GeolCarp_Vol66_No1_3

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, FEBRUARY 2015, 66, 1, 3—17 doi: 10.1515/geoca-2015-0007

Introduction

Hronicum, as a rootless multi-nappe unit in the tectonic struc-
ture of the Inner Western Carpathians, is characterized by domi-
nant Carboniferous/Permian volcanic-sedimentary sequences
defined by Vozárová & Vozár (1981, 1988) as the Ipoltica
Group. The Ipoltica Group (IG) is subdivided into the Nižná
Boca Formation (NBF – Late Pennsylvanian) and Malužiná
Formation (MF – Permian). Stratigraphic interpretation from
both lithostratigraphic units is based on lithology, palynology,
macroflora and sporadically isotopic/radiometric evidence.

The paper presents Nd and Sr isotopic data and the results

of  geochemical  study  of  Permian  Hronicum  basic  volcanics
and the associated system of subvolcanic doleritic dykes and
sills. The aim of our research was to detect the main isotopic
differences  between  individual  volcanic  eruption  phases  and
the similarity of subvolcanic dolerite dykes and sills. It can be
considered that Sr and Nd isotopes keep a record of geological
evolution (e.g. Allègre 2008) and thus, the isotopic composi-
tions  of  the  studied  volcanic  and  subvolcanic  basic  rocks
could  contribute  to  the  interpretation  of  the  magma  genesis,
the position of the magma chamber in relation to the continen-
tal  crust  and  upper  mantle.  Consequently,  they  can  solve  the
relationships between individual phases of volcanism in rela-
tion to basin evolution and individual phases of rifting.

Geochemistry and Sr, Nd isotopic composition of the Hronic

Upper Paleozoic basic rocks (Western Carpathians, Slovakia)

JOZEF VOZÁR

, JÁN SPIŠIAK

, ANNA VOZÁROVÁ

, JAKUB BAZARNIK

and JÁN KRÁi

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

jozef.vozar@savba.sk

Faculty of Natural Sciences, Matej Bell University, Tajovského 40, 974 01 Banská Bystrica, Slovak Republic; jan.spisiak@umb.sk

Faculty of Natural Sciences, Comenius University, Mlynská dolina, 842 15 Bratislava, Slovak Republic; vozarova@fns.uniba.sk

Polish Geological Institute – National Research Institute, Rakowiecka 4, 00-975 Warszawa, Poland; jakub.bazarnik@pgi.gov.pl

Dionýz Štúr State Geological Institute, Mlynská dolina 1, 817 04 Bratislava, Slovak Republic; jan.kral.ba@gmail.com

(Manuscript received July 14, 2014; accepted in revised form December 10, 2014)

Abstract: The paper presents new major and trace element and first Sr-Nd isotope data from selected lavas among the
Permian basaltic andesite and basalts of the Hronicum Unit and the dolerite dykes cutting mainly the Pennsylvanian
strata. The basic rocks are characterized by small to moderate mg

numbers (30 to 54) and high SiO

contents

(51—57 wt. %). Low values of TiO

(1.07—1.76 wt. %) span the low-Ti basalts. Ti/Y ratios in the dolerite dykes as well

as the basaltic andesite and basalt of the 1

eruption phase are close to the recommended boundary 500 between high-Ti and

low-Ti basalts. Ti/Y value from the 2

eruption phase basalt is higher and inclined to the high-Ti basalts. In spite of this

fact, in all studied Hronicum basic rocks Fe

* is lower than 12 wt. % and Nb/La ratios (0.3—0.6) are low, which is

more characteristic of low-Ti basalts. The basic rocks are characterized by Nb/La ratios (0.56 to 0.33), and negative
correlations between Nb/La and SiO

which point to crustal assimilation and fraction crystallization. The intercept for

Sr evolution lines of the 1

intrusive phase basalt is closest to the expected extrusions age (about 290 Ma) with an initial

Sr/

Sr ratio of about 0.7054. Small differences in calculated values I

document a partial Sr isotopic heterogeneity

source (0.70435—0.70566), or possible contamination of the original magma by crustal material. For Nd analyses of the
three samples, the calculated values

εCHUR (285 Ma) are positive (from 1.75 to 3.97) for all samples with only subtle

variation. Chemical and isotopic data permit us to assume that the parental magma for the Hronicum basic rocks was
generated from an enriched heterogeneous source in the subcontinental lithospheric mantle.

Key words: Western Carpathians, Hronicum Unit, Permian volcanics, geochemistry, Sr and Nd isotopic composition.

For precise determination of the geological position of

volcanic bodies and their stratigraphic stage more compre-
hensive information is needed. The main topics of our re-
search were focused on:

1. Stratification and genetic interpretation of the basic vol-

canic rocks of the Hronicum Unit in relation to basin evolu-
tion and its paleotectonic setting, with the use of Sm-Nd and
Sr-Sr isotope analyses;

2. The genetic relation of dykes in the Late Pennsylvanian

NBF – if they are related to the beginning of rifting or they
are comagmatic with Permian basalts.

In an effort to contribute to the solution of these problems,

we collected samples from a dolerite dyke (sample NT-1),
from the 1

eruption phase basaltic andesite and basalt (sam-

ples Ip-1 and NT-2) and from of the 2

eruption phase ba-

salts (samples Kv-2 and NT-3) for

Sr/

Sr and Nd-Sm

isotope analyses. The results are the first ever isotope data
from the Hronicum Late Paleozoic basic rocks.

Geological setting

The Hronicum Unit represents a system of higher nappes

which were characterized as the so-called rootless nappes
(lower Šturec nappe, higher Choč nappe – Biely & Fusán

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1967; Andrusov 1968; Andrusov et al. 1973). From the base
to the upper part, the Hronicum is composed of Upper Penn-
sylvanian to Jurassic members. In the present-day structure of
the Western Carpathians, the Upper Paleozoic of the Hronicum
Unit  are  mainly  preserved  in  the  basal  part  of  the  lower
(Šturec)  nappe.  It  may  be  delimited  in  various  areas  of  the
Western Carpathians territory (from the pre-Tertiary basement
of the Vienna Basin and the Malé Karpaty Mts in the west as
far as the Branisko and Suubica Mts in the east, from the Malá
Fatra Mts and basement of the Liptovská kotlina and Hornádska
kotlina depressions in the north to the Southern Veporicum in
the Stolické vrchy Mts) in the south. The best preserved frag-
ments of the Upper Paleozoic IG have been described from the
Nízke  Tatry  Mts  (lithostratigraphic  type  profiles  along  the
Ipoltica valley and near Nižná Boca and Malužiná villages).

The Upper Paleozoic lithostratigraphy of the Hronicum is

presented  by  two  formations  –  the  NBF  (Late  Pennsylva-
nian)  and  MF  (Permian),  belonging  to  the  IG  (Vozárová  &
Vozár 1981, 1988). The age of both formations is confirmed
by findings of the uppermost Pennsylvanian macroflora (Sitár
&  Vozár  1973),  Upper  Pennsylvanian/Permian  microflora
(Ilavská 1964; Planderová 1973, 1979) and scarce radiometric
U-Pb  dating  of  uranium  U-mineralization  (Rojkovič  1975,
1997 – Kravany beds 263—274 Ma). The 310—340 Ma age of
the presumed source area was indicated by the

Ar/

Ar dat-

ing of detrital mica from sandstones (Vozárová et al. 2005),
which suggests the age of the IG sedimentary basin younger
than 310 Ma. The position of the IG sedimentary sequence in
the underlier of the Lower Triassic Benkovský potok Forma-
tion (sensu Biely in Andrusov & Samuel (Eds.) 1984) has
been well documented.

The lithological and lithofacial characteristics, mineral com-

position of detritic material as well as the type of synsedimen-
tary  volcanism  (Vozárová  1981;  Vozárová  &  Vozár  1981,
1988)  permit  us  to  interpret  the  original  basin  as  a  conse-
quence of continental rifting in the post-collisional stage of the
Variscan orogeny (Vozárová 1996). All the above mentioned
data enable us to presuppose a sedimentary basin with a total
length of 450 to 550 km and a considerable width from sev-
eral to tens of km (Vozár 1977). The total thickness of the IG
sequence at present is 2200 to 2800 m. As a consequence of
tectonic  transport,  the  basal  part  of  the  NBF  is  tectonically
truncated. Therefore, the whole thickness of the former Penn-
sylvanian  Hronicum  basin  filling  is  unknown.  Based  on  the
findings  of  redeposited  older  Pennsylvanian  palynomorphs
(Ilavská 1964) and rock fragments (Vozárová 1981), it may be
assumed that the latest Kasimovian—Gzhelian NBF was former-
ly underlain by relative older strata perhaps of Moscovian age.

Besides the above mentioned features, lithology, stratigra-

phy, areal extent, thickness and incomplete preservation with

Fig. 1. Tectonic sketch of the Western Carpathians, Slovakia (Biely et al. 1996, modified by J. Vozár).

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regard  to  tectonic  amputation,  the  Upper  Paleozoic  of  the
Hronicum  Unit  differs  from  the  other  Upper  Paleozoic  oc-
currences in the Western Carpathians mainly in the presence
of the characteristic basic volcanism. The presence of volca-
nic  products  is  already  evident  in  the  upper  horizons  of  the
NBF  (sporadic  dacite  effusions  and  volcanoclastics).  They
are a testimony of volcanic activity already in the beginning
of rift-related basin formation. An essentially more intensive
Permian basaltic andesite and basalt volcanism is concentrated
into  two  distinct  eruption  phases  (within  the  1

and 3

megacycles of the MF defined by Vozárová & Vozár 1981,
1988), which document distinct magmatic activity with man-
ifestation of the linear type of volcanism connected with re-
gional rifting of continental crust. Numerous effusions have
been reported with thicknesses from 0.5 to 2.5 m of sheets of
lava,  traced  at  considerable  distances  (tens  to  hundreds  of
meters, sporadically also several km), as was documented in
the  Nízke  Tatry  Mts  (Vozár  1974).  This  thickness  testifies,
besides other features, to the polyphase character and fluidity
of  the  basic  magma.  Fluid  structures,  mainly  in  porous,
amygdaloidal, but also fine-grained and porphyritic varieties
are  frequently  documented  at  individual  lava  flows.  So,  to-
gether  with  evidences  of  transport  directions  in  sediments
and  paleomagnetic  measurements  (Muška  in  Vozárová  &
Vozár  1988)  it  is  possible  to  interpret  the  original  south-
north course and rift structure of the sedimentary basin. The
low viscosity and adequate relatively low grade of explosivity
are characteristic of mafic magmas and so the volcanoclastics
are mostly of the ash and sand grain size. Lapilli with a max-
imum  size  of  2 cm  were  found  only  sporadically  (Vozár
1971, 1974). Volcanoclastics are disproportionally less rep-
resented  in  relation  to  effusive  bodies.  The  indications  of
deposition  in  a  water  environment  were  observed  in  the  1

eruption phase and in the basal part of the 2

eruption phase.

They are represented by fine lamination of ash tuffs, low-scale
cross bedding, graded arrangement in small cycles (5—15 cm),
wavy bedding, and oscillatory ripple mark lamination. There
are  frequent  occurrences  of  thin  (5—20 cm)  layers  of  sedi-
ments and volcanoclastics between lava flows. The contacts
of volcanic effusions with sediments and volcanoclastics are
predominantly  caustic-metamorphosed.  Baked  crust  rich  in
Fe-pigment, epidote, chlorite, quartz, calcite veins, is usually
1 to 5 cm wide. The caustic contacts are uneven, marked by
unequal  penetration  of  lava  into  the  plastic  sediment,  also
with  indications  of  contamination.  Similarly,  the  contact  of
two  effusions  is  also  usually  bordered  by  cinder  structure
and contamination from the side of younger effusion.

At several profiles, mainly in the upper part of the 2

eruption  phase,  “pahoe-hoe”  structures  of  lavas  were
observed.  The  disintegrated  (brecciated)  lavas,  mainly  ob-
served  in  the  2

eruption phase, are usually bordering the

marginal  or  frontal  parts  of  effusions.  Even  though  not  all
structural marks documenting the character of volcanism are
well preserved, the Permian volcanics in the Hronicum Unit
are  the  best  preserved  paleovolcanics  in  the  whole  Western
Carpathians  especially  from  the  structural  point  of  view
(Fig. 1).  Compositionally,  the  basic  rocks  were  described
as  rift-related  continental  tholeiites  (Vozár  1997;  Dostal  et
al. 2003).

Methods

Samples NT-1, 2, 3 for Sr and Nd isotope analyses were

chemically prepared and measured in the Isotope Geochem-
istry Laboratory in the Institute of Geological Sciences of the
Polish Academy of Science, Krakow. The analyses were made
with a Multi-Collector Inductively Coupled Plasma Mass
Spectrometer (MC-ICP-MS) Neptune. The samples were di-
gested in three steps: firstly, with HF: HNO

, secondly, with

HNO

and finally, with HCl and HF, following the procedure

described  by  Anczkiewicz  et  al.  (2004)  and  Anczkiewicz  &
Thirlwall (2003). The samples were then dissolved in HCl for
loading  on  cation  exchange  columns  with  AG50Wx8  resin
(Anczkiewicz  et  al.  2004).  Final  separation  of  Sr  was  per-
formed by Sr-spec resin (Peryt et al. 2010) and Nd by Ln-spec
resin (Anczkiewicz & Thirlwall 2003). Nd isotopes were nor-
malized to

143

Nd/

144

Nd = 0.7219 to correct for mass bias. The

reproducibility of Nd standards over the period of analyses
was

143

Nd/

144

Nd = 0.512101 ± 8 (2 s.d. n = 3). Sr isotopes were

normalized to

Sr/

Sr = 0.1194 to correct for mass bias. The

reproducibility of Sr standards over the period of analyses
was

Sr/

Sr = 0.710261 ± 8 (2 s.d. n = 3). Isotope composi-

tions of Ip-1 and Kv-2 samples were taken from Vozárová et
al.  (2007).  They  were  also  chemically  prepared  and  mea-
sured in the Isotope Geochemistry Laboratory in the Institute
of  Geological  Sciences  of  the  Polish  Academy  of  Science,
Krakow.  The

εNd(0,t) values were calculated with parame-

ters for CHUR

143

Nd/

144

Nd = 0.512638,

147

Sm/

144

Nd = 0.1967

(Jacobsen & Wasserburg 1980; DePaolo 1981).

All the dated samples were analysed for major and trace

elements including rare earth elements in ACME Laborato-
ries  Ltd.,  Vancouver,  Canada.  Following  a  lithium  metabo-
rate/tetraborate  fusion  and  dilute  nitric  digestion,  major
elements  were  determined  by  inductively  coupled  plasma
(ICP) and trace and rare elements (REE) by inductively cou-
pled plasma mass spectrometry (ICP-MS). The analytical ac-
curacy  was  controlled  using  geological  standards  and  is
estimated to be within a 0.01 % error (1

σ, relative) for major

elements, and within a 0.1—0.5 ppm error range (1

σ, relative)

for  trace  elements  and  0.01—0.05 ppm  for  REEs.  Mineral
analyses were carried out on a CAMECA SX-100 four-spec-
trometer electron microprobe in the Laboratory of Electron-
Optical  Methods  of  the  State  Dionýz  Štúr  Geological
Institute in Bratislava using the standard procedures. The op-
erating  conditions  were:  15 kV  accelerating  voltage,  20 nA
focused  beam  current  (

ϕ 1—5 ηm) and 20—100 s counting

time depending on the analysed elements.

Mineralogical and petrological characteristics

Dolerite sills and dykes: They cut exclusively the strata of

the NBF. The thickness of individual sills varies from a few
meters to more than 50 m (Fig. 2). The observed lateral ex-
tent  of  individual  sills  attains  from  tens  of  meters  to  ~ 500
meters.  Subvertical  dykes  occur,  but  are  not  observed  fre-
quently.  Thermal  effects  around  intrusions  are  essentially
developed in shales and siltstones, where hornfelsing, calcifi-
cation,  and  silicification  of  the  host  rocks  are  observed.  The

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thickness of these altered zones attains up to 1—2 m, depend-
ing on the thickness of the dolerite bodies. The central parts of
the sills and dykes are medium-grained and show doleritic,
less commonly ophitic textures. The peripheral parts are fine-
grained and have principally a microdoleritic texture.

The mineral composition of dolerites consists of plagio-

clase  (45 vol. %),  clinopyroxene  (25 vol. %),  Mg-hornblende
(2 vol. %)  fine-grained  dark  matrix,  and  opaque  minerals
(magnetite,  titanomagnetite,  ilmenite  and  rutile)  (Fig. 3).
The detected secondary minerals are albite, chlorite, actino-
lite,  hydrogrossular,  and  occasionally  pumpellyite-prehnite,
described by Vrána & Vozár (1969). Ore minerals were de-
scribed by Rojkovič (1977), Ferenc & Rojkovič (2001) and
Olšavský & Ferenc (2002).

Clinopyroxenes in the less altered part of the dolerites are

generally  subhedral  to  euhedral  and  may  occur  as  discrete
crystals  as  well  as  aggregates.  Cracks  and  fractures  in  cli-
nopyroxenes may be filled with secondary minerals, mainly
chlorite, fibrous actinolite and hydrogrossular. For the most
part, the clinopyroxenes are fully replaced by the above men-
tioned  secondary  mineral  association.  Based  on  microprobe

analysis (Table 1), the clinopyroxenes represent a Ca-Mg-Fe
solid solution and can be expressed by the pyroxene quadri-
lateral system. According to IMA classification by Morimoto
et al. (1988), the observed clinopyroxenes are situated in the
diopside and augite range (Fig. 4). In general, the clinopy-
roxenes show an insignificant range of (Mg, Fe)

↔Ca substi-

tution. Commonly, during the initial stage of crystallization,
the composition of clinopyroxenes is Ca

48—50

42—43

07—08

As differentiation proceeds on further cooling, the clinopy-
roxenes become relatively more iron-rich, Ca

45—46

36—41

13—19

in composition. These clinopyroxenes coexist mar-

ginally with magmatic Mg-hornblende (Fig. 3c).

The subhedral and anhedral crystals of clinopyroxenes are

grouped radially or in an irregular mesh with lath-shaped crys-
tals of plagioclases. In the volcanics of the 2

eruption phase,

clinopyroxenes often fill the interstices between the flow ori-
ented laths of plagioclases. The selected chemical analyses of
clinopyroxenes (Table 1, samples NT-2 and NT-3) confirm
the presence of common rock-forming pyroxenes which can
be expressed by the pyroxene quadrilateral system (Morimoto
et al. 1988). In general, the basalt clinopyroxenes show an in-

Fig. 2. Permian tholeiite andesite-basalts (Ipoltica valley section, northern slope of Nízke Tatry Mts). a – sheet of lava, 1

eruption phase,

Malužiná Formation, b – detail of textures of 2

eruption phase, Malužiná Formation, c – detail on thermal contact – basalt flow (upper

part) and sediments of Malužiná Formation (lower part), d – laminated tuffs of Permian tholeitic basalts, Malužiná Formation, Hronicum,
Ipoltica valley, Nízke Tatry Mts.

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(Ca + Na)

1.75—1.78 Ca

and 0.16—0.13 Na

A part of the Mg-hornblende is of secondary
origin  and  evidently  derived  from  primary
pyroxenes  and  replaced  by  Fe-actinolite
through  magmatic-hydrothermal  activity  in
the  final  stage  (Table 2;  Figs. 3b,c, 5).
Compositional  variations  of  amphiboles
from the studied doleritic rocks in terms of
(Ca+Na+K=1.99—2.17)  and  Si  (7.18—7.94)
atoms per formula unit (apfu) indicate igne-
ous  origins  for  both  Mg-hornblende  and
Fe-actinolite  (after  Giret  et  al.  1980).
Mg-hornblendes  are  secondarily  altered
mainly  to  chlorite  and  fibrous  actinolite II.
In  this  case,  it  could  be  assumed  that  am-
phiboles  were  partially  affected  also  by  a
reaction  with  the  metamorphic  hydrother-
mal fluid alteration.

Plagioclases are dominant in the doleritic

rocks, where they form idiomorphic pris-
matic crystals, typical of pericline and albite
twinning. The chemical composition of pla-
gioclases is shown in Table 3. The composi-
tional ranges of plagioclases extend from
An

to An

. Ca-rich phases are preserved

only in the central part of the prismatic pla-
gioclase  crystals.  The  late-stage  magmatic
and metasomatic process replaced the com-
position  of  Ca-rich  plagioclases  towards
Na-rich albite phase. In this respect, the al-
bite  phase  forms  the  peripheral  part  of  pla-
gioclase crystals. Besides essentially Na and
Ca variations, the plagioclases contain insig-
nificant  contents  of  orthoclase  molecule,
varying  up  to  6  molar  percent  (Table 3).
Other ions which are present in very limited
amounts include Fe

and Sr.

Basaltic andesites and basalts: Volcanics

contain  phenocrysts  occupying  around
30 vol. %  of  the  rock  trapped  in  variable
amounts  of  volcanic  glass.  They  are  repre-
sented by plagioclases, clinopyroxenes, and
opaque  crystals,  such  as  titanomagnetite,
magnetite  and  ilmenite.  Compared  to  the
volcanics of the 2

eruption phase, the vol-

canic rocks of the 1

eruption phase exhibit

a higher grade of crystallinity. According to
the relative proportion of crystals and glass,
they demonstrate holocrystalline texture or a
combination of holocrystalline and hypo-
crystalline textures, while the 2

phase vol-

canics contain mostly hypocrystalline
textures. Depending on the relative position
within the individual flows, the volcanics of
the 1

eruption phase demonstrate inter-

granular, porphyric, subophitic and ophitic
textures. The 2

eruption phase volcanics

are more characteristic for intersertal and
pilotaxitic textures.

Table 1:

Selected

analyses

clinopyroxenes.

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Table 2: Selected analyses of amphiboles.

Plagioclases are the dominant phenocrysts in all basaltic

andesites and basalts and form typical lath-shaped crystals.
They represent a maximum of 80 % in lavas of the 1

erup-

tion phase and 65 % in lavas of the the 2

eruption phase

from the all phenocrysts. They usually show repeated albite
and/or pericline twinning on a microscopic scale. The peri-
cline and albite twinning often occur in one crystal. Selected
chemical analyses of plagioclases document prevalent inter-
mediate composition of the 1

eruption phase plagioclases,

Table 3: Selected analyses of plagioclases.

with An

41—61

and a small content of orthoclase molecule

(Or

1—3

). The relatively more basic plagioclases were identi-

fied in the volcanics of the 2

eruption phase, with An

61—77

In general, the plagioclases are optically homogeneous, but
the variation of An component within the individual plagio-
clase crystals from more calcic core to more sodic rim indi-
cates a continuous change in composition of plagioclase
crystals with falling temperatures. Among the secondary al-
terations of plagioclases, saussuritization is prevalent. Fine-

Sample NT-1

NT-2

Analyses

12/1 13/1 16/1 17/1 18/1 33/1 36/1 37/1 40/1 41/1

SiO

53.24

62.49

60.32

57.65

54.71

54.00

53.01

56.57

56.43

58.28

28.78 22.96 24.68 26.38 27.74 28.51 28.79 26.47 26.17 25.14

FeO

0.51 0.36 0.40 0.43 0.47 1.00 0.87 0.98 1.02 0.85

SrO

0.07 0.02 0.05 0.04 0.06 0.04 0.05 0.05 0.06 0.05

CaO

12.09 5.16 7.06 9.05

10.73

11.66

12.26 9.59 9.72 8.13

4.06 7.41 6.48 5.57 4.94 4.48 4.13 5.51 5.48 6.18

0.30 1.00 0.54 0.38 0.32 0.24 0.22 0.34 0.37 0.46

Sum

99.04 99.39 99.52 99.50 98.98 99.93 99.33 99.53 99.25 99.10

Formula based on oxygens
Si

2.46 2.82 2.74 2.63 2.51 2.48 2.45 2.59 2.59 2.67

1.57 1.22 1.32 1.42 1.50 1.54 1.57 1.43 1.42 1.36

0.60

0.25

0.34

0.44

0.53

0.57

0.61

0.47

0.48

0.40

0.36 0.65 0.57 0.49 0.44 0.40 0.37 0.49 0.49 0.55

0.02 0.06 0.03 0.02 0.02 0.01 0.01 0.02 0.02 0.03

X(Ca)

0.61 0.26 0.36 0.46 0.53 0.58 0.61 0.48 0.48 0.41

X(Na)

0.37 0.68 0.60 0.51 0.45 0.40 0.37 0.50 0.49 0.56

X(K)

0.02

0.06

0.03

0.02

0.01

0.02

0.03

Sample NT-1
Analyses

3/1 14/1 20/1 23/1 24/1 25/1 11 12 13 14 15 16

SiO

51.19 49.66 51.71 50.65 48.67 55.86 51.14 49.51 49.02 48.32 49.11 49.45

TiO

0.37 2.07 0.05 0.43 0.04 0.05 0.45 1.98 1.34 1.46 1.41 1.08

2.15 5.11 0.92 1.60 7.24 1.74 3.04 5.31 4.96 5.58 5.13 5.32

FeO

22.79 11.91 25.22 25.70 12.04 7.55 14.88 11.81 12.80 12.41 11.75 11.51

MnO

0.89 0.23 0.78 0.82 0.17 0.17 0.24 0.23 0.20 0.26 0.25 0.19

MgO

7.70

15.22 6.61 6.31

15.86

19.84

14.23 15.37 14.94 15.10 15.31 16.05

CaO

11.74 11.52 11.87 11.76 11.32 12.20 11.30 11.38 11.08 11.28 12.40 11.32

0.22 1.18 0.22 0.19 1.58 0.40 0.58 1.24 1.46 1.52 1.04 1.38

0.12 0.32 0.03 0.09 0.57 0.16 0.30 0.30 0.53 0.46 0.27 0.41

Total

97.16 97.23 97.42 97.57 97.49 97.97 96.16 97.11 96.34 96.40 96.66 96.70

Formula based on 23 oxygens
Si

7.78 7.18 7.94 7.79 7.02 7.79 7.54 7.16 7.20 7.09 7.19 7.17

0.22 0.82 0.06 0.21 0.98 0.21 0.46 0.84 0.80 0.91 0.81 0.83

Sum T

8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00

0.17 0.05 0.10 0.08 0.25 0.07 0.06 0.06 0.06 0.06 0.08 0.08

0.04 0.23 0.01 0.05 0.00 0.01 0.05 0.21 0.15 0.16 0.16 0.12

0.13 0.31 0.11 0.09 0.44 0.16 0.31 0.35 0.32 0.32 0.12 0.40

1.74 3.28 1.51 1.45 3.41 4.12 3.12 3.31 3.27 3.30 3.34 3.47

2.77 1.09 3.12 3.21 0.89 0.64 1.44 1.02 1.19 1.14 1.28 0.91

0.11 0.01 0.10 0.11 0.01 0.00 0.01 0.01 0.01 0.02 0.02 0.01

Sum C

4.96 4.97 4.95 4.99 5.00 5.00 5.00 4.97 4.99 4.99 5.00 4.98

0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00

0.00 0.04 0.00 0.00 0.12 0.08 0.08 0.06 0.07 0.07 0.03 0.08

0.00 0.01 0.00 0.00 0.01 0.02 0.02 0.01 0.01 0.02 0.02 0.01

1.91 1.78 1.95 1.94 1.75 1.82 1.78 1.76 1.74 1.77 1.94 1.76

0.06 0.16 0.05 0.06 0.13 0.07 0.09 0.17 0.18 0.14 0.03 0.15

Sum B

1.98 2.00 2.00 2.00 2.02 1.99 1.97 2.00 2.00 2.00 2.02 2.00

0.00 0.17 0.02 0.00 0.31 0.04 0.08 0.18 0.24 0.29 0.26 0.24

0.02 0.06 0.01 0.02 0.11 0.03 0.06 0.05 0.10 0.09 0.05 0.08

Sum A

0.02 0.23 0.02 0.02 0.41 0.07 0.13 0.23 0.34 0.37 0.31 0.31

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grained phylosilicates and occasionally pumpellyite were also
detected. As a result of hydrothermal processes, the plagio-
clases were replaced by secondary albite and exceptionally,
by K-feldspar.

As for accessory minerals, these rocks contain long-co-

lumnar crystals of apatite and oxides the latter are represented
by titanomagnetite and ilmenite. The magmatic ilmenite is
disintegrated to titanite and rutile in places.

Geochemistry

We classify our basaltic rocks on the basis of a TAS dia-

gram (Fig. 6). The projection points of the analyses are lying
in the field of trachyandesites and are located along the di-
viding line between alkali basalts and calc-alkali and/or
tholeiitic basalts (Vozár 1977; Dostal et al. 2003). It is likely
that their location was a result of a slight enrichment in alka-
lies during post-magmatic processes.

In order to make a more precise classification of the rocks

under study and possible genetic interpretations, we used dif-
ferent discrimination diagrams (Figs. 7, 8). In the Nb : Zr/4 : Y
diagram  (Fig. 7),  the  projection  points  of  the  analysed  ba-
salts are lying in the field of within-plate tholeiites, near the
field of volcanic arc basalts. In the second diagram showing
the dependence of contents Th : Hf/3 : Ta  (Fig. 8),  the  analy-
ses of the studied rocks plot to fieldD, which corresponds to
the composition of calc-alkali volcanic arc basalts. Another
diagram (Fig. 9) allows us to make a more precise differenti-
ation of these two basalt-originating environments. This dia-
gram distinguishes three basic geotectonic environments: the
field of volcanic arc basalts (subduction zone 1), the field of
continental  basalts  and  behind-arc  basalts  (2),  and  the  field
of  ocean  basalts  (different  types  of  mid-ocean  ridge  basalts
(MORB  3)).  In  this  diagram,  the  studied  rocks  are  lying  in

Fig. 4. Classification diagram of clinopyroxenes (Morimoto et al.
1988).

the field of continental basalts, which partly overlaps with
the field of volcanic arc basalts.

The REE normalized curve (Fig. 10) is rather flat with

a slight enrichment in light REE, and almost no Eu anomaly
is observed. To obtain better data on geochemical character-
istics, we also used trace element normalization to the com-
position of the primordial mantle (Fig. 11). Compared to the

Sample

NB-1 NT-1 NT-2 NT-3

SiO

51.46 51.17 57.05 54.64

TiO

1.76 1.50 1.07 1.21

16.20

17.73

16.32

17.97

9.38 8.83 9.89 7.05

MgO

4.98 5.18 2.12 3.15

CaO

6.88 7.50 2.77 7.60

MnO

0.18 0.15 0.24 0.10

5.09 3.70 6.62 4.41

0.34 1.44 1.27 0.60

0.31 0.25 0.60 0.24

LOI

3.20 2.20 1.80 2.90

Total

99.78 99.65 99.75 99.87

110

351

157

150

27.6

27.5

14.5

23.4

1.4

1.9

2.1

0.3

18.5

18.3

6.4

5.1

7.8

3.7

13.8

9.9

10.5

5.1

10.3

35.7

28.6

13.5

209.2

451.6

116.6

355.7

0.8

0.6

0.3

5.4

3.3

4.5

2.8

1.4

0.9

2.2

0.9

189

192

154

2.3

0.5

11.3

236.1

186.2

336.9

149.2

38.4

32.6

53.2

23.8

24.4

22.3

31.4

14.9

53.3

51.6

73.9

33.4

7.24

5.81

8.87

3.81

30.8

24.8

6.8

5.91

9.48

4.13

1.7

1.64

2.61

1.3

7.18

6.29

9.8

4.4

1.16

1.09

1.77

0.79

6.6

6.21

4.66

1.38

1.34

2.16

4.06

3.99

6.55

2.9

0.6

0.56

0.93

0.4

3.72

3.36

5.82

2.41

0.56

0.52

0.93

0.42

5.5

0.5

1.5

0.4

22.5

19.4

14.2

2.3

5.6

14.1

41.8

3.5

248

44.5

15.7

10.7

1.4

1.1

4.9

1.3

0.1

0.5

0.1

0.6

0.3

0.1

0.5

5.9

0.01

0.23

0.1

Table 4: Chemical composition of studied samples.

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Table 6: Nd isotope analysis data from the studied samples.

< 1 2 wt. % and low ratios of Nb/La (0.3—0.6), which is more
characteristic of LT basalts.

Isotopic data

Tables 5 and 6 show the results of isotopic analysis of Sr

and Nd. The measured

Sr/

Sr isotopic ratios in these sam-

ples are significantly different as a result of differences in

Rb/

Sr between the samples. The Sr evolution plot shows

that the intercept line for Sr evolution for basalt from the 1

intrusive phase (NT-2, IP-1) is closest to the expected extru-
sions age (about 290 Ma with an initial

Sr/

Sr about

0.7054 (Fig. 12). Small differences in the calculated values of
I

(Table 5) for the analysed samples may document a partial

Sr isotopic heterogeneity of the source (0.70435—0.70566),
or a possible contamination of the original magma by crustal
material. Moreover, the sample material could be altered to
various degrees after the eruption, and this process may have
changed the concentration of most incompatible elements
such as Rb, Ba and K, because these elements are known for
their high mobility.

For Nd analyses of the three samples, the calculated value

for

εCHUR (285) is positive for all samples and with only

subtle variations. (Table 6) (Figs. 13, 14).

Discussion

The geochemical data we obtained can be compared with

continental flood basalts (CFBs), whose extrusive ages are

Table 5: Sr isotope analysis data from the studied samples.

Fig. 12. Sr evolution diagram of samples analysed.

Fig. 13.

ε(Nd) evolution lines in samples analysed with CHUR and

DM sources.

Fig. 14. The position of NT-1, NT-2, NT-3 sample points in

εNd vs.

Sr/

Sr plot. MA – mantle array, dotted lines – position at 285 Ma.

close to our samples. Siberian continental basalts have ages of
250.3 ± 1.1 Ma  (Reichow  et  al.  2009;  Shelnut  &  Jahn  2011)
and  the  Emeishan  flood  basalt  ( ~ 260 Ma)  in  southwestern
China (Xu et al. 2001; Hou et al. 2011 and references therein),
large  igneous  provinces  which  erupted  during  the  Permian—

(285) —

143

Nd/

144

Nd.

CHUR

(285) – calculated parameters in time of extrusion (285 Ma).

Sm (ppm)

Nd (ppm)

147

Sm/

144

143

Nd/

144

Nd I

(285)

CHUR

(0)

CHUR

(285)

NT-1

5.662

24.144

0.141772

0.512625±10

0.512361

–0.25

1.75

NT-2

9.118 38.297 0.145052 0.512787±11

0.512517

2.91 4.79

NT-3

4.171 16.961 0.148671 0.512752±18

0.512474

2.22 3.97

(285) – calculated initial

Sr/

Sr in time of extrusion (285 Ma).

Rb (ppm) Sr (ppm)

Rb/

Sr/

Sr I

(285)

NT-1

35.7 451.6 0.229 0.706340±11

0.705413

NT-2

28.6 116.6 0.710 0.708539±9

0.705661

NT-3

13.5 355.7 0.110 0.704797±9

0.704352

Ip-1*

0.992

0.709483±15

0.705461

Kv-2*

0.318

0.706302±11

0.705014

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Triassic period. Up to now, the origin of flood basalts, which
are represented mainly by tholeiitic basalts, is highly disput-
able and a variety of models have been developed to explain
their origin, but their genesis and sources are very complex.
Generally, the following sources can be considered:

1) crustal contamination of MORB-like melts (Piccirillo et

al. 1989; Campbell & Griffiths 1990; Arndt et al. 1993;
Peate & Hawkesworth 1996; Campbell 2005);

2) melting of laterally heterogeneous subcontinental litho-

spheric mantle (Gallagher & Hawkesworth 1992; Sharapov
et al. 2008);

3) mixing depleted and enriched mantle (Ellam & Cox 1991);
4) mixing enriched mantle melts and crust (DePaolo &

Wasserburg 1979; Basu et al. 1998; Yan et al. 2007).

A subduction-related model has been presupposed by

Ivanov et al. (2008) for the southeastern part of the Siberian
Traps Large Igneous Province.

When comparing our data with those from the above menti-

oned areas, we can say overall consistency, even in the (

Sr/

Sr)t, and the

εNd(t) values, reduced to the age of extrusion.

In the case of the Siberian CFBs, Wooden et al. (1993)

concluded  that  the  dominant  volume  of  the  erupted  magma
originated from an asthenospheric mantle plume, but none of
the  lavas  are  interpreted  as  representing  asthenospheric
melts.  Moreover,  the  authors  suppose  that  the  dominant
source of the erupted magma was a mantle plume. However,
the compositions of the primary magmas were controlled by
the thickness of the lithosphere, which influenced the depth
of melting, the residual mineral assemblage, and the percent-
age of melting in the source region. The observed chemical
and isotopic characteristics of the lavas indicate magma res-
ervoirs  through  bulk  assimilation  and/or  partial  melting  of
crustal wall-rocks. Volumes of basaltic melt were produced
directly from the continental lithospheric mantle beneath the
Siberian craton (Wooden et al. 1993).

CFBs are likely to be a product of partial melting of man-

tle sources which represent primitive undifferentiated mate-
rial and are clearly different from MORBs. This is a proof of
crust contamination (DePaolo & Wasserburg 1979). For cor-
relation,  the  Emeishan  basalts  (Xu  et  al.  2001;  Xiao  et  al.
2004;  Zhang  et  al.  2006;  Liu  &  Zhu  2009  and  references
therein) are Permian—Triassic, they overlap the Permian car-
bonate  formation  and  are  covered  by  Triassic  sedimentary
sequences. Great CFB outpourings are genetically connected
with  “mantle  plume  activities”.  The  composition  of  radio-
genic isotopes of CFBs is out of the range of “plume sources”
defined by oceanic island basalts (OIB). Only in cases when
crust contamination can be excluded the lithospheric mantle
can play an important role together with a significant contri-
bution  of  plume  materials  (Chung  &  Jahn  1995).  However,
according to Hou et al. (2011) the Emeishan lavas cannot be
classified by TiO

contents and/or Ti/Y ratios simply. Their

high-Ti/lowTi characteristics are probably the results of dif-
ferent fractionating assemblages, so whether or not fractional
crystallization of Fe-Ti oxides occurred. According to these
authors this is the key factor that control the Ti abundance
and Ti/Y ratios in the residual melts, and therefore, neither
Ti-contents nor Ti/Y ratios can be reflect the nature of their
mantle source (Hou et al. 2011).

In fact, our petrographic observations show that there are

variable contents of Fe-Ti oxides in the MF basalts as the pri-
mary magmatic phase. Petrological modelling of Ganino et al.
(2008)  shows  the  possible  derivation  of  low-Ti  basalts  from
fractional crystallization of typical high-Ti basalts. These frac-
tional  crystallization  processes  may  have  been  accompanied
by  contamination  from  subcontinental  lithospheric  mantle
and/or continental crust (DePaolo 1981) and reflected by trace
element ratios Th/Ta and La/Nb (Neal et al. 2002).

The major issue in the study of continental basalts is to

identify their mantle source (Mahoney et al. 1982). The ob-
tained data reflect a contamination of LIL-depleted magmas
by two magmatic members; one is undoubtedly the continen-
tal crust and the other enriched mantle.

The MF basalts data suggest that the isotopic differences

in the analysed samples

Sr/

Sr (285 Ma)i,

εNd(285 Ma)

can be a result of 1) isotopic inhomogeneity of the source,
2) contamination of basalt magmas by crustal material. From
this perspective, then we can assume that sample NT-3
(2

eruption phase) represents the least contaminated mate-

rial and may correspond to the initial isotopic source.

The Sr evolution graph shows that during the extrusion of

the 1

eruption phase, the initial ratio

Sr/

Sr was 0.7054,

but for 2

eruption phase, it was 0.7051 (Fig. 12). With regard

to the isotopic composition of Sr, we can assume an identical
magmatic source. A higher ratio of

Rb/

Sr (0.992) in the

eruption phase is likely to have been caused by contami-

nation  of  the  extruding  magma  by  crustal  material.  This
trend is fully in line with the evolution of the Hronicum ter-
restrial  rift  with  the  progressing  extensional  regime  on  the
cooling  lithosphere,  in  which  more  links  were  made  to  the
mantle along deep faults.

The geochemistry of the Hronicum basic rocks corre-

sponds to the isotopic composition and implies source hetero-
geneity or a source mixing genetic model. Generally, the LT
basalts are interpreted as a derivation from a shallower litho-
spheric  mantle  which  underwent  assimilation  and  fractional
crystallization  (Wooden  et  al.  1993;  Arndt  et  al.  (1993);
Sharma 1997; Xu et al. 2001; Yan et al. 2007 and references
therein). The Hronicum basic rocks are characterized by low
Nb/La ratio, ranging from 0.56 to 0.33, and a negative corre-
lation  between  Nb/La  and  SiO

which indicates that the

evolved lavas underwent assimilation and fraction crystalli-
zation. This accounts for i) the nearly uniform major and
trace elements and isotopic composition of LT lavas, ii) high
(

Sr/

Sr)

ratios and iii) negative Nb-Ta anomalies.

The low values of the Th/Yb (0.77—1.45), Ta/Yb (0.10—0.21),

Nb/La (0.33—0.56), Th/La (0.22—0.14) and Ta/La (0.02—0.03)
ratios are characteristic of the Hronicum basic rocks and in-
dicate a significant crustal contamination. Contrasting to these
are the high Th/Ta ratios (5.5—9.3), which is in coincidence
with the model of crustal contamination and characterizes the
LT lavas (Lightfoot et al. 1993). Lightfoot et al. (1993) and
Hawkesworth et al. (1995) used the La/Sm ratio ( > 3) for dis-
tinguishing of crustal contamination for the Siberian traps. In
the Hronicum basic rocks these values are constantly higher
than 3 (La/Sm =3.3—3.8).

Similar results were reported by Dostal et al. (2003).

Based on these authors, the Permian basic rocks of the

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Malužiná Formation are compositionally rift-related conti-
nental tholeiites with enriched light REE patterns having
(La/Yb)

ratios between 2 and 5.5 and with mantle-normal-

ized patterns characterized by negative Nb-Ta anomalies.
According to their chemical composition, Dostal et al. (2003)
supposed a derivation of the Permian Malužiná Formation
basic rocks from the subcontinental lithospheric mantle with
a partial effect of crustal contamination.

In fact, the incompatible trace element patterns of the Hroni-

cum  basaltic  rocks  are  likely  to  be  related  to  a  lithosphere
mantle source and are dissimilar to the patterns of the oceanic
basalts or plume-related basalts, also described by Dostal et al.
(2003).  These  patterns  are  typical  of  many  continental  flood
basalt  provinces,  such  as  Paraná,  Columbia  River  plateau,
Ethiopia, Siberian and Emeishan CFBs (Piccirillo et al. 1988;
Dostal  &  Greenough  1992;  Hooper  &  Hawkesworth  1993;
Arndt et al. 1993; Sharma 1997; Kieffer et al. 2004; Reichow
et al. 2009; He et al. 2010 and references therein). The good
correlation  with  the  Siberian  traps  is  shown  by  the  Siberian
traps  normalized  patterns  of  the  Hronicum  basic  rocks
(Fig. 10b).  These  patterns  are  typical  of  subduction-related
rocks  as  well  as  some  within-plate  continental  tholeiites,
which were not associated with contemporary subduction pro-
cesses. The chemical composition of basalts suggests a possi-
ble  later  effect  of  older  subduction-related  processes  that
modified  the  lithospheric  mantle,  which  then  became  the
magma  source  (Hooper  &  Hawkesworth  1993).  High  Th/Nb
ratio ( > 0.17) corresponding to primitive mantle is characteris-
tic of subduction-related processes (Pearce 2008). In fact, the
Hronicum basic rocks have a high Th/Nb ratio, ranging from
0.33 to 0.55, which indicates the subduction signature.

Composition data confirm the previous model of Dostal et

al. (2003), which supposed the generation of parental magma
for  the  Hronicum  basic  rocks  from  an  enriched  heteroge-
neous source in the subcontinental lithospheric mantle. This
model is in concordance with the depositional model of the
Malužiná Formation sedimentary basin, which originated in
a  rifted  continental  margin  environment  supplied  from  the
continental  crust  and  a  dissected  magmatic  arc  (Vozárová
1990,  1998).  The  Permian  rift-related  sedimentary  basin  of
the  Hronic  Unit  was  situated  in  a  foreland  retro-arc  setting
on the continental crust. It was filled with clastic detritus de-
rived from a dissected Mississippian magmatic arc and from
the  Permian  syn-sedimentary  volcanic  centers,  as  is  docu-
mented  by  the  monazite  ages  (Demko  &  Olšavský  2007;
Vozárová et al. 2014). The abundance of rhyolite-dacite de-
tritus within the Hronicum Late Paleozoic clastic sediments
entitles us to assume the bimodal type of volcanism. During
the  Cretaceous  nappe  stacking  a  large  marginal  part  of  the
former sedimentary basin was tectonically cut off, which ex-
plains  why  only  its  distal  parts  with  continental  tholeiites
have remained to the present fabric.

Conclusion

The relics of the Hronicum Late Paleozoic sequences repre-

sent only a part of the Late Carboniferous – Permian basin in
the Inner Western Carpathians. Not only the character and dis-

tribution of sedimentary lithofacies, but also volcanics of fis-
sural type provide evidence of this original basin as a regional
rift system 450 km, perhaps more, in length. The mafic to in-
termediate  products  with  a  continental  tholeiitic  magmatic
trend are a specific feature of this basin. The Permian volca-
nics correspond to within plate basalts. The chemical charac-
teristics indicate that these volcanic rocks can be regarded as
tholeiites  related  to  deep  (decompression)  faults  in  an  exten-
sional  regime  with  formation  of  a  regional  rift  as  a  part  of  a
continental margin, or a back-arc setting on continental crust.
Chemical  and  isotopic  data  from  the  Hronicum  basic  volca-
nics suggest that the parental magma for the Hronicum basic
rocks was generated from an enriched heterogeneous source in
the subcontinental lithospheric mantle.

Acknowledgment: This study represents a partial output of
the Grants: APVV-0081-10, APVV-0546-11, APVV-14-0038,
VEGA 1/0095/12, 1/0141/015 and 1/0650/15. We are grate-
ful to Jaromír Ulrych and Rastislav Demko for constructive
comments on this paper and R. Anczkiewicz for kindly help
with isotope analyses obtained in Isotope Geochemistry Lab-
oratory (Polish Academy of Sciences, Kraków).

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