GeolCarp_Vol66_No6_515

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, DECEMBER 2015, 66, 6, 515—534 doi: 10.1515/geoca-2015-0042

Source areas of the Grybów sub-basin: micropaleontological,

mineralogical and geochemical provenance analysis (Outer

Western Carpathians, Poland)

MARTA OSZCZYPKO-CLOWES, PATRYCJA WÓJCIK-TABOL and MATEUSZ PŁOSZAJ

Institute of Geological Sciences, Jagiellonian University, Oleandry 2a, PL 30-063, Kraków, Poland;

m.oszczypko-clowes@uj.edu.pl; p.wojcik-tabol@uj.edu.pl;

(Manuscript received January 10, 2015; accepted in revised form August 22, 2015)

Abstract: The Grybów Unit occurring in the Ropa tectonic window was the subject of micropaleontological and geochemi-
cal investigation. Studies, based on calcareous nannofossils, proved that the level of reworked microfossil is not higher
than 22 % and it varies between two sections. Quantitative analyses of the reworked assemblages confirmed the domi-
nation of Cretaceous and Middle Eocene species. The Sub-Grybów Beds, Grybów Marl Formation and Krosno Beds
were assigned to the Late Oligocene and represent the terminal flysch facies. Detrital material accumulated in the
Oligocene sediments originated from the Marmarosh Massif, which is the eastern prolongation of the Fore-Magura
Ridge. The microscopically obtained petrological features agree with the chemical composition of the samples. Mica
flakes, rounded grains of glauconite, heavy mineral assemblage, including abraded grains of zircon, rutile and tourma-
line as well as charred pieces of plant tissues are reworked components. Enrichment in zircon and rutile is confirmed
geochemically by positive correlation between Zr and SiO

. Zr addition is illustrated on 10

×Al

—Zr—200

×TiO

and

Zr/Sc vs. Th/Sc diagrams. Interpretation of the A—CN—K diagram and variety of CIA and CPA values indicate that the
source rocks were intensely weathered granite-type rocks.

Key words: Grybów Unit, Ropa tectonic window, Oligocene, calcareous nannofossils, mineral composition, geochemistry,
recycling.

Introduction

In the Polish sector of the Magura Nappe eleven tectonic
windows of the Grybów Unit have been recognized (Fig. 1;
see also Książkiewicz 1972). This unit is composed predom-

inantly  of  Upper  Eocene—Oligocene  deposits  (Sikora  1960;
Kozikowski  1965;  Oszczypko-Clowes  &  Oszczypko  2004;
Oszczypko-Clowes  &  Ślączka  2006;  Oszczypko-Clowes
2008; Oszczypko & Oszczypko-Clowes 2011). The Grybów
Unit  (Świdziski  1963),  known  also  as  the  Ropa-Pisarzowa

Fig. 1. Tectonic map of the Northern Carpathians (compiled by Oszczypko-Clowes 2001). 1 – crystalline core of the Tatra Mts, 2 – High
Tatra and sub-Tatra units, 3 – Podhale flysch, 4 – Pieniny Klippen Belt, 5 – Magura Nappe, 6 – Grybów Nappe, 7 – Dukla Nappe,
8 – Fore-Magura thrust-sheet, 9 – Silesian Unit, 10 – Sub-Silesian Unit, 11 – Skole Unit, 12 – Miocene deposits upon the Carpathian,
13 – Stebnik (Sambir) Unit, 14 – Zgłobice Unit, 15 – Miocene of the Carpathian Foredeep, 16 – andesite, 17 – studied area.
Su – Siary, Ru – Rača, Bu – Bystrica, Ku – Krynica subunits.

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Unit (Kozikowski 1956), belongs to the Fore Magura Group
of units, which were formed just before the latest Oligocene
thrusting of the Magura Nappe onto the Fore-Magura sedi-
mentary area.

The aim of this study was to determine the provenance of

the clastic material, reconstruction of source rock lithology
as well as interpretation of the source area based on re-
worked microfossils.

The provenance of the siliciclastic facies sediments of the

Outer Carpathians has been studied during the last decades
(see Wójcik-Tabol & Ślączka 2013 with references therein).

Fig. 2. Geological map of the Ropa tectonic window (Sikora 1960; Oszczypko-Clowes 2008, changed).

Recycling processes often involve the cannibalistic turnover
of  the  sedimentary  mass  (McLennan  et  al.  1993;  Veizer  &
MacKenzie  2003),  thus  producing  shales  with  moderate
geochemical  maturity.  Heavy  minerals,  such  as  zircon  and
rutile are considered to be the most resistant to degradation
during sedimentary reworking. Zircon is a carrier mineral of
Zr and Hf. Rutile could have been attributed to TiO

contents

if titanium had not been easily incorporated by phyllosili-
cates. A ternary plot of 10

×Al

—Zr—200

×TiO

(Garcia et

al. 1991) shows an accumulation of Zr or TiO

due to detri-

tus recycling. The Zr/Sc vs. Th/Sc diagram (McLennan et al.

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1993) is used to illustrate an addition of reworked material
represented by zircon. The CIA index and A—CN—K plot
show of source rocks weathering. They also suggest the re-
cycling influence on distribution of major oxides.

Geological framework and studied sections

The oldest sediments of the Grybów Unit belong to the Ja-

worzynka  Beds  (Senonian—Paleocene)  described  from  the
Mszana  Dolna  tectonic  window  (see  Oszczypko-Clowes  &
Oszczypko  2004).  The  Jaworzynka  Beds  comprise  packets
of thick-bedded, biotitic sandstones and conglomerates over-
lain by thin-bedded, dark, non-calcareous flysch.

The Eocene is represented by the Hieroglyphic Beds

(Sikora 1960, 1970) or the Klęczany Beds (Kozikowski 1956)
developed  as  green,  grey  and  black  shales,  with  intercala-
tions of fine- to medium-grained glauconitic sandstones. To-
wards the top they pass into the Upper Eocene greenish marl
with abundant  Globigerina corresponding to the Sub-Meni-
lite  Globigerina  Marls  that  comprise  a  key-horizon  for  all
units of the Outer Carpathians (Olszewska 1983; Oszczypko
(Clowes) 1996; Leszczyński 1997).

The Oligocene strata are developed as a series of 150 m

thick  green,  grey  and  black  marls,  and  marly  shales  with
intercalations  of  thin-  to  medium-bedded,  micaceous  and
glauconitic  sandstones  of  the  Sub-Grybów  Beds  (S-GB;
Kozikowski 1956).

The Sub-Grybów Beds are followed by the Grybów Marl

Formation  (GMF  –  after  Oszczypko-Clowes  &  Ślączka
2006)  known  earlier  as  Grybów  shales  (Uhlig  1888;  Sikora
1960)  or  Grybów  Beds  (Kozikowski  1956).  Series  up  to
200 m thick contain black and brownish-black, platy splitting
marls,  rarely  interbedded  by  grey  marls  and  sandstones.
Thick lenses of ferruginous dolomites occur within the upper
part of this series. The highest part of the Grybów Marl For-
mation contains intercalations of siliceous marls with cherts.

Further up the section there is 400 m thick series of grey,

calcareous shales and micaceous sandstones regarded as the
Krosno  Beds  (Kozikowski  1956;  Oszczypko-Clowes  2008;
Oszczypko  &  Oszczypko-Clowes  2011).  However,  Ślączka
(1971)  and  Koráb  &  Ďurkovič  (1978)  proposed  that  they
may represent the Cergowa Beds, typical for the Dukla Unit.

The biostratigraphical framework was developed by Kozi-

kowski & Jednorowska (1957), Blaicher (1958), Olszewska
(1981), Smagowicz (in Burtan et al. 1992), Smagowicz (in
Cieszkowski 1992), Oszczypko-Clowes & Oszczypko (2004),
Gedl (2005), Oszczypko-Clowes & Ślączka (2006), Oszczypko-
Clowes (2008), Oszczypko & Oszczypko-Clowes (2011).

The Ropa tectonic window is located ca. 15 km SW from

Gorlice. Research interest was focused on two sections along
the Górnikowski and Chełmski creeks, left bank tributaries
of the Ropa River (Figs.1 and 2).

Both sections were described by Kozikowski (1956), Sikora

(1960, 1970), Ślączka (1973) and Oszczypko-Clowes (2008).
Sikora (1960, 1970) distinguished four thrust-sheets outcrop-
ping the Hieroglyphic Beds, Sub-Menilite Globigerina Marls,
Sub-Grybów Beds, Grybów Beds and Krosno Beds (Fig. 3).
During the latest field works these lithostratigraphic divisions

were recognized with the exception of the Hierolyphic Beds and
Globigerina  Marls  (Oszczypko-Clowes  2008).  Kozikowski
(1956) and Kozikowski & Jednorowska (1957) proposed that
the oldest strata of the Ropa tectonic window are represented
by  the  Sub-Grybów  Beds.  Oszczypko-Clowes  (2008)  con-
firmed  it.  The  S-GB  exposed  in  the  Górnikowski  and
Chełmski  brooks  at  the  top  of  thrust-sheet II  are  developed
as  brown  marly  mudstones  with  intercalations  of  green  and
black non-calcareous shales. Calcareous turbidites with Tbc
and Tabc Bouma intervals are more typical for the upper part
of  the  Sub-Grybów  Beds  (Fig. 3).  The  bluish,  micaceous,
fine-  to  medium-grained,  thick-bedded  sandstones  (up  to
1.2 m) intercalate the grey, green and black marly shales.

The Grybów Marl Formation can be seen in all thrust-

sheets (Figs. 2 and 3). The formation is composed of black,
hard marls alternated with dark grey soft marls and fine-
grained sandstones with Tab and Tbc Bouma intervals. The
upper part of the formation contains ferruginous dolomite
layers. In the highest part of the Grybów Marl Formation silic-
ified marls with layers of chert a few cm thick appear (Fig. 3).

The Jasło Limestone layer, exposed in the Górnikowski

brook ends the Grybów Marl Formation and forms the bor-
der with the overlying Krosno Beds (Kozikowski 1956;
Sikora 1960, 1970; Oszczypko-Clowes 2008) or Cergowa
Beds (Ślączka 1971; Koráb & Ďurkovič 1978).

Going up the sections the frequency of sandstone decreases

and marly pelites dominate. The pelites are represented by dark
grey marly shales with intercalations of thin-bedded, cross-lam-
inated calcareous sandstones (Fig. 3). According to Oszczypko-
Clowes (2008) it is better to correlate these beds with the
Krosno shale lithofacies than with the Cergowa Beds, which
are dominated by thick-bedded sandstones (cf. Ślączka 1971).

Samples and methods

All the samples were collected during the field work of the

first author. For the purpose of this work only selected sam-
ples from the Górnikowski and Chełmski brooks were used.

For the purpose of micropaleontological studies, all samples

were prepared using standard smear slide techniques for the
light microscope (LM) and then analysed with a Nikon-
Eclipse E 600 POL, at a 1000

× magnification using both par-

allel and crossed nicols. The applied taxonomic frameworks
are based upon Aubry (1984, 1988, 1989, 1990, 1999), Perch-
Nielsen (1985) and Bown (1998 and references therein).

Quantitative analyses were performed for the samples col-

lected from the Sub-Grybów Beds, Grybów Marl Formation
and  Krosno  Beds,  exposed  in  the  second  trust-sheet  along
the  Górnikowski  and  Chełmski  streams  (Figs. 2  and  3),  us-
ing  counts  of  300  specimens  per  slide.  In  order  to  analyse
and  calculate  the  percentage  abundance  of  autochthonous
and allochthonous assemblages the 5 % range error was ac-
cepted. The nominal values are presented in Tables 1 and 2.

To distinguish reworked from in-place nannofossils the

full  stratigraphic  ranges  of  species,  were  used.  Individual
species  older  than  the  youngest  assemblage  were  identified
as  reworked  taxa.  Issues  do  appear,  especially  concerning
long-ranging Cenozoic taxa such Braarudosphaera bigelowii,

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Cyclicargolithus floridanus, Coccolithus pelagicus and
Sphenolithus moriformis. These were counted as separate
group. In such a situation the calculated percentage value of
reworking should be interpreted as the minimum level of re-
working.

Representative samples of marls, clay shales and turbiditic

mudstones differing in colour (black, brownish, olive-green
and grey) were chosen for mineralogical and petrological in-
vestigations.  The  mineral  composition  of  rocks  was  deter-
mined  using  X-ray  diffraction  (XRD).  Fourteen  samples  of
rock  were  ground  before  testing  in  a  ceramic  mortar.  The
analyses were performed using a Philips X’Pert diffractome-
ter  with  the  generator  PW1870  and  the  vertical  goniometer
PW3020,  equipped  with  a  graphite  diffracted-beam  mono-
chromator.  CuK

α radiation was used with the applied volt-

age of 40 kV and 30 mA current. The random mounts were
scanned from 2—64° 2

Θ at a counting time of 1 second per

0.02° step.

Petrological features were studied in thin-sections of 13

samples  by  using  optical  microscopy  Nikon-Eclipse  E  600
POL, under transmitted light. The XRD and optical analyses
were  performed  at  the  Institute  of  Geological  Sciences,
Jagiellonian University, Kraków, Poland. The abbreviations
for  names  of  rock-forming  minerals  follow  Whitney  &
Evans (2010). Thirty samples of pelite rocks from the Ropa
tectonic  window  were  selected  for  geochemical  studies.
Samples were collected from each of the three thrust-sheets.
They represent a complete sequence from the S-GB through
the  GMF  to  the  Krosno  Beds.  Similar  lithotypes  were  used
for  comparison.  Many  data  reflect  chemical  variations  in
each  lithology.  The  rock  samples  were  crushed  and  hand-
pulverized in agate mortar and pestle to the fraction passing
200 mesh.  Sample  amounts  of  typically  0.2 g  dry  weight
pulp  were  decomposed  by  lithium  borate  fusion  and  dilute
acid digestion before a classical whole-rock analysis by ICP
emission  spectrometry.  ICP-OES  analyses  of  major  oxides
package  includes  SiO

, Al

, Fe

MgO, CaO, Na

O, TiO

, P

, MnO, Cr

and loss on ignition (LOI),

which is measured by weight difference after ignition at
1000 °C. Trace element contents were determined through
the ICP-MS technique (ACME Analytical Laboratories, Ltd.,
2013). Geochemical analyses were conducted at the ACME
Laboratory in Vancouver, Canada.

Contents of major, minor and trace elements in the studied

material were compared to those in the standard sediments:
Post-Archean  Australian  Shale  (PAAS  after  Taylor  &
McLennan  1985),  average  shales  (Wedepohl  1991)  and  up-
per  continental  crust  (UCC  –  after  Rudnick  &  Gao  2003;
Hu  &  Gao  2008).  The  Eu  anomaly  expressed  by  Eu/Eu*
ratio was calculated using Eu/Eu* = Eu

/(Sm

×Gd

)

0.5

ratio,

where

means element content normalized to UCC. The

Ce anomaly was calculated analogous, using the ratio
Ce/Ce* = Ce

/(La

×Pr

)

0.5

The A—CN—K triangular plot is based on the ratio between

, CaO* + Na

O and K

O (Nesbitt & Young 1984).

CaO* is the amount of CaO in the silicate fraction. If CaO
has affinity to carbonates, CaO* is equivalent to Na

(McLennan 1993; cf. Hofer et al. 2013). The chemical index
of alteration (CIA – Nesbitt & Young 1982) is used to de-

termine the degree of source area weathering. The formula
for calculating the CIA is as follows:

CIA = (Al

/Al

+ Na

O + K

O + CaO)*100.

The chemical proxy of alteration (CPA; Cullers 2000) was

used as a complement to the CIA when it is affected by CaO
from minerals other than silicates. The CPA is calculated as
follows:

CPA = (Al

/(Al

+ Na

O))*100.

Results

Calcareous nannofossils

Preservation and abundance

State of preservation is one of the methods used in identify-

ing  reworked  fossils  via  the  presence  of  very  intensive  me-
chanical damage as well as signs of etching, severe dissolution
and overgrowth. When considering all the investigated assem-
blages the preservation of calcareous nannofossils is moderate
(m)  or  predominantly  moderate-to-good  (m-g)  in  all  investi-
gated  samples  (Tables 1  and  2).  Nannofossils  show  minor
etching and minor-to-moderate over growth. A good to mod-
erate preservation of nannofossils indicates that little carbon-
ate dissolution has occurred in these sediments.

Biostratigraphy

Analyses, using the standard Martini zonation (1971), con-

firmed results obtained through earlier research (Oszczypko-
Clowes 2008). The obtained results for all the samples from
Ropa tectonic windows, are summarized in Table 3.

The FO of Cyclicargolithus abisectus is usually found

close  to  the  FO  of  Sphenolithus  ciperoensis  (zonal  marker
for the lower boundary of NP24 Zone) and thus can be used
to approximate the boundary of NP23 and NP24 (Martini &
Műller 1986). However, many authors believed that this spe-
cies  is  already  present  in  the  lower  part  of  the  NP23  (e.g.
Bukry 1973; de Kaenel & Villa 1996; Melinte 2005; Maiorano
& Monechi 2006; Melinte-Dobrinescu & Brustur 2008). The
size  of  coccolith  is  important,  smaller  sizes  are  character-
istic  of  the  upper  part  of  NP23  and  NP24,  greater  (greater
than  10  or  11  microns,  see  e.g.  De  Kaenel  &  Villa  1996;
Maiorano  &  Monechi  2006;  Śliwińska  et  al.  2012)  for  the
upper part of NP24.

Taking into account the absence of Transversopontis fibula,

Orthozygus  aureus,  Lanternitus  minutus  and  Chiasmolithus
oamaruensis,  which  has  the  LO  in  the  upper  part  of  NP23
(see Melinte 2005) it is possible to include the given samples
into  NP24  Zone.  In  addition,  Sphenolithus  dissimilis  Bukry
&  Percival  was  also  observed.  The  FO  of  these  species  is
characteristic for zone NP24 (see Perch-Nielsen 1985). How-
ever the size of Cyclicargolithus abisectus varies. C. abisec-
tus found in assemblages belonging to the Sub-Grybów Beds
were smaller than 10 microns, which can indicate the lower
part  of  NP24,  whereas  assemblages  from  the  Grybów  Marl
Formation  and  Krosno  Beds  contained  specimens  bigger
than 10 microns. This indicates the upper part of NP24.

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The zone assignment of NP25 is based on the first occur-

rence  (FO)  of  Sphenolithus  capricornutus  and  S.  conicus.
Slightly less abundant are Cyclicargolithus abisectus, Reticu-
lofenestra  lockeri,  S.  dissimilis  and  R.  dictyoda.  Dictyococ-
cites bisectus is present, though rare. The FO of Sphenolithus
conicus has been frequently used as the base of the NN1 zone,
however,  Bizon  &  Műller  (1979),  Biolzi  et  al.  (1981)  and
Melinte  (1995)  observe  the  FO  of  this  species  as  low  as  the
upper  part  of  the  NP25  zone.  This  zone  was  determined  in
thrust-sheet I of both sections, within the Krosno beds.

Species diversity and age determination of reworked as-

semblages

Forty four species were identified during quantitative anal-

yses  of  calcareous  nannoplankton.  The  difference  between
the  reworked  assemblages  of  the  two  sections  has  only  a
quantitative  character.  Qualitatively  these  assemblages  are
the same. The level of reworking is generally not too high. It
varies from 8 % to 11 % for the samples collected from the
Chełmski section and from 9 % up to 17 % in the case of the
Górnikowski  section  (Fig. 4,  Tables 1  and  2).  The  excep-
tions are samples 14/02/N and 17/02/N where the level of re-
working  reaches  the  value  of  20 %  and  22 %  respectively.
The greatest number of reworked specimens was observed in
samples 27/05/N and 26/05/N (11 % and 10 %, respectively)
taken from the Sub-Grybów Beds.

The reworked assemblage consists of Paleogene and Creta-

ceous  taxa.  In  the  Chełmski  section  the  Cretaceous  species
form  between  3 %  and  6 %  of  the  reworked  association
whereas in the case of the Górnikowski section it is between
3 % and 8 %, except for the sample 19/02/N with the value of
10 %  (Tables 1  and  2,  Fig. 4).  The  percentage  abundance  of
Paleogene species varies from 3 % up to 6 % (Chełmski sec-
tion ) and from 3 % up to 16 % (Górnikowski section). The
main  components  of  the  Paleogene  assemblage  (Tables 1
and  2)  are  Reticulofenestra  spp.,  Isthmolithus  recurvus,  and
Lanternithus  minutus.  Reticulofenestra  spp.  ranges  from  0
(samples 28/05/N and 5/06/N – Chełmski section; 19/02/N
and  27/02/N  –  Górnikowski  section)  up  to  3 %  (sample
27/05/N  –  Chełmski  section)  and  5 %  (14/02/N  –  Górni-
kowski  section).  The  abundance  of  Isthmolithus  recurvus
does  not  exceed  2 %  in  the  case  of  the  Chełmski  section,
whereas in the case of Górnikowski section it is higher, ap-
proaching  the  value  of  5 %  (sample  15/02/N).  The  most
abundant element of the assemblage is Lanternithus minutus.
The average content of this species for the Górnikowski sec-
tion is 3 %. In the Chełmski section it is much lower with the

result that 4 samples out of 15 did not contain Lanternithus
minutus (Tables 1 and 2).

The precise age determination of Paleogene assemblages

is not easy, especially as an overlap pattern of several index
species  is  visible.  The  only  typical  Lower  Eocene  taxon  is
Discoaster  lodoensis  (NP12—14).  The  most  abundant  are
long-ranging  species  including  Discoaster  barbadiensis
(NP10—20), Ericsonia formosa (NP21), Helicosphaera bram-
lettei  (NP14—23)  Lanternithus  minutus  (NP16—22),  Reticu-
lofenestra hillae (NP16—22) and R. umbilica (NP16—22).

Their stratigraphic ranges span from the Middle Eocene to

Early Oligocene. These taxa may constitute Middle Eocene,
Late Eocene or even Early Oligoceene assemblages. The pres-
ence of Middle Eocene could be dated by the Chiasmolithus
grandis (NP11—17).

The presence of Isthmolithus recurvus suggests that part of

the assemblage may be not older than Zone NP19—20 (Late
Eocene) and not younger than NP22 (Early Oligocene), as
R. umbilica is the index species for the upper limit of Zone
NP22).

Mineralogy and geochemistry

Mineral composition and petrographic features

The mineral composition of the material studied was car-

ried  out  using  X-ray  diffraction.  All  of  the  samples  studied
consist  of  quartz,  feldspar,  10 Å-phyllosilicates  (mica)  and
clay  minerals  (mixed-layer  I/S,  kaolinite  and  chlorite).
Quartz  peaks  are  the  most  intensive  in  the  mudstone  sam-
ples.  Taking  into  account  the  calcite  content,  the  Grybów
Marl  Formation  is  the  most  enriched,  whereas  the  Krosno
Beds  are  destitute  of  calcite.  The  XRD  pattern  of  the  marl
samples of the GMF (e.g. 17/05/N, 30/05/N, 33/05/N) weakly
register  the  peaks  of  clay  minerals.  However,  the  kaolinite
peak is always evident. Some mudstones and marly shales of
the S-GB and GMF (e.g. samples 18/02/N, 19/02/N, 35/02/N,
24/02/N and 33/05/N) display intensive peaks of Mg-Fe car-
bonates on the XRD pattern (Fig. 5).

Rhombohedra of carbonate minerals were microscopically

noted in many samples (e.g. 1/07/N, 26/05/N, 33/05/N). The
thin-section examinations reveal discrete lamination empha-
sized by parallel lying mica flakes and strips of organic mat-
ter. The S-GB and GMF contain abundant glauconite, whose
contents decrease in the Krosno Beds. Heavy minerals repre-
sented  by  abraded  grains  of  zircon,  rutile  and  tourmaline
were  recognized  in  the  silt  and  mudstone  samples  (1/07/N,
19/05/N,  20/02/N,  33/05/N;  Fig. 6)  and  also  in  the  clayey

Table 3: Biostratigraphy based on calcareous nannofossils (based on Oszczypko-Clowes 2008).

ROPA — CHEŁMSKI STREAM

THRUST SHEET I

THRUST SHEET II

THRUST SHEET III

Grybów Marl Formation (GMF)

Krosno Beds

Sub-Grybów Beds (S-GB) Grybów Marl Fm (GMF)

Krosno Beds

GMF

NP24 NP24

and

NP25

NP24 NP24

NP24

ROPA — GÓRNIKOWSKI STREAM

THRUST SHEET I

THRUST SHEET II

THRUST SHEET III

Krosno Beds

Sub-Grybów Beds (S-GB) Grybów Marl Fm (GMF)

Krosno Beds

GMF Krosno

Beds

NP25 NP24

NP24

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shales  (24/05/N).  Organic  matter,  an  important  component
of  the  black  and  brownish  samples,  is  comprised  mainly  of
the  remains  of  plants.  The  black  detritus  occurs  abundantly
in  the  dark  samples  (e.g.  1/07/N,  16/05/N,  19/05/N;  Fig. 6)
and,  with  a  lesser  frequency,  in  the  light-coloured  samples
(26/05/N,  28/05/N,  20/02/N).  Organic  matter  is  associated
with  pyrite  which  is  often  transformed  into  amorphous  Fe
oxyhydroxides (Fig. 6).

Chemical composition

Major elements

Major element compositions of the Grybów Unit samples

are shown in Table 4. The average compositions of Upper
Continental Crust (UCC – Rudnick & Gao 2003; Hu & Gao
2008), Post-Archean Australian Shale (PAAS – Taylor &
McLennan 1985) and average shales are also listed for com-
parison. Major element abundances in formations studied are
usually lower than that in standards, except for CaO, contents
of which are significantly higher in the samples. Owing to the

strongly calcareous character of the sediments, CaO dilutes
other chemical components. Samples 18/02/N and 24/05/N
from the Sub-Grybów Beds contain SiO

, Al

and CaO in

amounts comparable to these of the average shales. Few sam-
ples of moderately calcareous shales and mudstones of the
S-GB (18/02/N, 20/02/N, 1/07/N, 24/05/N) and the Krosno
Beds (34/05/N) resemble the average shales in respect of con-
tents of Al

or SiO

. Certain samples of the S-GB (19/02/N,

24/02/N, 24/05/N) and the GMF (16/05/N) from the second
thrust-sheet are enriched in Fe

relative to the standards.

The samples 1/07/N, 18/02/N and 24/02/N are also rich in
MgO. The highest amounts of MgO were recognized in two
samples 35/02/N and 32/02/N of the GMF and Krosno Beds,
respectively.

High field strength trace elements (Zr, Hf, Nb) and Th, U, REE

The concentrations of trace elements (TE) in the samples of

the Grybów Nappe from the Ropa tectonic window are shown
in Table 4. The material studied is generally depleted of TE
relative to the upper continental crust (UCC) and Post-

Fig. 5. The powder XRD patterns of samples representing the Sub-Grybów Beds, Grybów Marl Formation and Krosno Beds of the Grybów
Nappe from the Ropa tectonic windows. Ab – albite, Cal – calcite, Chl – chlorite, Dol – dolomite, Kln – kaolinite, Ms – muscovite,
Qz – quartz, Sme – smectite.

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Fig. 6. Thin-section microphotographs showing recycled specimens. a, b – silt-grained sample of the Sub-Grybów Beds 1/07/N, transmit-
ted light (TL), parallel polars; c – black mudstones of the GMF, sample 19/05/N, reflected light; d – black mudstones of the GMF, sample
19/05/N, TL, parallel polars; e – bluish-grey clayey shale of the S-GB, sample 24/05/N, TL, crossed polars; f – green marly shale of the
S-GB, sample 26/05/N, TL, parallel polars. Cb – carbonate minerals, Glt – glauconite, Ght – goethite, Hem – hematite, HM – heavy
minerals (undefined), Qz – quartz, Rt – rutile, TOM – terrestrial organic matter, Zrn – zircon.

Archean Australian shales (PAAS). Th and Nb mostly corre-
late with TiO

and Al

(Fig. 7). The higher concentrations

of TiO

, Th and Nb are found in the samples from the S-GB

(24/05/N and 18/02/N) and Krosno Beds (34/05/N) that con-
tain the highest amounts of Al

. TiO

co-occurring with Zr

and Y correlate positively also with SiO

(Fig. 7, Table 4). It is

particularly visible in the silt samples of the S-GB (20/02/N
and 1/07/N). Accumulation of TE and SiO

also occurs in the

samples of the S-GB and Krosno Beds (24/05/N and 34/05/N)
that are concomitantly enriched in Al

(Table 4).

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Table

Whole-rock

major,

minor,

and

rare-earth

element

abundances

for

the

Sub-Grybów

Beds,

Grybów

Marl

Formation

and

Krosno

Beds

the

Grybów

Nappe

from

the

Ropa

Grybów

tec-

tonic

window.

UCC

data

from

Rudnick

Gao

(2003)

and

Gao

(2008);

Post-Archean

Australian

Shale

(PAAS)

–

Taylor

McLennan

1985).

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Table 4: Continued.

An enhanced concentration of uranium,

predominantly oc-

curs in the black and brownish, marly shales of the GMF (maxi-
mal amounts of U are recognized in 15/05/N, 19/05/N, 20/05/N).
Contents of U reveal no correlation with Al

(Fig. 7).

Generally, the REE distribution in the material studied dif-

fers from that in UCC. Only two samples 22/02/N and 21/05/N
from the S-GB and Krosno Beds respectively are concurrent
to UCC. The distribution of REE normalized to UCC in the
samples  15/05/N  and  32/05/N,  from  the  GMF  and  Krosno
Beds  respectively  is  parallel  to  that  of  PAAS,  however  the
contents  measured  of  REE  are  lower  than  that  of  PAAS
(Fig. 8,  Table 4).  Most  of  the  samples  show  a  tendency  to-
wards decreasing heavy-REE (HREE) (Fig. 8). Two samples
from  the  S-GB  (24/02/N  and  1/07/N)  portray  the  climbing
trend. The UCC normalized REE patterns of many samples
(e.g.  19/02/N,  19/05/N,  27/02/N,  35/02/N,  37/02/N)  show
clearly  convex  curvatures  in  middle-REE  (MREE)  with  re-
spect  to  light-  and  heavy-REE  (Fig. 8).  MREE  enrichment
co-varying with P

was described in the samples 27/02/N,

35/02/N, 16/05/N, 20/05/N, of which 16/05/N, 20/05/N are
brown marly shales (Table 4). All these samples are concom-
itantly rich in MnO and Fe

(all Fe was measured as

). Some samples show MREE convex curvatures and

enrichment in MnO, Fe

and/or MgO in spite of low phos-

phorous content (19/05/N 18/02/N, 19/02/N, 33/05/N).

Some samples enriched in HREE also contain higher

amounts of Y (19/05/N), Zr (20/02/N, 24/02/N), or both, Zr
and Y (1/07/N, 18/02/N) (Table 4). Eu anomaly is slightly
negative, but several samples of the S-GB (26/05/N, 28/05/N,
20/02/N, 23/02/N, 24/02/N), GMF (15/05/N, 31/05/N,
31/02/N) and Krosno Beds (32/02/N) show Eu/Eu*

≥1. Cor-

relation between Eu/Eu* and Al

is clearly negative for

the S-GB and Krosno Beds. In the GMF, Eu/Eu* changes in-
dependently from Al

. Ce anomaly is positive (Ce/Ce* > 1)

in  all  samples  (Table 4).  Higher  values  of  the  Ce/Ce*  ratio
(1.08—1.24)  characterize  the  S-GB,  whereas  lower  Ce/Ce*,
ranging  from  1.02  to  1.12  were  measured  in  the  GMF  and
Krosno  Beds.  Correlation  of  Ce/Ce*  to  Al

is flat in the

GMF. In the S-GB and Krosno Beds, Ce anomaly correlates
positively with Al

(Fig. 7).

Interpretation

Source rocks and sedimentary processes

Major element chemistry employed to determine the

weathering of the source rocks can also deliver evidence of
recycled material presence. In the A—CN—K diagram (Fig. 9),
the samples of the Grybów Unit cluster in the upper part of
the triangle, along the A—K axis, pointing to the source in

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Fig. 7. Interactions between selected major and trace elements in the Sub-Grybów Beds, Grybów Marl Formation and Krosno Beds of the
Grybów Nappe from the Ropa tectonic window.

rock with chemical composition similar to granite. The CIA
values varying from 72.4 to 80.6 correlate with CPA that are
between 90.5 and 96.5. Both CIA and CPA indicate intense
weathering of the source rocks.

Sedimentary processes cause fractionation of stable weath-

ering quartz and heavy minerals from clay minerals. Th and
Nb correlate with TiO

and Al

suggesting affinity of Th,

Nb and TiO

to phyllosilicates. Positive correlation between

TiO

, Zr, Y and SiO

may imply presence of rutile and zir-

con sorted together with quartz (see Fig. 7). Ternary diagram
plotting 10

×Al

—Zr—200

×TiO

(Fig. 10) illustrates the

presence of sorting-related fractionations (Garcia et al.
1991). Zircon is a carrier mineral for Zr and HREE plus Y,
thus HREE and Y often co-vary with Zr. Accumulation of
TE and SiO

co-occurs sometimes with Al

(e.g. 24/05/N

and 34/05/N) suggesting that material is worse sorted.

The Zr/Sc ratio is a useful index of sediment recycling

(Hassan et al. 1999). When Zr/Sc is plotted against Th/Sc
(McLennan et al. 1993), Zr enrichment during sorting can be
evaluated. In the Zr/Sc vs. Th/Sc diagram (Fig. 11) samples
fall along a trend involving zircon addition suggestive of a
recycling effect.

Petrographic and geochemical indices of redeposition

An abundant matrix enclosing lithic particles within the

S-GB,  GMF  and  Krosno  Beds  determines  their  peculiar
geochemical  greywacke  character.  Occurrences  of  rounded
grains  of  heavy  minerals  and  stable  for  weathering  inert
macerals (inertinite) indicate enhanced contribution of recy-
cled material within the Grybów Nappe sediments. More pe-
lagic marls of the GMF contain smaller amounts of detritus.

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Fig. 8. Upper Continental Crust (UCC) – normalized REE patterns of the Sub-Grybów Beds, Grybów Marl Formation and Krosno Beds of
the Grybów Nappe from the Ropa tectonic window. UCC data from Rudnick & Gao (2003) and Hu & Gao (2008), Post-Archean Australian
Shale (PAAS – Taylor & McLennan 1985).

Fig. 9. A—CN—K diagram. A – Al

, CN – CaO* + Na

K – K

O, in molecular proportions (Nesbitt & Young 1984) for the

Sub-Grybów Beds, Grybów Marl Formation and Krosno Beds of
the Grybów Nappe from the Ropa tectonic window. CIA – Chem-
ical Index of Alteration (Nesbitt & Young 1982), Chl – chlorite,
Gbs – gibbsite, Ilt – illite, Kfs – K-feldspar, Kln – kaolinite,
Ms – muscovite, Pl – plagioclase, Sme – smectite. 1 – gabbro,
2 – tonalite, 3 – granodiorite, 4 – granite typical igneous rock
averages from Fedo et al. (1997). Solid arrow indicates the theoretical
weathering trend for granite.

Fig. 10. Ternary 10

×Al

—200

×TiO

—Zr plot (after Garcia et al.

1994) showing possible sorting trend for the Sub-Grybów Beds,
Grybów Marl Formation and Krosno Beds of the Grybów Nappe
from the Ropa tectonic window. For explanation see Fig. 7.

In a diagram of lg (SiO

/Al

) vs. lg (Fe

O), pro-

posed by Herron (1988) to classify the terrigenous sands and
shales, the samples are within the fields of shale and
greywacke (Fig. 12). Due to higher contents of Fe

two

samples of the S-GB (19/02/N, 1/07/N) are classified as
Fe-shale and Fe-sandstone respectively. Chemical composi-

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tion is inferred from the presence of glauconite, Fe-oxyhy-
droxides and Fe-Mg carbonates, which are confirmed by mi-
croscopic and XRD analysis (see Figs. 5, 6). Glauconite is a
frequent mineral in the S-GB and GMF. Detritus accumulat-
ed in sediments of the S-GB and GMF could be transported
from the shelf, where glauconite was formed.

Depositional redox conditions and the influence of diagenetic
processes

Negative correlation between Eu/Eu* and Al

supports

the authigenic origin of Eu anomaly, which generally re-
flects alteration of Eh conditions in the deposit (Elderfield &
Sholkovitz 1987). Negative Eu anomaly suggests reductive
conditions when the GMF was formed (e.g. 19/05/N, 30/05/N
and 37/02/N; MacRae et al. 1992). The reductive conditions

Fig. 11. Th/Sc vs. Zr/Sc provenance and recycling discrimination
plot (after McLennan et al. 1990) for the Sub-Grybów Beds, Gry-
bów Marl Formation and Krosno Beds of the Grybów Nappe from
the Ropa tectonic window. For explanation see Fig. 7.

Fig. 12. Lg (Fe

O) vs. lg (SiO

/Al

) diagram after Herron

(1988) for the Sub-Grybów Beds, Grybów Marl Formation and
Krosno Beds of the Grybów Nappe from the Ropa tectonic window.
For explanation see Fig. 7.

also exert influence on the U contents (Jones & Manning
1994) that are enhanced in the black samples of the GMF
(15/05/N, 19/05/N, 20/05/N). The concentration of U reveals
no correlation with Al

(see Fig. 7) supporting its non-ter-

rigenous derivation.

The Ce anomalies are more positive in the S-GB and de-

crease to mildly above unity in the GMF and Krosno Beds.
If  a  positive-trending  cerium  anomaly  had  indicated  oxic
conditions  and/or  a  sea-level  fall  (Elderfield  &  Sholkovitz
1987),  decreasing  of  oxide  availability  and/or  sea-level  rise
and  influences  of  precipitation  of  marine  carbonates  could
have  governed  during  deposition  of  the  GMF.  On  the  other
hand,  positive  correlation  of  Ce/Ce*  to  Al

in the S-GB

and Krosno Beds indicates rather a detrital contribution of
the Ce anomaly.

The distribution patterns of REE of material studied usually

differ from those of PAAS and UCC, because the REE distri-
bution of fine-grained deposits is chiefly influenced by depo-
sitional and subsequent processes (Murray et al. 1990, 1992).
Distributions  of  REE  vary  considerably  as  a  function  of  up-
take  of  REE  by  organic  and/or  oxyhydroxide  grain  coatings
(Palmer  1985;  Grandjean-Lécuyer  et  al.  1993;  Sholkovitz  et
al. 1994) and variations in redox conditions (e.g. Elderfield et
al. 1990). MREE-enrichment in phosphate (Byrne et al. 1996)
can be a result of selective REE scavenging by algae (Stanley
&  Byrne  1990)  or  bacteria  (Cruse  et  al.  2000).  The  strongly
convex pattern at MREE suggests either enrichment in MREE
or relative depletion in adjacent REE during deposition and/or
diagenesis.  MREE  enrichment  can  by  related  to  reductive
conditions  in  the  black  shales  (19/05/N,  30/05/N,  37/02/N)
or to diagenetic Fe-Mn-Mg mineralization (18/02/N, 19/02/N,
35/02/N,  33/05/N).  Phosphate  is  probably  a  carrier  phase  of
MREE in the samples 27/02/N, 35/02/N, 16/05/N, 20/05/N, of
which 16/05/N, 20/05/N are brown marly shales, therefore or-
ganic influence may also be considered for them.

Discussion

The position and age of the youngest deposits, beneath the

Magura Nappe sole thrust, determine both the minimal am-
plitude of the Magura Nappe overthrust as well as the time in
which the overthrusting of this unit begun. The youngest de-
posits from the Ropa tectonic window belong to the Late
Oligocene – NP24 and NP25 zones and record the termina-
tion of Fore-Magura basins.

Reworked microfossils correlated with mineral and chemi-

cal composition can provide information on the processes of
source rock erosion, transportation, sedimentation and pres-
ervation.

The allochthonous nannoflora consists of Cretaceous, Early,

Middle Eocene and Late Eocene-Early Oligocene taxa. Vari-
ous age distributions provide an insight into the Cretaceous
to Cenozoic sediment reworking history in the remnant flysch
basin (see also Švábenická et al. 2007; Oszczypko-Clowes
2012). Cretaceous species, as well as Early Eocene taxa, are
reworked into Middle Eocene sediments. These sediments,
probable formed low, consolidated basin slopes periodically
incorporated into gravity flows.

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The presence of reworked Oligocene nannofossils shows a

more or less continuous erosion of newly deposited sedi-
ments on the sea floor during the Late Oligocene.

The contribution of recycled material within the Grybów

Nappe sediments is inferred from occurrences of inertinite and
rounded grains of glauconite and heavy minerals. In the Zr/Sc
vs. Th/Sc diagram (Fig. 11) samples fall along a trend involv-
ing zircon addition suggestive of a recycling effect. The per-
centage of reworked species and visible discrepancy between
sections  can  be  clearly  associated  with  lithology  as  well  as
with the distance from the source area. The Górnikowski sec-
tions  are  characterized  by  higher  content  of  clastic  material.
The  samples  from  the  Chełmski  sections  contain  more  clay
fraction than the Górnikowski section samples, as is shown in
the diagram of lg(SiO

/Al

) vs. lg(Fe

O) (Fig. 12) and

by higher CIA and CPA values. Positive correlation between
TiO

, Zr, Y and SiO

(see Fig. 7), suggesting presence of rutile

and zircon sorted together with quartz is mostly evident for the
Chełmski section samples. It is confirmed by the ternary dia-
gram 10

×Al

—Zr—200

×TiO

(Fig. 10) illustrating the sorting-

related fractionations (Garcia et al. 1991). The Chełmski sections
display  more  distal  facies  of  turbidites.  The  GMF  collected
from here are enriched in U and MREE (Table 4, Figs. 7, 8) that
can  be  read  as  indicators  of  anoxic  and  reductive  conditions
during  deposition  and  early  diagenesis.  Bottom  water  was
hardly disturbed and freshened by declining turbidity currents.

The lack of Paleocene and Early Eocene nannofloral ele-

ments is probably due to the unavailability of sediments of
these ages for reworking processes. The diversity of Paleo-
cene and Early Eocene index species and their resistance to
degradation would permit them to be abundant in Cenozoic
flysch sediments. The same reworking pattern was observed
throughout the entire flysch belt of the Outer Dinaride nappe
front by Mikes et al. (2008).

During the Late Eocene—Oligocene, as results of regional

compression in the Alpine area, prominent paleogeographic
changes  took  place  in  the  Outer  Carpathian  sedimentary
area,  which  was  transformed  from  remnant  oceanic  basin
into a flexural foreland basin (Oszczypko 1999). It was man-
ifested  by  shallowing  of  all  sub-basins  and  isolation  from
oceanic areas (Van Couvering et al. 1981; Oszczypko-Clowes
2001).  The  deposition  of  deep-water  basinal  turbidites  was
substituted  by  pelagic  Submenilite  Globigerina  Marls
(SGM).  Finally  during  the  Rupelian  this  resulted  in  decline
of the circulation of currents, followed by the reduced oxy-
gen environment, with eutrophic population of microfossils,
and  deposition,  under  anoxic  bottom  water  conditions,  of
dark organic-rich shales of the Menilite formation (Bessereau
et  al.  1996;  Pícha  &  Stráník  1999;  Oszczypko-Clowes  &
Żydek  2012).  At  the  same  time  the  emerging  Fore-Magura
Ridge, which was the prolongation of the Marmarosh Massif
(Oszczypko  et  al.  2005)  separated  the  Dukla-Grybów  sub-
basin from the Magura Basin. The Oligocene Dukla succes-
sion  become  a  part  of  the  Silesian  Basin  that  was  supplied
from the south (Unrug 1968), as is proved by the analyses of
paleotransport  directions  indicating  the  transport  of  clastic
material from the south-east and the south.

The Oligocene—Early Miocene closing of the northern sec-

tor of the Outer Carpathian sedimentary area is manifested

by the deposition of the Krosno synorogenic lithofacies,
which occupied the Grybów-Dukla-Silesian/Sub-Silesian/
Skole and Boryslav-Pokuttya basin system.

During the latest Oligocene period the thrusting of the

Magura  Nappe  onto  the  Fore-Magura  (Dukla  and  Grybów)
sedimentary  area  began  to  occur.  From  latest  Oligocene  to
late  Badenian  (9—10 Ma;  see  Oszczypko  1998)  the  front  of
the Magura Nappe progressed towards the north. As a result
the  Grybów  Unit,  with  reduced  thickness,  is  wedged  be-
tween  the  Magura  Nappe  and  Dukla  Unit.  In  surface  expo-
sures the Grybów Unit reveals thrust sheet structure.

The Ropa tectonic window developed during the Middle

Miocene thrusting of the Magura Nappe against its foreland.

Conclusions

•

The youngest deposits from the Ropa tectonic window

belong to the Late Oligocene – NP24 and NP25;

•

The Grybów Succession records the terminal stage of the

Fore-Magura Basin development;

•

These synorogenic turbidites facies are characterized by

a medium level of reworked nanofossils;

•

A high contribution of recycled material is inferred from

presence of lithic grains, abraded heavy minerals (zircon and
rutile), rounded glauconite as well as inert macerals (iner-
tinite). Enrichment in zircon and rutile is confirmed geochem-
ically by positive correlation between Zr, SiO

and TiO

It is

also plotted on 10

×Al

—Zr—200

×TiO

and Zr/Sc vs. Th/Sc

diagrams. The source rocks are chemically similar to gran-
ites, that were affected by strong weathering shown in the
A—CN—K diagram, and by high values of CIA and CPA;

•

Chełmski sections display more distal facies of turbid-

ites. The sediments consist of less detritus, which represents
mainly clay fraction and is well-sorted. It corresponds to the
lower frequency of reworked nanofossils;

•

Brownish-black sediments of the GMF were formed un-

der anoxic and reductive conditions;

•

Post-depositional processes are recorded by Fe-Mn-Mg

mineralization, phosphate precipitation, REE fractionation
and U enrichment.

Acknowledgments: The authors wish to thank Katarína

Šarinová  and  Diego  Puglisi  for  their  constructive  criticism
and  detailed  review  of  the  manuscript.  Ján  Soták  is  also
gratefully  acknowledged  for  his  valuable  comments  on  the
manuscript. The research was undertaken as part of a Project
of  the  Polish  Ministry  of  Science  and  Higher  Education
Grant (No. N N307 531038).

References

Aubry M.P. 1984: Handbook of Cenozoic calcareous nannoplankton.

Book 1: Ortholithae (Discoasters). Micropaleontology Press,
Amer. Mus. Natur. Hist., New York, 1—265.

Aubry M.P. 1988: Handbook of Cenozoic calcareous nannoplank-

ton. Book 2: Ortholithae (Holochoccoliths, Ceratoliths and
others). Micropaleontology Press, Amer. Mus. Natur. Hist.,
New York, 1—279.

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Aubry M.P. 1989: Handbook of Cenozoic calcareous nannoplankton.

Book 3: Ortholithae (Pentaliths, and others) Heliolithae (Fasci-
culiths, Sphenoliths and others). Micropaleontology Press,
Amer. Mus. Natur. Hist., New York, 1—279.

Aubry M.P. 1990: Handbook of Cenozoic calcareous nannoplank-

ton. Book 4: Heliolithae (Helicoliths, Cribriliths, Lopadoliths
and others). Micropaleontology Press, Amer. Mus. Natur.
Hist., New York, 1—381.

Aubry M.P. 1999: Handbook of Cenozoic calcareous nannoplank-

ton. Book 5: Heliolithae (Zygolithus and Rhabdolithus). Micro-
paleontology Press, Amer. Mus. Natur. Hist., New York, 1—367.

Bessereau G., Roure F., Kotarba M., Kusmirek J. & Strzetelski W.

1996: Structure and hydrocarbon habitat of the Polish Car-
pathians. In: Ziegler P.A. & Horváth F. (Eds.): Peri-Tethys
Memoir 2: Structure and prospects of Alpine basins and fore-
lands. Mém. Mus. Nat. Hist. Natur. 170, 343—373.

Biolzi M., Műller C. & Palmieri G. 1981: Calcareous nannoplank-

ton. In: Gelati R. & Steininger F. (Eds.): In search of the Paleo-
gene—Neogene boundary stratotype. Part II. Riv. Ital. Paleont.
Stratigr. 89, 4, 460—471.

Bizon G. & Műller C. 1979: Remarks on the Oligocene/Miocene

boundary based on the results obtained from the Pacific and
the Indian Ocean. Ann. Géol. Pays Hellén. 1, 101—111.

Blaicher J. 1958: The microfauna of the Magura Series of the Gry-

bów region (Middle Carpathians). Geol. Quarterly 2, 385—399
(in Polish with English summary).

Bown P.R. (Ed.) 1998: Calcareous Nannofossil biostratigraphy.

British Micropalaeont. Soc. Ser., Kluwer Academic Publishers,
Cambridge, 1—315.

Bukry D. 1973: Low-latitude coccolith biostratigraphic zonation.

Init. Repts. Deep Sea Drill. Proj. 15, 127—149.

Burtan J., Cieszkowski M., Jawor E. & Ślączka A. 1992: Dąbrowa

–  Geology  of  the  Klęczany-Limanowa  tectonic  window.
[Dąbrowa-Budowa  okno  tektonicznego  Klęczan-Limanowej.]
In:  Zuchiewicz  W.  &  Oszczypko  N.  (Eds.):  A  guidebook  of
63

Annual Meeting of Polish Geological Society, Koninki,

17—19 September 1992. Jagiellonian Univ., Inst. Geol. Sci.,
Kraków, 171–179 (in Polish).

Byrne R.H., Liu X. & Schijf J. 1996: The influence of phosphate

coprecipitation on rare earth distribution in natural waters.
Geochim. Cosmochim. Acta 60, 3341—3346.

Cieszkowski M. 1992: Michalczowa zone: a new unit of the fore-

Magura zone, Outer West Carpathians, South Poland. [Strefa
Michalczowej – nowa jednostka strefy przedmagurskiej w za-
chodnich Karpatach fliszowych i jej geologiczne znaczenie.]
Zesz. Nauk. AGH, Geologia 18, 1—2, 1—125 (in Polish).

Cruse A.M., Lyons T.W. & Kidder D.L. 2000: Rare-earth element

behavior in phosphates and organic-rich host shales: an exam-
ple from the Upper Carboniferous of midcontinent North
America. In: Glenn C.R., Prévot L. & Lucas J. (Eds.): Marine
authigenesis: from global to microbial. SEPM Spec. Publ. 66,
445—453.

Cullers R.L. 2000: The geochemistry of shales, siltstones and sand-

stones of Pennsylvanian—Permian age, Colorado, USA: impli-
cations for provenance and metamorphic studies. Lithos 51,
181—203.

de Kaenel E. & Villa G. 1996: Oligocene—Miocene calcareous nan-

nofossil biostratigraphy and paleoecology from the Iberia
Abyssal Plain. Proc. ODP, Sci. Results 149, 79—145.

Elderfield H. & Sholkovitz E.R. 1987: Rare earth elements in the

pore waters of reducing nearshore sediments. Earth Planet.
Sci. Lett. 82, 280—288.

Elderfield H., Upstill-Goddard R. & Sholkovitz E.R. 1990: The rare

earth elements in rivers, estuaries, and coastal seas and their
significance to the composition of ocean waters. Geochim.
Cosmochim. Acta 54, 971—991.

Fedo C.M., Young G.M. & Nesbitt G.M. 1997: Paleoclimatic con-

trol on the composition of the Paleoproterozoic Serpent Forma-
tion, Huronian Supergroup, Canada: A greenhouse to icehouse
transition. Precambrian Res. 86, 201—223.

Garcia D., Coelho J. & Perrin M. 1991: Fractionation between TiO

and Zr as a measure of sorting within shale and sandstone se-
ries (Northern Portugal). Eur. J. Mineral. 3, 401—414.

Garcia D., Fonteilles M. & Moutte J. 1994: Sedimentary fraction-

ations between Al, Ti and Zr and the genesis of strongly pera-
luminous granites. J. Geology 102, 411—422.

Gedl P. 2005: Stop 1 – Ropa: palaeoenvironmental changes across

the Eocene—Oligocene boundary in the Flysch Carpatian ba-
sins. In: Excursion guide of 5

Micropaleontological Work-

shop, Szymbark, Poland, June 8—10, 2005. Instytut Nauk
Geologicznych PAN, Kraków, 65—68.

Grandjean-Lécuyer P., Feist R. & Albarède F. 1993: Rare earth ele-

ments in old biogenic apatites. Geochim. Cosmochim. Acta 57,
2507—2514.

Hassan S., Ishiga H., Roser B.P., Dozen K. & Naka T. 1999:

Geochemistry of Permian Triassic shales in the Salt range, Pa-
kistan: implications for provenance and tectonism at the Gond-
wana margin. Chem. Geol. 168, 293—314.

Herron M.M. 1988: Geochemical classification of terrigenous sands

and shales from core or log data. J. Sed. Petrology 58, 820—829.

Hofer G., Wagreich M. & Neuhuber S. 2013: Geochemistry of fine-

grained sediments of the upper Cretaceous to Paleogene Gosau
Group (Austria, Slovakia): Implications for paleoenvironmen-
tal and provenance studies. Geosci. Frontiers 4, 449—468.

Hu Z. & Gao S. 2008: Upper crustal abundances of trace elements:

A revision and update. Chem. Geol. 253, 205—221.

Jones B. & Manning D.A.C. 1994: Comparison of geochemical in-

dices used for the interpretation of paleoredox conditions in
ancient mudstones. Chem. Geol. 111, 111—129.

Koráb T. & Ďurkovič T. 1978: Geology of Dukla Unit (East-Slova-

kian Flysch). Geologický Ústav Dionýza Štúra, Bratislava,
1—196 (in Slovak with English summary).

Kováč M., Plašienka D., Soták J., Vojtko R., Oszczypko N., Less G.

& Králiková S. (in print): Western Carpathians Palaeogene pa-
leogeography and basin development: a case study within the
scope of the ALCAPA terrane.

Kozikowski H. 1956: Ropa-Pisarzowa unit, a new tectonic unit of

the Polish flysch Carpathians. Biul. Inst. Geol. 110, 93—137 (in
Polish with English summary).

Kozikowski H. & Jednorowska A. 1957: The problem of the age of

the Grybow Beds and so called “Gray chalk” in the vicinity of
Gorlice. [Problem wieku warstw grybowskich i tzw. “szarej
kredy” z okolic Gorlic.] Przegl. Geol. 5, 3, 100—137 (in Polish
with English summary).

Książkiewicz M. 1972: Geology of Poland, v. IV Tectonics, part 3

Carpathians. [Budowa geologiczna Polski , t. IV Tektonika, cz.
3 Karpaty.] Wyd. Geol., Warszawa, 1—228 (in Polish).

Leszczyński S. 1997: Origin of the Sub-Menilite Globigerina Marl

(Eocene—Oligocene transition) in the Polish Outer Carpathians.
Ann. Soc. Geol. Pol. 67, 367—427.

MacRae N.D., Nesbitt H.W. & Kronberg B.I. 1992: Development

of a positive Eu anomaly during diagenesis. Earth Planet. Sci.
Lett. 109, 585—591.

Maiorano P. & Monechi S. 2006: Early to Late Oligocene calcareous

nannofossil bioevents in the Mediterranean (Umbria-Marche ba-
sin, central Italy). Riv. Ital. Paleont. Stratigr. 12, 261—273.

Martini E. 1971: Standard Tertiary and Quaternary calcareous nan-

noplankton zonation. In: Farinacci A. (Ed.): Proc. II. Planktonic
Conf. Roma 1970, Vol. 2. Edizioni Tecnoscienza, Rome,
729—785, pls. 1—4.

Martini E. & Müller C. 1986: Current Tertiary and Quaternary cal-

careous nannoplankton stratigraphy and correlations. Newslett.

533

PROVENANCE ANALYSIS OF THE GRYBÓW SUB-BASIN (OUTER W CARPATHIANS, POLAND)

GEOL

EOL

EOLOGICA CARPA

OGICA CARPA

OGICA CARPATHICA

THICA

THICA, 2015, 66, 6, 515—534

Stratigr. 16, 2, 99—112.

McLennan S.M., Hemming D.K. & Hanson G.N. 1993: Geochemi-

cal approaches to sedimentation, provenance, and tectonics.
Geol. Soc. Amer., Spec. Publ. 284, 21—40.

McLennan S., Taylor S., McCulloch M. & Maynard J. 1990:

Geochemical and Nd-Sr isotopic composition of deep-sea tur-
bidites: Crustal evolution and plate tectonic associations.
Geochim. Cosmochim. Acta 54, 2015—2050.

Melinte M. 1995: Changes in nannofossil assemblages during the

Oligocene—Lower Miocene interval in the Eastern Carpathians
and Transylvania. In: Abstracts 10

RCMNS, Bucharest 1995.

Rom. J. Stratigraphy 76, suppl. 7, 171—172.

Melinte M. 2005: Oligocene palaeoenvironmental changes in the

Romanian Carpathians, revealed by calcareous nannofossils. In:
Tyszka J., Oliwkiewicz-Miklasinska M., Gedl P. & Kaminski
M. (Eds.): Methods and applications in micropalaeontology.
Stud. Geol. Pol. 124, 341—352.

Melinte-Dobrinescu M. & Brustur T. 2008: Oligocene—Lower Mio-

cene events in Romania. Acta Palaeont. Rom. 6, 203—215.

Mikes T., Báldi-Béke M., Kazmer M., Dunkl I. & von Eynatten H.

2008: Calcareous nannofossil age constraints on Miocene flysch
sedimentation in the Outer Dinarides (Slovenia, Croatia, Bosnia-
Herzegovina and Montenegro). In: Siegesmund S., Fugenschuh
B. & Froitzheim N. (Eds.): Tectonic aspects of the Alpine-Di-
naride-Carpathian system. Geol. Soc. London, Spec. Publ. 298,
335—363.

Murray R.W., Buchholtz Tenbrink M.R., Jones D.L., Gerlach D.C.

& Russ G.P. III 1990: Rare earth elements as indicators of dif-
ferent marine depositional environments in chert and shale.
Geology 18, 268—271.

Murray R.W., Buchholtz Tenbrink M.R., Gerlach D.C., Russ G.P.

III & Jones D.L. 1992: Interoceanic variation in the rare earth,
major, and trace element depositional chemistry of chert: Per-
spectives gained from the DSDP and ODP record. Geochim.
Cosmochim. Acta 56, 1897—1913.

Nesbitt H.W. & Young G.M. 1982: Early Proterozoic climates and

plate motions inferred from major element chemistry of lutites.
Nature 199, 715—717.

Nesbitt H.W. & Young G.M. 1984: Prediction of some weathering

trends of plutonic and volcanic rocks based on thermodynamic
and kinetic considerations. Geochim. Cosmochim. Acta 48,
1523—1534.

Olszewska B. 1981: On same assemblages of small foraminifers of

the windows series of Sopotnia Mała, Mszana Dolna, Szczawa
and Klęczany. Biul. Inst. Geol. 331, 141—163 (in Polish with
English summary).

Olszewska B. 1983: A contribution of the knowledge of planktonic

foraminifers of the Globigerina Submenilite Marls of the Polish
Outer Carpathians. Kwart. Geol. 27, 546—570 (in Polish).

Oszczypko (Clowes) M. 1996: Calcareous nannoplankton of the

Globigerina Marls (Leluchów Marls Member), Magura Nappe,
West Carpathians. Ann. Soc. Geol. Pol. 66, 1—15.

Oszczypko N. 1998: The Western Carpathian Foredeep – develop-

ment of the foreland basin in front of the accretionary wedge and
its burial history (Poland). Geol. Carpathica 49, 6, 415—431.

Oszczypko N. 1999: From remnant oceanic basin to collision-related

foreland basin – a tentative history of the Outer Western Car-
pathians. Geol. Carpathica, Spec. Issue 50, 161—163.

Oszczypko N. & Oszczypko-Clowes M. 2011: Stratigraphy and tec-

tonics of the Świątkowa Wielka Tectonic Window (Magura
Nappe, Polis Outer Carpathians). Geol. Carpathica 62,
139—154.

Oszczypko N., Ślączka A. & Żytko K. 2008: Tectonic subdivision

of Poland: Polish Outer Carpathians and their fore-deep.
Przegl. Geol. 10, 927—935 (in Polish with English summary).

Oszczypko N., Oszczypko-Clowes M., Golonka J. & Krobicki M.

2005: Position of the Marmarosh Flysch (Eastern Carpathians)
and its relation to the Magura Nappe (Western Carpathians).
Acta Geol. Hung. 48, 3, 259—282.

Oszczypko-Clowes M. 2001: The nannofossil biostratigraphy of the

youngest deposits of the Magura Nappe (East of the Skawa river,
Polish Flysch Carpathians) and their palaeoenvironmental con-
ditions. Ann. Soc. Geol. Pol. 71, 139—188.

Oszczypko-Clowes M. 2008: The stratigraphy of the Oligocene de-

posits from the Ropa tectonic window (Grybów Nappe, West-
ern Carpathians, Poland). Geol. Quarterly 52, 127—142.

Oszczypko-Clowes M. 2012: Reworked nannofossils from the

youngest flysch deposits in the Magura Nappe (Outer Western
Carpathians, Poland) – A case study. Geol. Carpathica 63,
407—421.

Oszczypko-Clowes M. & Oszczypko N. 2004: The position and age

of the youngest deposits in the Mszana Dolna and Szczawa tec-
tonic windows (Magura Nappe, Western Carpathians, Poland).
Acta Geol. Pol. 54, 339—367.

Oszczypko-Clowes M. & Ślączka A. 2006: Nannofossil biostrati-

graphy of the Oligocene deposits in the Grybów tectonic win-
dow (Grybów Unit, Western Carpathians, Poland). Geol.
Carpathica 57, 473—482.

Oszczypko-Clowes M. & Żydek B. 2012: Paleoecology of the Late

Eocene Early Oligocene Malcov Basin based on the calcareous
nannofossils – a case study of the Leluchów section (Krynica
Zone, Magura Nappe, Polish Outer Carpathians). Geol. Car-
pathica 63, 2,149—164.

Palmer M.R. 1985: Rare earth elements in foraminifera tests. Earth

Planet. Sci. Lett. 73, 85—298.

Perch-Nielsen K. 1985: Cenozoic calcareous nannofossils. In: Bolli

H., Saunders J.S. & Perch-Nielsen K. (Eds.): Plankton strati-
graphy. Cambridge University Press, 11, 427—554.

Pícha F. & Stráník Z. 1999: Late Cretaceous to early Miocene de-

posits of the Carpathian foreland basin in southern Moravia.
Int. J. Earth Sci. 88, 475—495.

Rudnick R.L. & Gao S. 2003: The composition of the continental

crust. In: Holland H.D. & Turekian K.K. (Eds.): Treatise on
geochemistry, the crust. Elsevier-Pergamon, 1—64.

Sholkovitz E.R., Landing W.M. & Lewis B.L. 1994: Ocean particle

chemistry: The fractionation of rare earth elements between
suspended particles and seawater. Geochim. Cosmochim. Acta
58, 1567—1579.

Sikora W. 1960: On the stratigraphy of the series in the tectonic

window at Ropa near Gorlice (Western Carpathians). Kwart.
Geol. 4, 152—170 (in Polish with English summary).

Sikora W. 1970: Geology of the Magura Nappe between Szymark

Ruski and Nawojowa. Biul. Inst. Geol. 235, 5—121.

Stanley J.K., Jr. & Byrne R.H. 1990: The influence of solution

chemistry on REE uptake by Ulva lactuca L. in seawater.
Geochim. Cosmochim. Acta 54, 1587—1595.

Ślączka A. 1971: Geology of the Dukla Unit. Prace Inst. Geol. 1,

1—63 (in Polish with English summary).

Ślączka A. 1973: Field trip 1 – Grybów, Polany, Berest, Krzyżówka.

[Wycieczka 1 – Grybów, Polany, Berest, Krzyżówka.] In:
Żytko K. (Ed.): A geological guidebook to the Eastern Flysch
Carpathians. Wyd. Geol., 78—87 (in Polish).

Ślączka A. (Ed.) 1976: Atlas of paleotransport of detrital sediments

in the Carpathian-Balkan Mountain System. Inst. Geol.,
Warszawa.

Ślączka A., Kruglow S., Golonka J., Oszczypko N. & Popadyuk I.

2006:  The  general  geology  of  the  Outer  Carpathians,  Poland,
Slovakia  and  Ukraine.  In:  Golonka  J.  &  Picha  F.  (Eds.):  The
Carpathians  and  their  foreland:  Geology  and  hydrocarbon  re-
sources. Amer. Assoc. Petrol. Geol. Mem. 84, 221—258.

Ślączka A., Renda P., Cieszkowski M., Golonka J. & Nigro F.

2012: Sedimentary basin evolution and olistolith formation:

534

OSZCZYPKO-CLOWES, WÓJCIK-TABOL and PŁOSZAJ

GEOL

EOL

EOLOGICA CARPA

OGICA CARPA

OGICA CARPATHICA

THICA

THICA, 2015, 66, 6, 515—534

The case of Carpathian and Sicilian region. Tectonophysics
568—569, 306—319.

Śliwińska K., Abrahamsen N., Beyer C., Brünings-Hansen T., Thom-

sen E., Ulleberg K. & Heilmann-Clausen C. 2012: Bio- and
magnetostratigraphy of Rupelian—mid Chattian deposits from
the Danish land area. Rev. Palaeobot. Palynol. 172, 48—69.

Świdziński H. 1963: Les couches de Grybów et leur importance

pour latectonique des Karpates. Resume des communications.
Congr. Geol. Assoc. Karpat.-Balk., Warszawa—Kraków, 6,
191—193.

Švábenická L., Bubík M. & Stráník Z. 2007: Biostratigraphy and

paleoenvironmental changes on the transition from the Menilite
to Krosno lithofacies (Western Carpathians, Czech Republic).
Geol. Carpathica 58, 237—262.

Taylor S.R. & McLennan S.M. 1985: The continental crust: Its com-

position and evolution. Blackwell Scientific, Oxford, 1—312.

Uhlig V. 1888: Ergebnisse geologischer Aufnahmen in den west-

galizischen Karpathen. Jb. Geol. Reichsanstalt 38, 85—264.

Unrug R. 1968: Silesia Ridge as a source area for clasticmaterial in

flysch sandstone of Beskid Śląski and Wyspowy (Polish West-

ern Carpathians). [Kordyliera śląska jako obszar źródłowy
materiału klastycznego piaskowców fliszowych Beskidu
Śląskiego i Beskidu Wysokiego (polskie Karpaty zachodnie).]
Rocz. Pol. Tow. Geol. 38, 1, 81—164.

Van Couvering I.A., Aubry M.P., Berggren Q.A., Bujak J.P.,

Naesen C.W. & Wieser T. 1981: Terminal Eocene event and
the Polish connections. Palaeogeogr. Palaeoclimatol. Palaeo-
ecol. 36, 321—362.

Veizer J. & Mackenzie F.T. 2003: Evolution of sedimentary rocks.

In: Holland H.D. & Turekian K.K (Eds): Treatise on geoche-
mistry. Sediments, diagenesis and sedimentary rocks. Elsevier,
Pergamon, 369—4077.

Wedepohl K.H. 1991: Chemical composition and fractionation of

the continental crust. Geol. Rdsch. 80, 2, 207—223.

Whitney D.L. & Evans B.W. 2010: Abbreviations for names of

rock-forming minerals. Amer. Mineralogist 95, 185—187.

Wójcik-Tabol P. & Ślączka A. 2013: Provenance of Lower Creta-

ceous deposits of the western part of the Silesian Nappe in Po-
land (Outer Carpathians): evidence from geochemistry. Ann.
Soc. Geol. Pol. 83, 113—132.