  in  most  of
the samples and strongly depleted
only  in  one  sample.  The  Ba  en-
richment  of  the  three  samples  is
related to the presence of  K-feld-
spar  and  barite,  occurrence  of
which  was  also  confirmed  by  our
petrographic  observations.  Nb
(1.7—12.1 ppm)  and  Tb  (0.13—
0.97 ppm) are depleted in all stud-
ied  samples.  The  Sr  content
(25.3—460.4 ppm)  of  the  studied
sandstones is variable, as there are
some  slightly  enriched,  depleted
and  also  strongly  depleted  sam-
ples. This variability is caused by
many  influences  on  Sr  in  low

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GEOLOGICA CARPATHICA, 2013, 64, 1, 23—38

temperature depositional environments (Fairbridge 1972). For
instance, the distribution of Sr can be affected by the presence
of Ca, fractionation of Sr can result from the weathering of feld-
spars, particularly plagioclase, and additional Sr can be incor-
porated in diagenetic carbonate, as also noticed in the Malužiná
Formation sandstones. K and Rb have a trend comparable to
that of Nb (Fig. 4). The two former elements are mainly hosted

in micas and K-feldspar (Heier & Billings 1970); thus, alter-
ation of these minerals will dominate the fractionation of these
elements. The high field strength elements (e.g. Hf, Zr, Y)
generally show consistent interrelationships, as do the large ion
lithophile elements (Th and U) and selected rare earth ele-
ments (La, Ce, Nd, Sm, Tm, and Yb), though clear relationships
are sometimes not completely obvious between them (Fig. 4).

Table 1: ICP-determined major, trace and rare earth element abundances for the Malužiná Formation sandstones.

Sample

10-VD 11-VD 12-VD 13-VD 16-VD 17-VD 18-VD 19-VD 20-VD 21-VD 22-VD 23-VD

Major elements (wt. %)
SiO

82.73

71.32

75.54

76.94

69.08

72.32

84.02

85.03 77.34

79.57

80.29

79.53

TiO

0.08

0.39

0.3

0.61

0.34

0.16

0.05 0.06

0.12

0.36

0.32

9.55

14.98

12.62

12.02

13.94

12.21

7.88

8.11 10.65

11.01

10.01

10.24

1.27

2.41

2.56

1.9

2.57

2.04

1.96

0.9

0.73

0.97

2.47

2.94

MnO

0.02

0.06

0.04

0.05

0.04

0.02

0.02 0.05

0.09

0.04

0.05

MgO

0.16

1.26

0.58

0.43

0.73

0.53

1.58

0.7

0.21

0.54

0.76

0.67

CaO

0.35

0.77

1.08

1.29

3.1

3.09

0.09

0.21 2.31

0.92

0.18

0.29

4.18

4.83

4.61

4.64

3.88

3.97

1.73

2.22 4.7

3.98

3.89

3.85

0.79

1.41

0.88

2.12

1.72

0.64

1.76 0.79

1.19

0.41

0.64

0.05

0.09

0.1

0.08

0.16

0.09

0.04

0.03 0.04

0.05

0.06

LOI

0.5

2.3

1.3

3.6

3.5

1.8

0.9

2.4

1.4

1.3

Total

99.68

99.82

99.83

99.85

99.92

99.93 99.28

99.84

99.87

99.89

O/K

5.29

3.43

4.61

5.27

1.83

2.31

2.70

1.26 5.95

3.34

9.49

6.02

O/Na

0.19

0.29

0.22

0.19

0.55

0.43

0.37

0.79 0.17

0.30

0.11

0.17

+ MgO 1.43

3.67

3.14

2.33

3.30

2.57

3.54

1.60 0.94

1.51

3.23

3.61

/SiO

0.12

0.21

0.17

0.16

0.20

0.17

0.09

0.10 0.14

0.14

0.12

0.13

CIA

Trace elements (ppm)
Sc

1.4

9.8

2.9

5.6

3.5

4.9

1.8

1.6

2.6

4.8

9.4

13.4

8.2

11.3

10.2

6.3

7.1

5.6

9.7

10.1

9.3

14.7

3.5

4.5

7.2

38.1

3.7

13.2

2293.7

5.8

33.9

13.7

10.5

10.2

13.6

11.5

6.9

7.9

9.5

8.5

9.7

20.5

40.9

32.3

77.4

22.1

44.6

22.3

17.7

28.4

176

252.2

417.6

460.4

222.1

221.5

25.3

66.7

107.4

116.7

128.8

107.5

7.2

19.9

14.7

15.1

18.8

4.5

4.8

8.6

11.4

8.2

14.7

49.9

252.6

162.7

109.6

342.9

158.4

76.7

43.7

58.7

71.3

90.4

86.2

1.8

7.4

6.3

10.6

6.9

2.7

1.7

2.5

6.9

6.1

0.4

2.1

2.2

1.9

3.6

2.6

1.5

0.4

0.9

0.8

1.4

1999

433

266

268

320

441

415

3185

541

292

221

1.6

7.7

5.1

3.6

10.3

4.7

2.3

2.1

2.2

2.5

2.6

0.2

0.6

0.5

0.9

0.5

0.2

0.4

0.5

0.8

0.9

0.8

1.6

1.2

0.5

0.7

32.5

5.8

7.8

10.1

3.7

4.8

3.1

5.9

166.9

2.6

8.7

4.6

3.4

10.5

6.4

12.2

8.2

2.4

3.4

4.1

8.8

7.9

0.5

2.2

1.7

1.4

2.9

1.7

0.7

0.8

0.7

0.8

1.4

Rare earth elements (ppm)
La

12.9

46.9

31.4

32.5

35.6

10.9

7.4

7.5

13.7

20.3

22.8

24.8

93.3

57.8

56.4

63.9

21.5

16.8

16.7

26.7

43.8

49.4

3.11 10.09

6.53

6.61

8.95

7.31

2.31

2.02 2.34

3.59

4.36

5.84

11.8

37.3

24.2

33.4

27.8

7.8

7.6

10.1

15.1

15.4

22.4

2.17 5.68

3.86

4.16

5.98

4.53

1.03

1.47 2.31

2.88

2.36

3.82

0.52 1.09

0.94

1.02

1.38

1.03

0.19

0.32 0.58

0.83

0.61

0.93

1.71 4.24

3.02

3.27

5.14

3.66

0.68

1.11 2

2.44

1.66

3.27

0.27 0.65

0.48

0.55

0.8

0.57

0.13

0.18 0.32

0.4

0.29

0.52

1.37 3.66

2.77

2.89

4.38

2.96

0.86

0.95 1.57

1.99

1.52

2.73

0.24 0.7

0.52

0.55

0.83

0.6

0.16

0.17 0.3

0.38

0.29

0.51

0.61 2.03

1.49

1.54

2.39

1.72

0.51

0.44 0.8

0.98

0.81

1.33

0.09 0.31

0.22

0.23

0.37

0.24

0.08

0.07 0.11

0.15

0.13

0.21

0.59 2.02

1.46

1.41

2.32

1.64

0.58

0.44 0.69

0.86

1.33

0.08 0.29

0.21

0.2

0.35

0.24

0.09

0.07 0.1

0.13

0.2

REE

60.26 208.26

134.9

135.33

185.29

151.8

46.82

39.04 45.42

70.13

92.52

115.29

GEOCHEMISTRY OF THE PERMIAN SANDSTONES FROM THE MALUŽINÁ FORMATION (SLOVAKIA)

GEOLOGICA CARPATHICA

GEOLOGICA CARPATHICA, 2013, 64, 1, 23—38

Table 1: Continued from previous page.

Sample

26-VD 27-VD 30-VD 31-VD 32-VD 33-VD 34-VD 36-VD 38-VD 39-VD 40-VD 42-VD 43-VD

Major elements (wt. %)
SiO

74.22 67.83 72.71 72.97 75.25 75.85 74.03 72.52 74.29 76.6

75.14 77.52 80.11

TiO

0.37 0.63 0.44 0.44 0.22 0.35 0.3

0.54 0.38 0.33 0.4

0.3

0.11

12.51 13.31 13.73 13.3

13.48 12.46 12.31 13.74 13.19 12.18 13.08 11.89 11.47

2.15 3.66 2.75 2.89 1.71 2.99 2.71 2.6

2.42 2.15 2.14 1.86 0.61

MnO

0.06 0.08 0.04 0.04 0.02 0.03 0.04 0.07 0.04 0.03 0.05 0.03 0.01

MgO

1.09 1.01 1.03 1.36 0.8

0.81 0.88 1.8

0.48 0.41 0.68 0.49 0.08

CaO

1.47 3.3

0.75 0.74 0.42 0.5

1.57 0.83 1.23 0.75 1.36 0.72 0.42

3.4

2.97 5.29 4.86 4.41 3.27 3.45 3.5

5.08 5.03 4.41 4.4

5.66

1.4

2.08 1.16 1.15 1.71 1.45 1.53 0.97 0.92 0.85 1.2

1.01 0.46

0.09 0.16 0.1

0.1

0.06 0.09 0.09 0.06 0.1

0.09 0.11 0.07 0.04

LOI

3.1

4.8

1.9

1.8

2.2

3.3

1.8

1.5

1.3

1.6

0.9

Total

99.86 99.83 99.9

99.85 99.88 100

99.91 99.93 99.93 99.92 99.87 99.89 99.87

O/K

2.43 1.43 4.56 4.23 2.58 2.26 2.25 3.61 5.52 5.92 3.68 4.36 12.30

O/Na

0.41 0.70 0.22 0.24 0.39 0.44 0.44 0.28 0.18 0.17 0.27 0.23 0.08

+ MgO 3.24 4.67 3.78 4.25 2.51 3.80 3.59 4.40 2.90 2.56 2.82 2.35 0.69

/SiO

0.17 0.20 0.19 0.18 0.18 0.16 0.17 0.19 0.18 0.16 0.17 0.15 0.14

CIA

Trace elements (ppm)
Sc

8.5

6.4

8.6

4.3

4.2

2.9

4.1

3.8

0.8

15.1

18.7

14.2

13.1

13.2

15.9

9.4

8.2

7.8

5.4

3.3

2.7

3.6

3.8

2.5

5.7

1.6

5.1

3.3

5.9

3.2

11.8

13.7

12.8

12.4

11.5

11.9

13.8

11.6

10.5

12.2

10.1

8.2

51.4

86.4

43.4

43.1

49.4

44.9

46.8

33.7

32.4

43.8

37.5

12.6

102.2 126 217.8 223.3 109 110.8 126.2 152.7 438.6 242.1 370.2 268.3

252.3

30.7

16.1

15.7

11.3

11.5

17.8

14.7

16.5

12.6

7.5

198.4 354.8 179.9 213.4 136.8 132.5

96.6 169.8 129.9 118.4 159.9 134.7

83.6

7.6

12.1

8.6

8.3

4.7

5.9

12.1

7.2

7.3

7.5

6.8

2.4

7.9

2.4

2.6

1.9

1.4

1.7

4.2

1.5

1.4

2.3

1.7

0.6

245 316 328 226 492 257 544 338 228 390 328 212

1175

6.3

10.5

4.9

5.9

3.8

3.3

2.7

4.6

3.6

3.7

4.7

3.7

2.2

0.6

0.7

0.4

0.5

0.7

0.9

0.7

0.2

1.5

2.3

1.2

1.1

0.6

0.9

0.8

1.4

1.1

0.9

0.5

6.7

15.3

7.9

5.1

2.2

10.2

12.9

7.9

4.7

4.2

4.3

14.5

7.8

8.9

6.9

4.9

8.9

6.7

8.7

6.3

5.9

2.2

2.5

2.7

1.9

1.2

1.1

2.1

1.9

1.5

1.9

1.4

0.9

Rare earth elements (ppm)
La

22.6

30.6

21.2

24.6

23.2

15.3

28.5

39.1

37.8

19.7

46.4

66.6

44.2

53.4

51.7

32.7

33.6

53.6

63.2

70.3

67.3

42.6

38.5

5.31 7.61 5.19 5.92 5.73

3.72

4.66 6.4

6.97

7.69

7.61

4.97 4.53

20.3

29.6

20.4

23.1

21.6

14.8

17.7

24.8

23.4

28.6

28.1

17.6

17.1

4.09 6.33 3.67

4.15 3.28

2.56

3.35

4.09

3.78

4.29

4.46

3.28 2.68

0.93 1.29 0.82

0.95 0.75

0.62

1.05

0.92 1

0.98

1.04

0.79 0.67

3.63 5.78

3.39 2.39

2.22 3.2

3.41

3.07

3.36

3.47

2.63 2.02

0.61 0.97

0.5

0.56 0.36

0.34

0.49

0.54

0.45

0.49

0.52

0.42 0.27

3.16 5.16

2.61

2.81

2.01 2

2.73

3.03

2.44

2.42

2.82

2.32 1.37

0.69 1.03

0.57

0.55

0.37

0.43

0.54

0.58

0.48 0.5

0.6

0.44 0.24

1.94 3.05

1.68

1.57

1.15

1.39

1.59

1.75

1.46

1.43

1.72

1.31 0.63

0.31 0.44

0.27

0.25

0.17

0.21

0.25

0.27

0.22

0.27 0.2

0.1

1.98 2.9

1.69

1.55

1.11

1.31

1.46

1.85

1.38

1.39

1.65

1.12 0.53

0.29 0.41

0.25

0.24

0.16 0.2

0.23

0.27

0.21

0.2

0.25

0.17 0.09

REE

112.24 161.77 106.05 123.04 113.98 77.8

91.85 130.01 147.06 160.97 157.61 98.85 88.43

The trace element relationships illustrate the chemical coher-
ence and uniformity of the Malužiná Formation sandstones.

Rare earth elements

The rare earth elements (REE) concentrations of the

Malužiná Formation sandstones are shown as chondrite-nor-

malized patterns in Fig. 5. The sandstones have REE contents,
ranging  between  39—208 ppm  with  an  average  of  114 ppm,
comparable to average UCC (143 ppm; Taylor & McLennan
1985).  The  chondrite-normalized  REE  distribution  patterns
are about the same for all Malužiná Formation sandstones and
are  similar  to  that  of  the  average  Post-Archean  Australian
Shale  (PAAS;  Taylor  &  McLennan  1985).  The  sandstones

VĎAČNÝ, VOZÁROVÁ and VOZÁR

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GEOLOGICA CARPATHICA, 2013, 64, 1, 23—38

show slight LREE-enriched and relatively flat HREE patterns
with negative Eu anomalies (Fig. 5). Negative Eu anomalies
are only very slightly marked.

Discussion

Sorting and weathering effects

The Th/U ratio in most upper crustal rocks is typically about

3.5 to 4.0 (McLennan et al. 1993). During sedimentation, U is
readily oxidized to the soluble U

state and may be lost to ore

deposits, leading to an elevation in the Th/U ratio. Thus, Th/U
ratios may be useful in interpreting sedimentary recycling his-
tories  (McLennan  et  al.  1990).  In  sedimentary  rocks,  Th/U
values  higher  than  4.0  may  indicate  intense  weathering  in
source  areas  or  sediment  recycling,  meaning  derivation  from
older sedimentary rocks (Asiedu et al. 2000; Rahman & Suzuki

2007).  Th/U  ratios  in  the  Malužiná  Formation  sandstones
range  from  2.9  to  7.9,  with  an  average  of  4.9,  indicating  the
derivation of these sediments from unequally weathered frag-
ments  of  the  upper  crust.  The  Th/U  versus  Th  plot  for  the
Malužiná  Formation  sandstones  (Fig. 6)  shows  a typical  dis-
tribution  similar  to  the  average  values  of  fine-grained  sedi-
mentary  rocks  reported  by  Taylor  &  McLennan  (1985)  and
follows the normal weathering trend (McLennan et al. 1993).
The trend of depleted mantle sources in a few samples is de-
rived  from  the  addition  of  detrital  material  from  the  eroded
synsedimentary  continental  tholeiites.  This  is  also  docu-
mented  by  the  presence  of  basic  volcanic  rock  fragments  in
our  samples  and  by  the  occurrences  of  the  Malužiná  Forma-
tion  sandstones  along  with  basic  volcanics  and  their  tuffs
which have a tholeiite magmatic trend (Fig. 1b; Vozár 1997;
Dostal et al. 2003).

Since a number of heavy minerals are dominated by ele-

ments that are trace elements in most sedimentary rocks (e.g.
Zr in zircon, REE in monazite and allanite), it is possible to
evaluate the role of heavy mineral concentration during sedi-
mentary sorting (McLennan 1989). The sedimentary sorting
and  recycling  can  be  monitored  by  a plot  of  Th/Sc  against
Zr/Sc  (McLennan  et  al.  1993).  A  simple  positive  correlation
between  Th/Sc  and  Zr/Sc  ratios  is  exhibited  by  first-cycle
sediments,  whereas  there  is  a  substantial  increase  in  Zr/Sc
with far less increase in Th/Sc in recycled sediments (Asiedu
et al. 2000; Rahman & Suzuki 2007). However, if first-cycle
sediments  are  derived  from  largely  plutonic  sources,  they
could  also  show  a  trend  of  increased  Zr/Sc  and  almost  con-
stant Th/Sc (Roser & Korsch 1999). On the Th/Sc versus Zr/Sc
diagram, the Malužiná Formation sandstones follow a general
trend  which  is  consistent  with  that  of  first-cycle  sediments
(Fig. 7).  This  suggests  their  direct  derivation  from  igneous
and,  according  to  our  thin-section  observations,  also  from
metamorphic rocks. From Figs. 6 and 7 it can be, therefore,

Fig. 4. Multi-element diagram of the Malužiná Formation sandstones
normalized to the composition of the average upper continental crust
(UCC). The elements are arranged from left to right in order of in-
creasing compatibility in a small fraction melt of the mantle. The
average UCC data are from Taylor & McLennan (1981).

Fig. 5.  Chondrite-normalized  REE  diagram  for  sandstone  samples
from  the  Malužiná  Formation.  Note  the  similarity  in  the  patterns
with LREE enrichment, flat HREE distributions and the ubiquitous
negative Eu-anomaly. REE chondrite-normalizing factors are from
Boynton  (1984).  Post-Archean  Average  Australian  Shale  values
from Taylor & McLennan (1985).

Fig. 6. Plot of Th/U versus Th for the Malužiná Formation sand-
stones (after McLennan et al. 1993).

GEOCHEMISTRY OF THE PERMIAN SANDSTONES FROM THE MALUŽINÁ FORMATION (SLOVAKIA)

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GEOLOGICA CARPATHICA, 2013, 64, 1, 23—38

inferred that the bulk of the Malužiná Formation sandstones
were directly derived from igneous and metamorphic rocks
that had undergone some degree of weathering.

Nesbitt & Young (1982, 1984, 1989) introduced a chemical

index of alteration (CIA), which provides a means of quanti-
fying the degree of weathering (chemical alteration) to which
silicate materials have been subjected. The CIA is calculated
according to CIA=[(Al

)/(CaO*+Na

O+K

O+Al

)] 100,

where  the  oxides  are  expressed  as  molar  proportions  and
CaO*  is  CaO  in  silicates  only  (as  opposed  to  that  in  phos-
phates  or  carbonates).  However,  if  CaO < Na

O, then the

molecular CaO is accepted as approximate CaO* (McLennan
1993). This applies to all studied Malužiná Formation sand-
stones. To calculate a reliable CIA, a rock needs to contain
less than 75 wt. % SiO

and less than 1 wt. % CaO. Both these

conditions are met for the majority of the studied sandstones
(Table 1),  making  our  interpretation  of  the  CIA  values  reli-
able. High CIA values (i.e. 76—100) indicate intensive chemi-
cal  weathering  in  the  source  areas.  Conversely,  low  CIA
values  (i.e.  50  or  less)  indicate  the  near  absence  of  chemical
alteration  or  unweathered  source  areas,  and  consequently
might  reflect  cool  and / or  arid  conditions  (Fedo  et  al.  1995).
Low CIA values can also be interpreted as a result of an ex-
tremely  high  erosion  rate.  The  CIA  values  for  the  Malužiná
Formation sandstones vary from 45 to 68, with an average of
55,  indicating  low  to  moderate  chemical  weathering  of  the
source  area.  Consequently,  they  reflect  arid  conditions  and
an extremely high erosion rate. The average CIA value (55)
of  the  Malužiná  Formation  sandstones  is  comparable  to
those of feldspar (50), unweathered felsic plutonic and vol-
canic  rocks  (45—55)  as  well  as  the  UCC  (50)  (Fedo  et  al.
1995).  The  CIA  values  of  the  studied  sandstones  are  also

plotted in the Al

—(CaO* + Na

O)—K

O (A—CN—K) dia-

gram (Fig. 8), which may express much of the chemical varia-
tion resulting from weathering. Unweathered rocks cluster
along the left-hand side of the plagioclase-K-feldspar join line
in the A—CN—K system (Nesbitt & Young 1984). The weath-
ered material moves away from the source rocks along a line
subparallel to the Al

—(CaO* + Na

O) join due to prior re-

moval of Ca and Na in preference to Al and K (Fig. 8). The
composition of the source rocks can also be predicted back
along the trend. All the samples studied here plot a little away
from the plagioclase-K-feldspar join line and parallel to the
Al

—(CaO* + Na

O) edge, supporting the conclusion that

the Malužiná Formation sandstones were derived from an in-
termediate igneous source terrain in general. Although the ef-
fect of post-depositional processes in altering the mineralogy
and chemistry cannot be completely neglected, both the tex-
tural and the chemical immaturity of the investigated sand-
stones strongly suggest that their bulk chemistry, including the
Na

O enrichment (Table 1), was inherited from the source area.

The Rb/Sr ratios of sediments also monitor the degree of

source-rock  weathering  (McLennan  et  al.  1993).  During
weathering  (and  in  many  cases,  diagenesis),  there  is
a substantial increase in the Rb/Sr ratio of most rocks. This is
because  Rb

, a large alkali trace element (1.72

for 12-fold

Fig. 7. Plot of Th/Sc versus Zr/Sc for the Malužiná Formation sand-
stones (after McLennan et al. 1993). Analysed sandstone samples,
which are less affected by sedimentary sorting and recycling, show
a simple correlation for these ratios. This relationship is interpreted
as due to the compositional variations of the provenance.

Fig. 8. The Malužiná Formation sandstones plotted on the Al

—

(CaO* + Na

O)—K

O diagram (A—CN—K) after Nesbitt & Young

(1984,  1989)  and  Fedo  et  al.  (1995).  The  relation  between  the  CIA
scale (Nesbitt & Young 1982) and the triangle is shown on the right
side  of  the  diagram.  The  A—CN—K  diagram  shows  the  weathering
trends for average granite and average gabbro. The advanced weath-
ering trend for granite is also shown. The solid line linking crosses is
the  compositional  trend  in  pristine  average  igneous  rocks  (data  of
Le Maitre 1976). B – basalt, Ga – gabbro, Di – diorite, Da – dac-
ite, G – granite, Rh – rhyolite. The horizontal solid line is the pla-
gioclase-K-feldspar join. The data are plotted as molar proportions and
the compositions of plagioclase, K-feldspar, muscovite, illite, kaolinite
and smectite are shown. Modal carbonate cement is trivial, however,
and the calculated proportions are thus close to actual values. CaO*
represents the CaO associated with the silicate fraction of the sample.

VĎAČNÝ, VOZÁROVÁ and VOZÁR

GEOLOGICA CARPATHICA

GEOLOGICA CARPATHICA, 2013, 64, 1, 23—38

coordination), is more readily retained on exchange sites of
clays than the smaller Sr

(1.26

for eight fold coordina-

tion). The Malužiná Formation sandstones have an average
Rb/Sr ratio of 0.29, and this value is close to that of the aver-
age upper continental crust (0.32) but significantly lower than
the average Post-Archean Australian Shale (0.80; McLennan
et al. 1983). This suggests that the degree of source area weath-
ering was most probably low to moderate rather than intense.

The Al—Ti—Zr ternary diagram monitors the effects of sort-

ing processes (Garcia et al. 1994). On this diagram, mature
sediments consisting of both sandstones and shales show
a wide range of TiO

/Zr variations, whereas immature sedi-

ments of sandstones and shales show a more limited range of
TiO

/Zr variations (Asiedu et al. 2000). On the Al—Ti—Zr dia-

gram, the Malužiná Formation sandstones are confined in
the centre with a limited range of TiO

/Zr variations, sug-

gesting poor sorting and rapid deposition of the studied
sandstones (Fig. 9). This is completely corroborated by their
sedimentary structures and mineral composition.

(Fig. 10). These petrographical features imply a source area
in which granitic and gneissic rocks plus sedimentary and
metasedimentary rocks dominated, while andesitic to basaltic
volcanic rocks were much less abundant.

The Malužiná Formation sandstones have high K

O and Rb

concentrations and a uniform K/Rb ratio of 242 that lies close
to a typical differentiated magmatic suite or “main trend” with
a ratio of 230 (Fig. 11; Shaw 1968). This feature emphasizes

Fig. 9. Al—Ti—Zr plot for the Malužiná Formation sandstones. The
solid contour refers to the observed range of compositions in clastic
sediments. CAS refers to the fields of calc-alkaline suites and SPG
refers to fields of strongly peraluminous granites (after Garcia et al.
1994).

Fig. 10. Triangular QFL plot showing framework modes for the Per-
mian Malužiná Formation sandstones: Q is total quartzose grains, in-
cluding monocrystalline Qm and polycrystalline Qp varieties; F is
total feldspar grains; L is total unstable lithic fragments. Provenance
fields from Dickinson & Suczek (1979).

Fig. 11. Distribution of K and Rb in the Malužiná Formation sand-
stones relative to a K/Rb ratio of 230 ( = main trend of Shaw 1968).
Average upper and lower continental crust from Taylor & McLennan
(1985).

Source-rock compositions and provenance

As apparent from the Results section and the previous

chapter,  the  mineral  and  chemical  composition  of  the
Malužiná Formation sandstones is a record of characteristics
of  the  source  area.  Therefore,  whole-rock  geochemistry  of
the investigated sandstones can be used as a suitable tool for
unravelling  their  provenance.  Our  following  interpretations
based on chemical composition are in agreement with petro-
graphic analysis which indicates that the detrital constituents
of  the  Malužiná  Formation  sandstones  were  derived  from
a basement  uplift  and  recycled  orogen  tectonic  provenance

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Fig. 12. Plot of La/Th versus Hf for the Malužiná Formation sand-
stones (compositional fields are after Floyd & Leveridge 1987).

the chemically coherent nature of the sandstones and deriva-
tion  mainly  from  acid  to  intermediate  magmatic  rocks.  As
mentioned  above,  the  original  material  of  the  Malužiná  For-
mation  sandstones  was  only  slightly  weathered  and  was  de-
posited rapidly. Therefore, there was no further redistribution
in or component removal from the original material. The uni-
form K/Rb ratio indicates that diagenesis and very low-grade
metamorphism  was  isochemical  in  the  Malužiná  Formation,
and there was no or very little elemental redistribution.

A plot of La/Th against Hf (Fig. 12) provides a useful tool

for  bulk  rock  discrimination  between  different  arc  composi-
tions and sources (see also Asiedu et al. 2000). Felsic compo-
sition-dominated arcs have low and uniform La/Th ratios (less
than 5) and Hf contents of about 3—7 ppm. With the progres-
sive unroofing of the arc and/or incorporation of sedimentary
basement rocks, the Hf content increases via the release of zir-
con  (Floyd  &  Leveridge  1987).  The  compositions  of  the
Malužiná  Formation  sandstones  suggest  derivation  mainly
from  felsic  igneous  rocks  with  minor  mafic  input  (Fig. 12).
This minor mafic input is also documented by the scarce oc-
currences of basic lathwork rock fragments in the framework

of the studied sandstones. Only two samples have Hf concen-
trations above 10 ppm, which is much higher than considered
to be typical of felsic rocks. This may be indicative of a pas-
sive margin tectonic setting and a sedimentary source, which
is well-documented by our observations of sedimentary rock
fragments in thin sections from these sandstones.

The ferromagnesian trace elements Cr, Ni, Co, and V show

a generally similar behaviour in magmatic processes, but they
may  be  fractionated  during  weathering  (Feng  &  Kerrich
1990). Very high levels of Cr and Ni have been used by vari-
ous authors (e.g. Hiscott 1984; Wrafter & Graham 1989) to in-
fer  an  ultramafic  provenance  for  sediments.  The  elevated
values  of  Cr  ( > 150 ppm)  and  Ni  ( > 100 ppm)  and  a ratio  of
Cr/Ni  between  1.3—1.5  are  diagnostic  of  ultramafic  rocks  in
the  source  region  (Garver  et  al.  1996).  Higher  Cr/Ni  ratios
probably indicate derivation of these elements from mafic vol-
canic rocks (Garver & Scott 1995). The Malužiná Formation
sandstones  have  low  levels  of  Cr  (14—109 ppm;  on  average
43 ppm)  and  Ni  (5—19 ppm;  on  average  10 ppm),  and  Cr/Ni
ratio of 4.61. This may suggest either a minor amount of ma-
fic  input  into  the  depositional  system  or  else  that  trace  ele-
ments  could  have  travelled  into  the  depositional  basin  as
adsorbed ions on clays (McCann 1991). Vanadium concentra-
tions (8—57 ppm; on average 33 ppm) of the Malužiná Forma-
tion sandstones are relatively higher than the levels commonly
recorded  in  sediments  (about  20 ppm),  and  given  that  V is
concentrated  in  mafic  rocks,  they  suggest  some  mafic  input
into  the  depositional  system  (McCann  1991).  On  the  other
hand, the slightly higher content of vanadium in our samples
may also be a result of concentration of heavy minerals.

The high field strength elements (HFSE) such as Zr, Nb, Hf,

Y, Th are preferentially partitioned into melts during crystalli-
zation (Feng & Kerrich 1990), and as a result these elements
are  enriched  in  felsic  rather  than  mafic  sources.  These  ele-
ments  are  thought  to  reflect  provenance  compositions  as  a
consequence of their generally immobile behaviour (Taylor &
McLennan 1985). The REE and Sc also give an indication of
source  compositions  because  of  their  relatively  low  mobility
during  sedimentation  (Bhatia  &  Crook  1986).  REE  and  Th
abundances are higher in felsic than in mafic igneous source
rocks and in their weathered products, whereas Co, Sc, and Cr
are  more  concentrated  in  mafic  than  in  felsic  igneous  rocks
and in their weathered products. Mafic and felsic source rocks
differ  significantly  in  their  ratios  of  Eu/Eu*,  La/Sc,  Th/Sc,
La/Co, Th/Co, and Cr/Th and hence provide useful informa-
tion about the provenance of sedimentary rocks (e.g. Cullers

Table 2: Range of elemental ratios of the Permian Malužiná Formation sandstones compared to elemental ratios in sediments derived from
felsic rocks, mafic rocks, and in the upper continental crust.

– After Cullers et al. (1988), Cullers (1994, 2000), and Cullers & Podkovyrov (2000).

– After Taylor & McLennan (1985) and McLennan (2001).

Elemental ratio

Maluziná Formation

sandstones (n = 25)

Ranges in sediments

from felsic sources

Ranges in sediments

from mafic sources

Upper continental

crust

Eu/Eu*

0.64–0.97 0.40–0.94 0.71–0.95

0.63

La/Sc

3.17–19.70 2.50–16.3 0.43–0.86

2.21

Th/Sc

0.98–5.90 0.84–20.5 0.05–0.22

0.79

La/Co

2.22–24.63 1.80–13.8 0.14–0.38

1.76

Th/Co

0.74–7.38 0.04–3.25 0.04–1.40

0.63

Cr/Th

1.67–15.86

4.00–15.0

25.00–500

7.76

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GEOLOGICA CARPATHICA, 2013, 64, 1, 23—38

et  al.  1988;  Cullers  1994,  2000;  Cullers  &  Podkovyrov
2000). In this study, the Eu/Eu*, La/Sc, Th/Sc, La/Co, Th/Co,
and Cr/Th values of the Permian Malužiná Formation sand-
stones are more similar to values for sediments derived from
felsic source rocks than to those for mafic source rocks (Ta-
ble 2),  suggesting  prevalent  derivation  from  felsic  source
rocks. The higher LREE/HREE ratios and negative Eu anoma-
lies  (0.64—0.97)  of  the  Malužiná  Formation  sandstones  also
bear the characteristics of felsic source rocks (after Taylor &
McLennan 1985; Wronkiewicz & Condie 1989).

A discriminant function diagram has been proposed by

Roser & Korsch (1988) to distinguish between sediments
whose provenance is primarily mafic (first-cycle basaltic and
lesser andesitic detritus), intermediate (dominantly andesitic
with subordinate rhyolitic and dacitic detritus) or felsic igne-
ous (acid plutonic and volcanic detritus) and quartzose sedi-
mentary (mature polycyclic quartzose detritus). Their study
was based upon 248 chemical analyses in which Al

/SiO

O/Na

O and Fe

3(tot)

+ MgO proved the most valuable dis-

criminants.  A plot  of  the  first  two  discriminant  functions
based upon the oxides of Ti, Al, Fe, Mg, Ca, Na and K most
effectively  differentiates  between  the  four  provenances
(Fig. 13).  In  this  diagram,  the  majority  of  the  Malužiná  For-
mation sandstones plot on the felsic igneous provenance field
suggesting  that  the  source  area  for  the  Malužiná  Formation
sandstones had an average felsic composition. Using the ratio
discrimination  diagram  in  which  discriminant  functions  are
based upon the ratios of TiO

, Fe

3(tot)

, MgO, Na

O and K

all to Al

(Fig. 14), the Malužiná Formation sandstones plot

in the felsic and intermediate igneous provenance fields. This
distribution may indicate a significant contribution of detritus

Fig. 13. Discriminant function diagram using major elements for the
provenance  signatures  of  the  Malužiná  Formation  sandstones  (dia-
gram  after  Roser  &  Korsch  1988).  Fields  for  predominantly  mafic,
intermediate and felsic igneous provenances are shown with the field
for  a quartzose  sedimentary  provenance.  The  Malužiná  Formation
sandstones plot in the felsic igneous provenance field demonstrating
that  they  are  derived  from  a silicic  crystalline  (plutonic-metamor-
phic) terrain with a lesser intermediate-acid volcanic component.

from continental transform boundaries or rifted continental
margins. Both these tectonic settings expose deep-seated plu-
tonic rocks with dominant feldspathic detrital material.

Figure 4 shows a multi-element diagram of the Malužiná

Formation sandstones normalized to the average UCC (Taylor
& McLennan 1981). The figure shows that, with the excep-
tion of the high Ba values and low Nb, Sr and Tb values, the
Malužiná  Formation  sandstones  have  compositions  similar
to  those  of  the  average  UCC  and  PAAS.  This  feature  indi-
cates that the sandstones were derived mainly from the upper
continental  crust,  for  which  granitic  composition  is  charac-
teristic.  As  discussed  earlier,  the  high  Ba  values  for  the
Malužiná  Formation  sandstones  reflect  a significant  pres-
ence of K-feldspar.

Tectonic setting of source area

The mineralogy of the Malužiná Formation sandstones

clearly indicates their derivation from predominantly acid ig-
neous  rocks,  with  less  admixture  of  clastic  detritus  from
synsedimentary acid to intermediate/basic volcanic rocks and
from low-grade metasedimentary rocks. According to the in-
terpretations of Dickinson & Suczek (1979), Dickinson et al.
(1983)  and  Ingersoll  (1990),  these  types  of  clastic  detritus
may  be  derived  from  uplifted  basement  blocks  or  a  rifted
continental  margin  (Fig. 10).  The  latter  tectonic  setting  and
rapid  erosion  and  transport  are  also  well-documented  by  the
compositional diagnostic features of the Malužiná Formation
sandstones,  which  include  the  lowest  polycrystalline/mono-
crystalline quartz ratios, the lowest content of lithic fragments,
and nearly equal amounts of plagioclase and alkali feldspars.

Although most studies of tectonic setting of the source

area have relied on interpretations based upon sandstone
mineralogy, several studies have shown that major- and

Fig. 14. Discriminant function diagram using major element ratios
for the provenance signatures of the Malužiná Formation sand-
stones (diagram after Roser & Korsch 1988). Fields for dominantly
mafic, intermediate and felsic igneous provenances are shown with
the field for a quartzose sedimentary provenance.

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GEOLOGICA CARPATHICA, 2013, 64, 1, 23—38

Fig. 15. Tectonic discrimination diagram of Roser & Korsch (1986)
for the Permian Malužiná Formation sandstones.

Fig. 16. Major element composition plots of the Malužiná Formation sandstones for tectonic setting discrimination (after Bhatia 1983). Plot
of TiO

and Al

/SiO

versus Fe

+ MgO. (Fe

represents total iron as Fe

.) Dashed lines mark the major fields representing various

tectonic settings.

trace-element  geochemistry  also  reflect  provenance  differ-
ences  that  depend  upon  tectonic  setting  (e.g.  Bhatia  1983;
Bhatia  &  Crook  1986;  Roser  &  Korsch  1986;  Skilbeck  &
Cawood  1994).  Both  trace  elements  (particularly  relatively
immobile elements such as La, Y, Th, Zr, Hf, Nb, Ti, and Sc)
and major elements have proved to be useful in studies of the
tectonic setting of the source area.

The SiO

content and K

O/Na

O ratios in sandstones ap-

pear to be particularly sensitive indicators of geotectonic set-
ting of the source area. Roser & Korsch (1986) present
a chemical model, based on K

O/Na

O ratios and SiO

con-

tent, for discriminating the tectonic setting of the source area
(Fig. 15). By using these chemical parameters, they were

able to discriminate between samples from three major tec-
tonic settings: passive margin (PM), active continental mar-
gin  (ACM),  and  oceanic  island  arc  margin  (ARC).  Some
overlaps  occur  between  the  composition  fields  shown  in
Fig. 15,  but  overall  the  discriminating  power  of  the  tech-
nique  appears  to  be  reasonably  good  (Armstrong-Altrin  &
Verma 2005; Boggs 2009). On a K

O/Na

O versus SiO

dia-

gram, the Malužiná Formation sandstones may be classified
as having an active continental margin provenance (Fig. 15).
Hence the Malužiná Formation sandstones may represent
quartz-intermediate sediments derived from a tectonically ac-
tive continental margin adjacent to active plate boundaries.

Sandstones from oceanic island arc, continental island arc,

active continental margin, and passive margin settings are
variable in composition, particularly in their Fe

3(tot)

+ MgO,

/SiO

, K

O/Na

O and Al

/(CaO + Na

O) contents.

Bhatia (1983) used this chemical variability to discriminate
between the different tectonic settings on a series of bivariate
plots, two of which are shown in Fig. 16. On these plots, most
of the Malužiná Formation sandstones fall in the general area
of active continental margin field (Fig. 16).

Bhatia & Crook (1986) identified the elements La, Th, Zr,

Nb, Y, Sc, Co and Ti as the most useful in discriminating be-
tween  sandstones  from  different  tectonic  environments.  Dis-
tinctive  fields  for  four  environments  –  oceanic  island  arc,
continental  island  arc,  active  continental  margin  and  passive
margin – are recognized on bivariate plots of La vs. Th, La/Y
vs. Sc/Cr, Ti/Zr vs. La/Sc and the trivariate plots La—Th—Sc,
Th—Sc—Zr/10  and  Th—Co—Zr/10.  On  a  Ti/Zr  vs.  La/Sc  plot
(Fig. 17), the Malužiná Formation sandstones again plot mainly
in the field of active continental margin sediments. This distri-
bution  suggests  that  substantial  amounts  of  detritus  were  de-
rived from acid igneous rocks of a dissected magmatic arc and
from  granite-gneisses  and  siliceous  volcanics  of  an  uplifted

VĎAČNÝ, VOZÁROVÁ and VOZÁR

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GEOLOGICA CARPATHICA, 2013, 64, 1, 23—38

basement.  The  original  depositional  basin  of  the  Malužiná
Formation  sandstones  was  probably  developed  on  a  rifted
thick  continental  crust  behind  an  active  continental  margin.
This  tectonic  setting  can  also  comprise  rocks  of  older  fold
belts.  The  present  interpretation  is  in  good  agreement  with
previous  studies  (Vozárová  &  Vozár  1988;  Vozár  1997;
Dostal et al. 2003).

Paleogeographical reconstruction

The Permian sedimentary basin of the Malužiná Formation

originated as a consequence of post-Variscan extensional tec-
tonics.  It  was  a  part  of  a  large  geodynamic  zone  connected
with  the  internal  part  of  the  Variscan  orogenic  domain,  in
which rift-related and strike-slip continental post-orogenic ba-
sins were developed during the Pennsylvanian-Permian period
(Vozárová  et  al.  2009).  Relics  of  the  volcano-sedimentary
Malužiná  Formation  sequences  are  present  in  the  Western
Carpathians  within  the  basal  part  of  the  Hronicum  rootless
nappe system. The mineral composition and geochemistry of
the  Malužiná  Formation  sandstones  permitted  us  to  interpret
the  character  of  the original basement rocks. With respect to
our  results,  the  Malužiná  rift  system  originated  on  a  high-
grade crystalline core complex penetrated with huge masses of
syn- and late-orogenic igneous rocks, what is characteristic for
the  Variscan  terranes  of  the  Central  Western  Carpathians
(Biely et al. 1996; Vozárová et al. 2009 and references therein).
The axial part of the former rift-trough is designated by the
occurrences  of  continental  tholeiites,  from  which  a  variable
amount  of  clastic  grains  were  derived  into  the  former  sedi-
mentary basin. The small admixture of low-grade metasedi-
mentary lithic fragments could be derived from the Variscan
orogenic  zone.  Based  on  these  facts  we  suppose  that  the
Hronicum rift-related basin originated on the continental crust
parallel to the Variscan orogenic belt.

Fig. 17. Ti/Zr versus La/Sc plot of the Malužiná Formation sand-
stones for tectonic setting discrimination (after Bhatia & Crook 1986).

Conclusions

The geochemistry of the Permian sandstones from the

Malužiná Formation in the Malé Karpaty Mts was studied to
determine their source-area weathering, provenance, and the
tectonic setting of the source area.

The Permian Malužiná Formation sandstones have domi-

nantly  quartzofeldspathic  and  quartzolithic  composition  with
predominance  of  quartz.  They  are  classified  as  arkose,  subar-
kose, lithic subarkose, and feldspathic litharenite. The Malužiná
Formation  sandstones  contain  abundant  feldspars,  volcanic,
fine-grained igneous (aplitic) and metasedimentary lithic grains,
indicating  that  the  detrital  constituents  were  derived  from
a basement uplift and recycled orogen tectonic provenance.

The CIA values for the Permian Malužiná Formation sand-

stones  vary  from  45  to  68  with  an  average  of  55,  indicating
low  to  moderate  chemical  weathering  of  their  source  area.
Consequently,  they  reflect  arid  conditions  and  an  extremely
high erosion rate. The average CIA value (55) is a little above
than that of the CIA value (50) of the upper continental crust.

Eu/Eu*, La/Sc, Th/Sc, La/Co, Th/Co and Cr/Th ratios in-

dicate  derivation  of  these  sandstones  from  felsic  source
rocks.  In  the  same  way,  the  predominantly  felsic  composi-
tion  of  the  Malužiná  Formation  sandstones  is  supported  by
the REE plots. Thus, the existence of huge complexes of ma-
fic/ultramafic rocks in the source region is most unlikely.

The geochemical characteristics preserve the signatures of

a felsic and intermediate igneous provenance for the Permian
Malužiná  Formation  sandstones.  This  is  in  good  agreement
with  framework  mineralogy.  Tectonic  discrimination  dia-
grams  suggest  mostly  an  active  continental  margin  setting
for the Malužiná Formation sandstones.

The Malužiná Formation sandstones were derived espe-

cially from fault-bounded, uplifted basement areas in conti-
nental-block  provenances,  where  high  relief  and  rapid
erosion  of  uplifted  sources  gave  rise  to  quartzofeldspathic
sands  of  classic  arkosic  character.  The  Malužiná  Formation
sandstones could have been accumulated in basins related to
transform ruptures of continental blocks, incipient rift blocks,
or zones of wrench tectonism within continental interiors.

The Malužiná rift system originated on a high-grade crys-

talline  core  complex  penetrated  with  huge  masses  of  syn-
and  late-orogenic  igneous  rocks,  as  characteristic  for  the
Variscan  terranes  of  the  Central  Western  Carpathians.  A
variable amount of clastic grains were derived from the con-
tinental  tholeiites  into  the  former  sedimentary  basin.  The
small  admixture  of  low-grade  metasedimentary  lithic  frag-
ments could be derived from the Variscan orogenic zone. We
suppose  that  the  Hronicum  rift-related  basin  originated  on
the continental crust parallel to the Variscan orogenic belt.

Acknowledgments: The authors are grateful to two anony-
mous  reviewers  for  their  positive  criticism  that  helped  im-
prove  the  manuscript.  This  work  was  supported  by  the
Slovak  Research  and  Development  Agency  under  the  Con-
tract  No.  APVV-0438-06  and  APVV-0546-11,  the  Slovak
Scientific  Grant  Agency  (Grant  No.  VEGA-2/0100/11  and
VEGA-1/0095/12),  and  Comenius  University  in  Bratislava
(Grant No. UK/236/2010).

GEOCHEMISTRY OF THE PERMIAN SANDSTONES FROM THE MALUŽINÁ FORMATION (SLOVAKIA)

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GEOLOGICA CARPATHICA, 2013, 64, 1, 23—38

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