Geological Quarterly, 2012, 56 (1): 169-186 Trace element geochemistry of the Early to Late Cretaceous deposits of the Grajcarek thrust-sheets - a palaeoenvironmental approach (Małe Pieniny Mts., Pieniny Klippen Belt, Poland) Patrycja WÓJCIK-TABOL and Nestor OSZCZYPKO Wójcik-Tabol P. and Oszczypko N. (2012) - Trace element geochemistry of the Early to Late Cretaceous deposits of the Grajcarek thrust-sheets - a palaeoenvironmental approach (Małe Pieniny Mts., Pieniny Klippen Belt, Poland). Geol. Quart., 56 (1): 169-186. The chemical composition of the Cretaceous deposits of the Grajcarekthrust-sheets (Pieniny Klippen Belt, Poland) has been investigated to provide information on palaeoenvironment and provenance of pelagic and turbiditic particles. The material studied shows large varia- tions in terrigenous and biogenic content. Phyllosilicates (mirrored in amounts of Al2O3, average 15 wt.%) and carbonates (6 wt.% of CaO) are common mineral components of the deposits excluding the Cenomanian radiolarian shales (CRS) that are enriched in silica (mean content of SiO2 is 64 wt.%). “Immobile” elements may be accommodated by phyllosilicates and accessory minerals (i.e. zircon, xenotime, apatite and Ti-oxides). Heavy minerals are significant within the Szlachtowa Fm. High field strength elements (HFSE) in the Malinowa Fm. are housed in secondary apatite and Fe-oxides. Lithophile trace elements (LILE) concentrations in the material studied are lower/comparable to Post-Archean Australian Shale (PAAS). Ba concentration in the CRS probably reflects enhanced bioproductivity. Interaction between major oxides, distributions of “immobile” and lithophile elements suggest that variation in trace elements through the succession was mainly controlled by the terrigenous input. The material studied was sourced from intermediate to felsic rocks of the Czorsztyn (Oravic) Ridge. The Szlachtowa Fm. and CRS are more mature than others due to low contents of clay minerals. The Szlachtowa Fm. also contains recycled material. The CRS correspond to the oceanic anoxic event 2 (OAE 2) whereas the “Black Flysch” of the Szlachtowa and Opaleniec formations may be related to the Early Cretaceous OAE 1. Patrycja Wójcik-Tabol and Nestor Oszczypko, Institute of Geological Sciences, Jagiellonian University, Oleandry 2 a, 30-063, Kraków, Poland, e-mails: p.wojcik-tabol@ uj.edu.pl, nestor.oszczypko@uj.edu.pl (received: March 24, 2011; accepted: December 22, 2011). Key words: Western Carpathians, Grajcarek thrust-sheets, “Black Flysch”, trace el e ments geo chem is try. INTRODUCTION The Upper Jurassic-Lower Cretaceous black shales are world-wide sedimentary phenomena (Bernoulli, 1972; Schlanger and Cita, 1982; Bralower et al, 1993; Wang et al, 2011). Deposition of organic carbon-rich facies during the Cre- taceous was on a scale that has not since been repeated. Forma- tion of black shales associated with oceanic anoxic events (Schlanger and Jenkyns, 1976) was commonly succeeded by de- position of a hemipelagic, iron-rich succession, known as the Cretaceous Oceanic Red Beds (CORBs; Hu et al., 2005). In the northern periphery of the Tethys, black shales were well-devel- oped in the Outer (Flysch) Carpathians (e.g., Książkiewicz, 1962; Ślączka and Kamiński, 1998; Golonka et al., 2009). They occur in the Skole Nappe (Spas Shales of the Barremian-Albian age) and Sub-Silesian/Silesian nappes (Verovice Shales dated on Barremian to early Aptian). In the Silesian Nappe, black shales are followed by the turbiditic Lhota Fm. The Spas Shales and Lhota Fm. directly precede the Barnasiowka Radiolarian Shale Formation, which contains siliceous, green and black shales with manganiferous horizons. These black shales corre- spond to the Bonarelli Level that is equivalent to the Cenomanian-Turonian event of oceanic anoxia (OAE 2). The Barnasiowka Fm. is overrain by the Upper Cretaceous Varre r gated Shales. In the Fore-Magura and the Magura Nappe the Cretaceous black shales in general are unknown, because these nappes are tectonically detached at the base of the Late Creta- ceous red shales (Oszczypko, 2004, 2006). The chemical composition of sedimentary rocks is an im- portant record of the geological evolution of the sedimentary basin and adjacent area through time (Taylor and McLennan, 1985). The domain of the Outer Carpathian basins evolved dur- ing the Jurassic and Cretaceous into a rifted passive margin of the European plates. Development of the basin was controlled 170 Patrycja Wójcik-Tabol and Nestor Oszczypko during Late Jurassic-Aptian times by normal faulting and syn-rift subs idence that was accompanied in the Weste rn Carpathians by the extrusion of alkali basalts ranging in age from Barremian to Aptian (cf. Oszczypko, 2006). Different magmatic, metamorphic and sedimentary rocks, derived mainly from continental crust, have been shown to be the chief or only source of turbiditic deposits of the Outer Carpathians basins. Ultrabasic rocks indicative of oceanic crust played a role in supplying material to the rocks of the southern part of the Magura Nappe only (Winkler and Ślączka, 1992, 1994). “Black Flysch” of the Grajcarek Suc- cession was supplied with detrital material derived from ero- sion of the Czorsztyn ridge (Krawczyk and Słomka, 1986, 1987; Golonka et al., 2000), uplifted since the Valanginian to Albian/Cenomonian (Birkenmajer, 1977). The “Black Flysch” sandstones (see Łozinski, 1956, 1959, 1966) contain heavy mineral assemblages typical of continental crust. In the latest Albian-Cenomanian, siliciclastic source areas were cut off (cf. Oszczypko, 2006). Concentrations of certain trace elements (e.g., REE, Sc, Th) provide information of source rocks, because they are not affected by secondary processes (McLennan et al., 1993; Cullers, 2000). By contrast, mobile ele- ments (such as Na and Ca) can be used to evaluate the degree of chemical weathering, that reflects palaeoclimate in the source area at the time of deposition (Nesbitt and Young, 1982). The present paper concerns provenance of the detrital com- ponents of the Cretaceous deposits from the Grajcarek thrust-sheet. We pay special attention to weathering of the source area, sorting and recycling as processes that change the chemistry of deposited material. The succession studied con- sists of various lithotypes representing changing depositional environments in the southern part of the Magura Basin. The Jurassic or Early Cretaceous age of the Szlachtowa and Opaleniec formations (known also as “Black Flysch”) is a subt ject of long-term controversy. Oszczypko et al. (2004) pret sented new arguments to suggest the Albian-Cenomian age of these sediments, whereas Birkenmajer et al. (2008) proposed a Jurassic age. In recent years we have documented (see Oszczypko et al., 2004; Wójcik-Tabol and Oszczypko, 2010) that the transition between the Lower Cretaceous black shales and the Upper Cre- taceous red sediments in the Grajcarek Succession is similar to that described from more northern nappes of the Outer Carpathians. In this paper we support this concept by prove- nance studies. The geochemical indices of the deposits of the Grajcarek Succession are compared with published data concerning the Cretaceous sections from the Pieniny Klippen Belt (PKB), Outer Carpathians and other geological settings (Brumsack, 1980; Bellanca et al., 1997; Hofmann et al., 2001; Neuhuber and Wagreich, 2011). GEOLOGICAL SETTING The Małe Pieniny Mts. are located in the southern part of the Pohsh Western Carpathians, between the Dunajec River Valley in the west and the Polish/Slovak state boundary to the east and south (Fig. 1). The area studied occupies the contact zone between the Magura Nappe and the PKB. The boundary between the Magura Nappe and the PKB runs along the Grajcarek Stream (Fig. 1C). The Magura Nappe, situated north of stream, is composed of Paleogene flysch deposits belonging to the Krynica Slice (see Fig. 1B; Birkenmajer and Oszczypko, 1989; Oszczypko and Oszczypko-Clowes, 2010). These de r posits are composed mainly of thick- to medium-bedded turbidites of the channel-lobe facies. Along the Grajcarek Val- ley the Magura Nappe contact with narrow, strongly deformed the peri-Pieniny Klippen Belt Zone, known as the Grajcarek Unit (Birkenmajer, 1979). The Grajcarek Succession comprises Jurassic, Cretaceous and Paleocene, pelagic and flysch deposits of the Magura Suc- cession, incorporated in the structure of the PKB. The Szlachtowa and Opaleniec formations termed “Black Flysch” are up to 220 m thick. These “Black Flysch” facies are followed by 2-10 m of Cenomanian radiolarian shales (Hulina Fm. sensu Birkenmajer, 1977), variegated shales of the Turonian-Campanian Malinowa Fm. (20-100 m) and coarse clastic deposits of the Jarmuta Fm. (Maastrichtian-Paleocene) reaching 100-400 m (Birkenmajer, 1977). STUDIED SECTIONS The exposures studied are located in the upper course of the Sztolnia Stream along a 250 m section (Oszczypko et al., 2004; Birkenmajer et al., 2008), which comprises three sections (A, B and C; see Fig. 2). In the Sztolnia Stream A section the Szlachtowa Formation is represented mainly by dark grey and black, marly shales, claystones and siltstones, and fine-grained, calcareous sandstones containing abundant mica flakes. This formation is overrain by the Opaleniec Fm. composed of the light grey, marly claystones with intercalations of spotty lime- stones and sideritic dolomites. In the Sztolnia Stream B section this formation is developed as a sequence of dark grey, greenish sometimes bioturbated shales with pyrite concretions. Lenses and beds of grey, spotty limestones and sideritic dolomites have thicknesses not exceeding a few dozen centimetres. The Opaleniec Formation is overlain by the CRS composed of man- ganese shales, radiolarian shales with pyrite framboids and radiolarites. These strata have been described by Birkenmajer (1977) as the Hulina Formation (Albian-Cenomanian). The green and black non-calcareous shales and radiolarites of the CRS (Hulina Fm.) have been collected from exposures on the S slope of Hulina Mt. (Fig. 2). In the Sztolnia Stream (sections A-C; see Fig. 2) the sili- ceous shales of the CRS are followed by cherry-red and green, argillaceous shales of the Malinowa Formation (Birkenmajer, 1977; Birkenmajer and Oszczypko, 1989). The lowermost part of the Malinowa Fm. (section A) on the north limb of the small anticline contains a 1 m-thick bed of light, fine-grained sand- stone overlain by 10 cm of green radiolarite, whereas on the S limb of the anticline, the green radiolarite (5 cm) occurs at the base of a cherty limestone (see Oszczypko et al., 2004). Trace element geochemistry of the Early to Late Cretaceous deposits of the Grajcarek thrust-sheets. l7l Fig. 1. Location of the area studied within the content of main geological units A - simplified tectonic scheme of the Alpine orogens; PKB - Pieniny Klippen Belt (after Kovac et al., 1998, modified); B - central part of Polish Carpathians (after Oszczypko and Oszczypko-Clowes, 2009); C - detailed division of the Małe Pieniny Mts. (after Birkenmajer, 1979, simplified) ANALYTICAL METHODS In this study, 48 samples representing various lithotypes (e.g., fine-grained rocks, radiolarite shales, marly shales) were analysed geochemically using a Perkin Elmer Elan 6000ICP at the ACME Analytical Laboratories, Ltd. in Vancouver, Can- ada. Total abundances of the major oxides and several minor elements (SiO2, Al2O3, Fe2O3, CaO, MgO, Na2O, K2O, MnO, TiO2 and P2O5) are reported on a 0.2 g sample analysed by ICP-emission spectrometry following Lithium meTabo- rate/tetraborate fusion and dilute nitric digestion. Loss on igni- tion (LOI) is by weight difference after ignition at 1000°C. Rare earth and refractory elements (Ba, Co, Cs, Ni, Rb, Sc, Sr, Th, V, Y, Zr) are determined by ICP mass spectrometry fol- lowing the Lithium meTaborate/tetraborate fusion and nitric acid digestion of a 0.2 g sample. In addition a separate 0.5 g split is digested in Aqua Regia and analysed by ICP mass spec- trometry to report the precious and base metals. Concentrations of major and minor elements were com- pared to the Post-Archean Australian Shale (PAAS; Taylor and McLennan, 1985). For selected elements comparison to the Upper Continental Crust (UCC; Taylor and McLennan, 1985) was applied. The values of Eu anomaly were calculated using Eu/Eu* ratio, where Eu = Eu normalized to PAAS (EuPAAS) and Eu* = (SmPAAS X GdPAAS)0'5. GEOCHEMISTRY Statistics of major and trace element composition are shown in the Tables 1-4. The inter-elemental relationships have been evaluated using the Pearson’s correlation factor (Ta- bles 5 and 6) and shown in bivariate and triangular diagrams (Figs. 3-9). l72 Patrycja Wójcik-Tabol and Nestor Oszczypko Fig. 2. Lithological log of the Sztolnia sections (based on Oszczypko et al., 2012); A, B — main Sztolnia Stream (Big and Small waterfalls); section C — left tributory of the Sztolnia Stream; lower run of the Sztolnia Stream (Hulina Mt. section after Birkenmajer, 1977) MAJOR ELEMENTS Compared to the PAAS, most samples are enriched in CaO at the expense in SiO2. Only siliceous samples of the Cenomanian radiolarian shales (CRS) are relatively enriched of SiO2, especially shales from the Hulina section. They also con- tain the lowest amounts of Al2O3 relative to other samples (Ta- ble 1). A triangular diagram SiO2 - Al2O3 X 5- CaO X 2 (Fig. 3) plots the majority of the samples near the PAAS with admix- ture of various CaO amounts. Only CRS are shifted towards the SiO2 corner. SiO2 primarily represents biogenic silica in radiolarian shales and quartz within siliciclastic samples. Con- centration of Al2O3 reflects phyllosilicate content. The bivariate diagram SiO2vs. Al2O3 (Fig. 4) shows negative corre- lation between concentrations of SiO2 and increasing amounts of phyllosilicate within the CRS. Positive correlation between SiO2 and Al2O3 for the rest of the formations is explained by the presence of detrital components - quartz admixed with aluminosilicates. Ratios of SiO2/Al2O3 suggest the commonly occurrence of clay minerals in the material studied. The sam- ples of CRS show a SiO2/Al2O3 ratio typical of feldspars, but it could be affected by abundant biogenic silica. The presence of feldspar is not confirmed on the Al2O3 vs. K2O diagram (Fig. 4). With the exception of the Hulina sam- ples, the material studied contains K2O in amounts quite similar to that in PAAS (Table 1).In the diagram the samples fall paral- lel to an ideal muscovite line, but shifted to higher Al2O3 con- tents because of accompanying minerals (e.g., kaolinite). The correlation factors of Al2O3to K2O exceed 0.86 (Table 5). Taking to account the Na2O contents, only the Opaleniec Fm. is close to PAAS, whereas the rest of the formations are de- pleted (Table 1). The Na2O vs. M2O3 diagram (Fig. 4) shows two trends: 1) a positive correlation for the Opaleniec Fm. and CRS (mainly mudstones of the Sztolnia sections); 2) a progres- sive decline in Na2O contents relative to increasing Al2O3 con- centrations in the Szlachtowa and Malinowa formations that can be explained by an admixture of kaolinite in the Szlachtowa Fm. and other mintrtls in the Malinowa Fm., where kaolinite was not found. Table 1 Major element statistical data for the samples from the Grajcarek Succession St. dev - standard deviation, m - mean, n - number of samples, ICV - Index of Compositional Variability, CIA - Chemical Index of Alteration, PI A - Plagioclase Index of Alteration Table 2 High field strength trace elements (HFSE) statistical data [ppm] for the samples studied For explanati o ns see Table 1 Trace element geochemistry of the Early to Late Cretaceous deposits of the Grajcarek thrust-sheets... 173 T a b l e 3 174 Patrycja Wójcik-Tabol and Nestor Oszczypko The diagram of Fe2O3 to Al2O3 (Fig. 4) shows positive cor- relation between oxides in the Szlachtowa Fm. (r = 0.57), and CRS from the Hulina section (r = 0.74) and Malinowa Fm. (r = 0.59) (Table 5). A Fe2O3/Al2O3 ratio yields 1:4 that is typi- cal for detrital siliciclastic sediments. Glauconite was not found, but chlorite is a common clay constituent in every for- mation. High concentrations of Fe2O3 and no linkage to Al2O3 in the CRS and Opaleniec Fm. can be explained by occurrence of pyrite, confirmed during thin-section examination. Relative to PAAS, the samples are depleted in TiO2 (mean values vary from 0.4 ±0.13 for the Hulina samples to 0.7 ±0.1 for the Szlachtowa Fm.). The TiO2-Al2O3 diagram (Fig. 4) shows constantly positive correlations between oxides for ev- ery formation (r >0.68; Table 5). The correlation between TiO2 and phyllosilicates (probably the clay fraction) are consistent due to weathering. HIGH FIELD STRENGTH TRACE ELEMENTS (HFSE): Zr, Th, U, Y, Hf, Nb, REE The material studied contains lower amounts of Zr, Th, Nb and earth trace elements (REE) than PAAS, whereas concen- trations of U and Y are comparable to those of PAAS. In gen- eral, the Malinowa and Szlachtowa formations contain the highest amounts of HFSE, while the CRS of the Hulina section show the strongest depletion in them (Table 2). Accumulation of HFSE shows posttive linkage to Al2O3 and K2O (Table 5). However, inthe Szlachtowa Fm., the distri- bution of Zr, Hf and Y is independent of or negatively related to Al2O3 and K2O. In the Opaleniec Fm. concentrations of Nb have no correlation to K2O. The Malinowa Fm. reveals nega- tive correlation of U with K2O and Al2O3. In the material studied HFSE are preferentially linked to minerals of the mica type having a tight association with Al2O3 and K2O. Irregular accumulation of Zr, Y, Nb and U suggests that elements have affinity to accessory minerals (i.e. zircon, xenotime and Ti-oxides). Zr and Hf are the most affected by density-related fraction- ation. Their amounts in sedimentary rocks are controlled by zir- con and due to a combination of resistance to weathering and high density: this mineral undergoes sorting-related fraction- ation (Taylor and McLennan, 1985). In the contrast, Th and Nb in clastic rocks are commonly hosted by resistate minerals such as Ti-oxkles and apatite, which follow the fate of the clay-sized component. They are not seriously involved by sorting-related fractionation. Interaction between Nb, Th, TiO2, P2O5 and Zr (Table 6) show that Th and Nb have common affinity with Ti phases and the clay fraction. Th could be also retated with zircon. In the Malinowa Fm. and CRS Th and Nb are possibly also hosted by phosphates. Nb and Th reveal different behaviour in the “Black Flysch”. Amounts of Nb do not depend on Zr concentration. In the Opaleniec Fm. Th barely correlates to Ti. Thus, only Nb is related with Ti phases, whereas Th is hosted by zircon. § Distributions of U and Y are partly controlled by Al2O3, | K2O and TiO2 concentrations (Table 6). U canbe hostedby zir- con, as is suggested by positive correlation with Zr (r = S 0.17-0.69). O Trace element geochemistry of the Early to Late Cretaceous deposits of the Grajcarek thrust-sheets. 175 Table 4 Selected average elemental ratios for the samples studied For explanations see Table 1 The average Th/U ratios vary from 3.29 ±1.2 in the Opaleniec Fm. to 4.5 ±1.1 in the Malinowa Fm. With the ex- ception of the Opaleniec Fm., the samples have Th/U ratios higher than UCC - 3.8. Some samples of the Malinowa Fm. re- veal Th/U ratios that reach that of the PAAS - 4.7 (Table 2). All this suggests that the material studied was affected by weather- ing. The lowest degree of weathering probably characterizes the Opaleniec Fm. Elevated U concentration within the Opaleniec Fm. is linked with the accumulation of Co, V, Ni and Cr (Table 3). Yttrium is the maj or conttituent of phosphate xenotime minerals, which is in agreement with positive correlation of Y with P2O5 concerning almost the entire succession (excluding the Malinowa Fm.; Table 6). The total contents of rare earth elements (TREE) correlate positively with Al2O3 and K2O (Table 6), thus REE have affin- ity to phyllosilicates. Adsorption of REE by Fe-oxides coating the mineral particles is possible due to positive correlation of TREE to Fe2O3 (Table 6). An involvement of REE with heavy minerals (zircon and xenotime) is considered as well. The role of Ti-oxides in concentrations of REE is limited to the Malinowa Fm. and CRS. Lack of correlation between REE and TiO2 for the “Black Flysch” negates the importance of Ti-ox- ides (Table 6). Average values of the (La/Yb)PAAS ratio rangmg between 0.94 in the Malinowa Fm. and 1.06 in the Szlachtowa Fm. (Ta- ble 2) are comparable with those proposed by Condie (1991) for terrigenous materials. Meanvalues ofEu/Eu* ratiovary ina narrow range: 1.005-1.06 (Table 2). Hence Eu anomalies are higher than those of PASS and UCC - 0.6 (Taylor and McLennan, 1985). Eu concentrates within plagioclase (Nath et al., 1992). Most of the Eu released during plagioclase dissolu- tion could have been trapped by clay minerals by adsorption producing a positive Eu anomaly. HFSE have the abihty to be incorporated into crystalhne structures and/or adsorb onto surfaces of phyllosilicates (Tay- lor and McLennan, 1985). Certain accessory minerals accom- modate the HFSE as well. The most possible is the occurrence of zircon and phosphate minerals (mainly apatite and xenot time) and Ti-oxides. The Szlachtowa Fm. contains heavy minerals (zircon, xenotime and Ti-oxtdes) in amounts higher than in other for- mations. The Malinowa Fm. exhibits high accumulation of HFSE corretatve with the clay fraction and TiO2 as well as with apatite and Fe-oxides that probably are secondary phases. LARGE ION LITHOPHILE TRACE ELEMENTS (LILE): Rb, Cs, Ba, Sr Relative to the PAAS, the samples are significantly det pleted in Ba, but concentrations of Cs in CRS, Sr in the “Black Flysch” and Rb in the Malinowa Fm. and CRS of the Sztolnia sections are occasionally similar to that in PAAS (Table 3). Cs and Rb contents show tight linkage to K2O and AfiO3, suggest- ing their affintty to phyllosilicates. Amounts of Sr cortetate negatively with Al2O3 and K2O. An explanation could be an as- sociation of Sr with Ca within calcareous samples (Table 5). K2O, Cs and Rb co-occur in feldspars and are incorporated into clays during chemtcal weathering. In contrast, Sr and Na2O tend to be leached (Nesbitt et al., 1980). Sr behaves like Ca, which is lost significantly in initially weathered rocks and con- tinues to be lost during later stages of weathering. Sr is trapped from sea water by settled calcite. The barium distribution is simtiar that of K2O and Al2O3, though the CRS contain extraordinary high amounts of Ba con- comitant with low contents of Al2O3 and K2O (Table 5). The Ba concentration probably results from the organic productivity rise. This idea is supported by negative correlation of SiO2 with Al2O3 (Table 5), indicating a supply ofbiogenic silica (Arthur and Premoli Silva, 1982) and accumulation of organic matter. Abundant radiolarian tests recognized in thin-section also sug- gests enhanced bioproductivity. 176 Patrycja Wójcik-Tabol and Nestor Oszczypko Table 5 Pearson correlation coefficients (r) between selected major and minor elements for the samples from the Grajcarek Succession Trace element geochemistry of the Early to Late Cretaceous deposits of the Grajcarek thrust-sheets. 177 Tab. 5 cont. COMPOSITIONAL ALTERATION AND PROVENANCE MATURITY The index of compositional variability proposed by Cox et al. (1995) can be applied in mudrocks as a measure of compositional maturity. It is defined as [(Fe2O3 + K2O + Na2O+ + CaO + MgO + MnO + TiO2)/Al2O3]. Non-clay silicates con- tain a lower proportion of Al2O3 than do clay minerals, thus ICV values for clay minerals are in the range of 0.03-0.78, and for feldspars in the range of 0.54-0.87. The ICV values of most samples are higher than 1 (Table 1) because of the calcareous character of the samples and elevated contents of CaO and MgO. Only non-calcareous CRS display values that are within range of feldspar. These data agree with the interpretation of bivariate diagram SiO2 vs. Al2O3 (Fig. 4). The CRS and certain samples of the Szlachtowa Fm. seem to be more mature among the material studied. SUBAERIAL WATHERING PATTERNS The most widely used chemical index to determine the de- gree of source-area weathering is the Chemical Index of Alter- ation (Nesbitt and Young, 1982). The index is calculated using the molecular proportions: CIA = [Al2O3/(Al2O3 + CaO* + Na2O + K2O)] x 100 where: CaO* is the amount of CaO incorporated in the silicate fraction. CIA values ranging from 70 to 75 in Phanerozoic shales re- flect muscovite, illite and smectite composition and indicate a moderately weathered source. CIA values close to 100 charac- terize residual clays enriched in kaolinite and Al oxy-hydrox- ides produced under strong weathering conditions. The samples studted are calcareous and the CIA values were calculated without CaO. Thus, the index has only minor meaning during estimation of the degree of weathering. The Szlachtowa Fm. and the CRS of the Hulina section show the highest values of the index (average - 80), whereas the Malinowa and Opaleniec formations reveal the lowest (average - 77; Table 1). The degree of chemical weathering canbe also estimated using the Plagioclase Index of Alteration (PIA; Fedo et al., 1995) after the proportions: PIA = [(M2O3 - K2O)/(Al2O3 + CaO* + + Na2O - K2O)] x 100 where: CaO* is only CaO from the silicate fraction. Unweathered plagioclase has a PIA value of 50. The PAAS display higher PIA - 79. The samples show very high PIA val- ues (calculated without CaO), averaging from 92 in the Opaleniec and Malinowa formations to 95 in the Szlachtowa Fm. and Hulina samples of the CRS (Table 1). The assumption that the Opaleniec Fm. shows the lowest degree of weathering was earlier shown by the low Th/U ratio. In the triangular diagram A-CN-K (Fig. 5) estimated with- out CaO (to eliminate the effect of calcite admixture), the sam- ples plot at the A-K join, between the A corner (chlorite, kaolinite) and the illite point. Very low amounts of Na2O are crucial. Low values of Na2O/Al2O3 ratio suggest the presence of clay minerals and strong weathering leading to Na leaching. Low K2O/Al2O3 ratios (average 0.21-0.24) also reflect the presence of clay minerals. Material derived by intense weather- ing associated with recycling of older sediments generally con- tains a high portion of illite. The presence of recycled illite is shown by negative/absent correlation between Na2O and K2O 178 Patrycja Wójcik-Tabol and Nestor Oszczypko Table 6 Pearson correlation coefficients (r) between selected major and minor elements for the samples from the Grajcarek Succession Trace element geochemistry of the Early to Late Cretaceous deposits of the Grajcarek thrust-sheets. 179 Tab. 6 cont in the Malinowa Fm. (r = -0.16) and the Szlachtowa Fm. (r = 0.06; Table 5). Intense weathering produces fractionation of the LREE/HREE. Preferential retention of HREE in solution may cause an increase in (La/Yb)PAAS. The highest values of (La/Yb)PAAS appear within the Szlachtowa Fm. (1.06 ±0.08) and CRS (1.03 ±0.09). The Opaleniec Fm. displays values varying widely (standard deviation is 0.12). The lowest values of (La/Yb)PAAS characterize the Malinowa Fm. (0.94 ±0.02) (Table 2). Values of (La/Yb)PAAS show positive correlation with PIA and CIA. The high values of CIA, PIA indexes and A-CN-K dia- gram indicate that material of the Szlachtowa Fm. and CRS from the Hulina section is more weathered than the material of the Opaleniec and Malinowa format ions. This is sup- ported by distributions of Cs and Rb corretative to K2O as well as REE fractionation, and Th/U ratios. The relatively high Cs and low concentrations of Zr, Hf in CRS may be at- tributable to the long-distance transport of aeolian dust (Nesbitt et al., 1980). PROVENANCE TECTONIC SETTING Ternary La-Th-Sc diagram (Bhatia and Crook, 1986) has been used to constrain the provenance and tectonic settings for the deposition of the succession studied. The deposits plot within the continental islands arc (Fig. 6), which is partly in agreement with the major element tectonic discrimination shown in the K2O/Na2O vs. SiO2 diagram (Fig. 7). Most of the samples plot within the fields of active continental margin and island arc. The CRS are shifted to the passive margin field due to the high silica content, which distorts the proper interpretation. SORTING AND RECYCLING The distribution of the chemical components is mainly de- termined by the mechanical properties of the host minerals. The process basically fractionates Al2O3 (clay minerals) from SiO2 (quartz and feldspars). Sorting also fractionates TiO2, mostly present in clay minerals and Ti-oxides, from Zr and Hf hosted in zircon, and sorted with quartz. The ternary diagram 10 x Al2O3-200 TiO2-Zr (Fig. 8) may illustrate the presence of sorting-related fractionation (Garcia et al., 1991). The samples are near to PAAS. Most of the samples cluster without visible variation as regards amounts of Al2O3, TiO2 and Zr. Only “Black Flysch”, especially the Szlachtowa Fm., shows a mixing trend. Changes in the Al2O3/Zr ratio may be a recycling effect. Zr enrichment during sorting can also be evaluated using the bivariate diagram Zr/Sc vs. Th/Sc (Fig. 9). The Zr/Sc ratio is an index of sediment recycling, while Th/Sc ratio is controlled by chemical dif- ferentiation (McLennan etal., 1993). The sam- ples are clustered along the primary compositional trend, near the andes ite point, but the Szlachtowa Fm. falls along a trend in- volving minor zircon addition. Fig. 3. Triangular plot SiO2—A^O3 x 5-CaO x 2 PAAS refers to Post-Archean Australian Shale (after Taylor and McLennan, 1985) 180 Patrycja Wójcik-Tabol and Nestor Oszczypko Fig. 4. Bivariate diagrams of major element composition for the Cretaceous succession of the Grajcarek thrust-sheets Fe2O3/Al2O3 = 1:4 regarded as typical for detrital siliclastic sediments represents an iron content of phyllosilicates; for other explanations see Figure 3 MAFIC-FELSIC SIGNATURE Sc, Ni and Co that are housed in basic rocks (Taylor and _ , . , , McLennan, 1985). Relative to PAAS, the malerial studied is Certain trace elements or the ratios between them have been enriched in transition metals including Ni, Sc, Co and Zn. Ex- U to f ^ rocuk c°mPositioa The concentration of Zr, ceptional enrichment in V and depletion in Cr distinguish the La and Th is higher in the silicic igneous rocks in contrast to Cr, crs of the Hulina section (Table 2). Trace element geochemistry of the Early to Late Cretaceous deposits of the Grajcarek thrust sheets. 181 CIA 100r 90 80 70 60 50 A Ka A Ka Fig. 5. Ternary A—CN—K plot and Chemical Index of Alteration The dashed line shows the theoretical weathering trend from a typical granite source rock; G - granite, Il - illite, Ka - kaolinite, Ks - K feldspar, M - muscovite, Pl - plagioclase, S - smectite; for other explanations see Figure 3 La La Fig. 6. Ternary diagram between light REE (La), incompatible element (Th) and compatible element (Sc) showing similarity of samples studied to PAAS Tectonic discrimination boundaries: ACM - active continental margin, CIA - continental island arc, OIA - oceanic island arc; for other explanations see Figure 3 Cr/Th ratios are simttar to these of PAAS (7.5) and UCC (7.76) for the CRS of the Hulina section. Ratios are little higher for other samples. The highest ratios are shown by the CRS of the Sztolnia sections (Table 4). With the exception of the CRS, the La/Co and Th/Co ratios reach those of UCC (La/Co - 1.76; Th/Co - 0.63) and PAAS (La/Co - 1.65, Th/Co - 0.64; Ta- ble 4). It is worth to noting that concentrations of Co were prob- ably increased by diagenetic pyritization. The importance of felsic supply is confirmed by the La-Th-Sc plot, and Cr/V vs. Y/Ni diagram (Bathia and Crook, 1986). In the ternary diagram La-Th-Sc, the samples fall in a field close to PAAS (Fig. 6). The La/Sc and Th/Sc ra- tios are quite simttar to those of Upper Continental Crust (La/Sc - 2.21; Th/Sc - 0.79) and PAAS (La/Sc - 2.37, Th/Sc - 0.9; Table 4). On the basis of the mixing curve between granite and the mafic-ultramafic end-member in the Cr/V vs. Y/Ni diagram (Fig. 9) any share of mafic-ultra- mafic matter in the material studied is doubtful. Considering the above, the material studied, enriched in incompatible elements, appears to be sourced from intermediate to felsic rocks. However, the CRS of the Sztolnia sections con- tain relatively high amounts of mafic Cr and Sc. DISCUSSION The transition from black shales to red/varie- gated deposits within the Cretaceous succession has been recorded mostly from epicontinental seas and carbonate platforms, and deep-sea en- vironments of the Tethyan and Attantic oceans (Jenkyns, 1980; Schlanger and Cita, 1982; Ar- thur and Premoli-Silva, 1982; Bralower et al., 1993; Hu et al, 2005; Wojcik-Tabol, 2006; Wang et al., 2011). Sikora (1962) and Ksiqzkiewicz (1977) have noted this pattern and postutated that the “Black Flysch” deposhs almost always dip be- neath the Cretaceous variegated shales (Golonka and Rqczkowski, 1984a, b). The Cre- taceous deposits of the Grajcarek Succession display similarity to the Cretaceous sequences that are known from the Polish Outer Carpathians i.e. the Spas Shales and Verovice Beds (Oszczypko, 2006). Horwitz (1929) first distinguished the “Black Flysch” (or “black Cretaceous”) of the Verovice type section as representing the Barremian to Aptian/Albian. Oszczypko et al. (2004) have demonstrated the Cretaceous age of the Szlachtowa Formation, as well as of the Opaleniec Formation. Mineral composition and geochemistry have become a basis of comparison of the “Black Flysch” deposits with the Albian equiva- lents from the Pieniny Klippen Belt (Upper Kapusnica Fm.) and Outer Carpathians (Lhota Fm.). The Szlachtowa and Opaleniec formations contain clay mineral assemblages including illite/smectite and kaolinite, similar to the Lhota Fm. of the Silesian Nappe (Wojcik-Tabol and Slqczka, 2009) and the Kapusnica Fm. of the PKB. Kaolinite enrichment probably reflects widespread accu- mulation of material weathered under constantly warm and hu- mid conditions (Chamley, 1989). The influence of weathering is confirmed by high values of the CIA, PIA indexes, the A-CN-K diagram, distribution of Rb and Cs, as well as REE fractionation and the Th/U ratios. In terms of maj or element contents, the Szlachtowa and Opaleniec formations correlate with the Kapusnica Fm. of the PKB. The concentrations of redox-sensitive elements have 182 Patrycja Wójcik-Tabol and Nestor Oszczypko Si02[%] Fig. 7. Diagram of tectonic discrimination based on K2O/Na2O vs. SiO^ For explanations see Figure 3 been discussed by Wojcik-Tabol and Oszczypko (2010). These authors have stated that the “Black Flysch” studied was depos- ited in dysoxic/anoxic environments of an oceanic anoxic event 1 (sensu Schlanger and Jenkyns, 1976). Accumulation of U, Th, Mo, As correlative to S suggests that the environment of the Grajcarek sub-basin was strongly anoxic. The material studied is relatively enriched in REE posi- tively correlated to Al2O3, Zr, Y, TiO2 that suggest affinity of REE to phyllosilicates and heavy minerals. Concentrations of “immobile” elements (Zr, Ti, Rb, Nb) suggest contamination of black shales by terrigenous material derived from intermediate-felsic rocks, as was concluded from Y/Ni vs. Cr/V and (V + Ni + Cr) vs. (Zr + Ti) diagrams (Wójcik-Tabol and Oszczypko, 2010). The same was esti- mated for the Lhota Fm. deposited in the Silesian Basin (Wójcik-Tabol and Ślączka, 2009). As a result of the post-rift subsidence, the Early/Late Creta- ceous “Black Flysch” of the Grajcarek Succession was depos- ited at the southern edge of the Magura Basin. This part of the basin was supplied with detrital material derived from erosion of the Czorsztyn paleo-Ridge (Krawczyk and Słomka, 1986, 1987; Golonka et al., 2000), uplifted since the Valanginian to Albian/Cenomonian interval (Birkenmajer, 1977). The “Black Flysch” sandstones contain heavy mineral assemblages rich in garnet, and subsequently staurolite, kyanite and bioiite (see Łoziński, 1956, 1959, 1966), that indicates erosion of continen- tal-type crust. Taking to account the REE patterns, the material studied has been compared to the Lower Cretaceous marlstones of the Venetian Prealps representing a section through southern conti- nental margin of the Tethys Ocean (Bellanca et al., 1997). The Szlachtowa, Opaleniec formations and CRS of the Sztolnia sections show values of Eu/Eu* and La/Yb similar to those of dark shales within the Albian Scaglia Variegata Formation de- posited in the southern Tethys. Bellanca et al. (1997) proposed that sea water was the most immediate REE source in the calcareous deposits. REE scav- enging may be attributed to adsorptive removal onto the surface coatings of the suspended particles and/or precipitation of Fe-sulphides. REE distribution was influenced by the chemis- try of the waters of the Tethys Ocean. The siliceous facies of the CRS are quite similar to the Cenomanian-Turonian interval (CTI) known from the Outer Carpathians (Barnasiówka Radiolarian Shales Forma- tions; see Bąk, 2007; Wójcik-Tabol and Ślączka, 2009) and Pieniny Klippen Belt (Magierowa Mbr.; see Wójcik-Tabol, 2006). Deposits of the CTI consist of silica and asso- ciated clay minerals including illite/smectite and chlorite (Wójcik-Tabol and Oszczypko, 2010). Increasing amounts of illite and chlorite is typical for the CTI (compare with the Bonarelli level from the Umbria-Marche Basin; Turgeon and Brumsack, 2006) due to cooling of climate and accelerated physical weathering (Chamley, 1989). The CRS studied are characterized by decreasing amounts of detrital elements such as Zr, Ti, Rb and Nd as well as a nega- tive correlation between Al2O3 and SiO2 that indicates diminishing input of terrigenous material (Wójcik-Tabol and Oszczypko, 2010). These geochemical features are in agreement with decreasi ng trends of Ti/Al Fig. 8. Ternary 10 x Al2O3—200 x TiO2—Zr plot showing possible sorting trend For explanations see Figure 3 Trace element geochemistry of the Early to Late Cretaceous deposits of the Grajcarek thrust sheets. 183 Zr/Sc Fig. 9. Provenance and source signature diagrams of the studied Cretaceous succession of the Grajcarek Succession A - bivariate diagram Zr/Sc vs. Th/Sc shows index of sediment recycling against indicator of chemical differentiation; the samples are mainly clustered along the primary compositional trend; B - bivariate diagram Cr/V vs. Y/Ni and Rb/Al ratios up to the siliceous shales of the BRSF and the lowest values of Al/(Al + Fe + Mn; Bąk, 2007). The concentrations of Ba, Sc, Th, REE and “immobile” ele- ments in the CRS approximate these to the Magierowa Mbr. (Wójcik-Tabol, 2006). Radiolarites from the Hulina section are more simiiar to the Barnasiówka Fm. due to low amounts of “immobile” elements and Mn enrichment (Bąk, 2007; Wójcik-Tabol and Ślączka, 2009). The numerous radiolarian- rich layers probably reflect upwelling circulation and increased productivity at the margin of the Carpathian Basin (Bąk, 2007) that may have been affected by eustatic sea level rise. Flooding of the source areas limited detrital input. Contents of maj or and “immobile” elements (e.g., Zr, Ti, Rb) within the CRS are comparable to those of CT black shales from the Demerara Rise - Western Atianiic (see Brumsack, 2006) the Bonarelli Level from the Venetian Prealps (Bellanca et al., 1997) and Umbria-Marche Basin of Central Italy (Brumsack, 2006; Turgeon and Brumsack, 2006). On the other 184 Patrycja Wójcik-Tabol and Nestor Oszczypko hand, the CRS studied are not sufficiently rich in redox-sensi- tive elements (Mo, Zn, Cu, As, V, Ni) relative to the Cenomanian-Turonian black shales from Tethys, the North At- lantic, and the ceniral North Pacific (Brumsack, 1980, 2006; Arthur et al., 1990; Bralower et al., 1993). A possible explana- tion might be diiuiion effect caused by enhanced terrigenous input into the Grajcarek Sub-basin. Red marls and shales of the Malinowa Fm. that represents the Upper Cretaceous oceanic red beds (CORB) foliow the CRS. They occur in a broad belt extending from the Caribbean across the Central Atlantic, Europe to Eastern Asia and record chang ing depositional conditions from anoxic/dysoxic to oxic. The Malinowa Fm. studied resembles other CORBs (see Neuhuber and Wagreich, 2011 and references therein). The most significant similarity occurs between the Malinowa Fm. and clayey CORB of the Mazak Fm. from the Czech Republic (Jiang et al., 2009) and Turonian variegated shales from the Polish Outer Carpathians (Bąk, 2007). Deposition of the Malinowa Formation might have been in- fluenced by several processes: excess of organic carbon burial, global cooling, and/or intensification of bottom circulation (Wójcik-Tabol and Oszczypko, 2010). Recently in the Czorsztyn Succession of the Pieniny Klippen Belt, in Ukraine (Veliky Kamenets; cf. Krobicki et al., 2004, 2008) and in the valley of the Vah in Slovakia (Vrsatec; cf. Spisiak et al., 2008, 2011), sub-marine volcanic rocks have been described (melanephelinites and alkaline basalts), that are not older than Cenomanian. This group can also include blocks of baialt from the Biała Woda, known as olistoliths in the Jarmuta Formation. These volcanic rocks correspond to oce- anic island alkali basalts or within-plate alkali basalts (Krobicki et al., 2004, 2008; Birkenmajer and Lorenc 2008; Spisiak et al., 2008, 2011). According to Spisiak et al. (2011), volcanic activ- ity was probably generated during passive asthenospheric man- tle upwelling, associated with lithospheric stretching and thin- ning of the Czorsztyn (Oravic) Ridge. Studied material falls in the field of CIA, because it was sourced from intermediate to felsic rock. However, the CRS contain admixture of mafic ele- ments that suggest basaltic volcanism during Cenomanian The volcanic activity was followed by the subsidence and deepening in the Magura Basin beneath the carbonate com- pensation depth level (see Oszczypko and Oszczypko-Clowes, 2006). This resulted in deposition of red shales of the Malinowa Formation (Turonian-Campanian) followed by coarse-grained sandstones and conglomerates of the Jarmuta Formation (Maastrichtian to late Paleocene), that contain chromian spinels derived from oceanic crust (Oszczypko and Salata, 2005). Slight admixture of the mafic elements (Cr, Sc) occurs within the CRS of the Sztolnia sections. The Malinowa Fm. contains relatively high amounts of Cr, but this may reflect the presence of recycled phases. CONCLUSIONS 1. The Grajcarek Succession was deposited at the southern edge of the Magura Basin. The bulk samples are characterized as mixtures of detrital matter comparable to PAAS with vary- ing amount of biogenic components. The Cenomanian radiolarian shales are depleted in terrigenous particles. The eustatic sea level rise and flooding of the source areas caused reduction in detrital supply and produced an organic productiv- ity rise that is recorded by increased Ba concentrations. 2. The terrigenous materials such as phyllosilicates and heavy minerals accommodate “immobile” elements. The Szlachtowa Fm. contains heavy minerals (zircon, xenotime and Ti-oxides) in amounts higher than in other formations. Amor- phous Fe-hydroxide coatings on grains and/or phosphates could potentially constitute an important host for HFSE in the Malinowa Fm. 3. Due to low contents of clay minimls the CRS and Szlachtowa Fm. seem to be more mature than other formations. The CRS are probibly contaminated by aeolian dust. The Szlachtowa Fm. coniains small addition of recycled particles (zircon). The occurrence of recycled phases (illite) is assumed within the Malinowa Fm. The material of the Szlachtowa Fm. and CRS were affected by more advanced weathering than the material of the Opaleniec and Malinowa formations. 4. Material of the Grajcarek Succession appears to be sourced from intermediate to felsic rocks that represent conti- nental island arcs. Detritic material was derived from erosion of the Czorsztyn Ridge, uplifted since the Valanginian to Albian/Cenomonian. The Cenomanian deposits contain an ad- mixture of the mafic elements that correspond with sub-marine volcanism recognized in the Czorsztyn Succession of the Pieniny Klippen Belt by other authors. 5. The sections studied display a transition from relatively shallow marine, anoxic black shales to well-oxygenated deep-water red beds of the of the Malinowa Formation. This process was typical for global transition of the Lower Creta- ceous black shales to Upper Cre taceous oceanic red beds. This kind of succession has been observed in all the sections studied by us in the Małe Pieniny Mts., and suggests a com- mon sedimentary history represented by these profiles. Acknowledgments. This work has been supported by the Polish Ministry of Science and Higher Education (grant 2 PO 4D 080 29 to PWT and grant 1997/PO1/2006 to NO). R. Hannigan (University of Massachusetts) and anonymous re- viewer are thanked for comments on the manuscript. S. Oszczepalski (Polish Geological Institute - National Re- search Institiite) is acknowledged for help with editorial re- marks. Trace element geochemistry of the Early to Late Cretaceous deposits of the Grajcarek thrust sheets. 185 REFERENCES ARTHUR M. A. and PREMOLI SILVA I. (1982) - Development of wide- spread organic carbon-rich strata in the Mediterranean Tethys. In: Na- ture and Origin of Cretaceous Carbon-Rich Facies (eds. S. O. Schlanger and M. B. Cita): 7-54. Academic Press, London. ARTHUR M. A., BRUMSACK H. J., JENKYNS H. C. and SCHLANGER S. O. (1990) - Stratigraphy, geochemistry and paleoceanography of organic carbon-rich Cretaceous sequences. In: Cretaceous Resources, Events and Rhythms (eds. R. N. Ginsburg and B. Beaugoin): 75-119. Elsevier, Amsterdam. BĄK K. (2007) - Environmental changes during the Cenomanian-Turo- nian boundary event in the Outer Carpathian Basins: a synthesis of data from var t ous tectonic-facies units. Ann. Soc. Geol. Pol., 77: 171-191. BHATIA M. R. and CROOK K. A. W. (1986) - Trace element characteris- tics of graywackes and tectonic discrimination of sedimentary basins. Contrib. Miner. Petrol., 92: 181-193. BELLANCA A., MASETTI D. and NERI R. (1997) - Rare earth elements in limestone/marlstone couplets from the Albian-Cenomanian section (Venetian region, northern Italy): assessing REE sensitivity to envi- ronmental changes. Chem. Geol., 141 (3-4): 141-152. BERNOULLI D. (1972) - North Atlantic and Mediterranean Mesozoic fa- cies: a compartson. Initial Rep. Deep Sea Drill. Proj. (eds. C. D. Hollister, J. I. Ewing etal.), 11: 801-871. BIRKENMAJER K. (1977) - Jurassic and Cret aceous lithostratigraphic units of the Pieniny Klippen Belt, Carpathians, Poland (in Polish with English summary). Stud. Geol. Pol., 45. BIRKENMAJER K. (1979) - Przewodnik geologiczny po pienińskim pasie skałkowym. Wyd. Geol., Warszawa. BIRKENMAJER K. and OSZCZYPKO N. (1989) - Cretaceous and Palaeogene lithostratigraphic units in the Magura Nappe, Krynica Subunit, Carpathians (in Poli sh with Engl ish summary). Ann. Soc. Geol. Pol., 59 (1-2): 145-181. BIRKENMAJER K. and LORENC M. W. (2008) - Lower Cretaceous ex- otic intraplate basaltoid olistolith from Biała Woda, Pieniny Klippen Belt, Pot and: geochem t stry and provenance. Stud. Geol. Pol., 131: 237-246. BIRKENMAJER K., GEDL P., MYCZYŃSKI R. and TYSZKA J. (2008) - “Cretaceous Black Flysch” in the Pieniny Klippen Belt, West Carpathians, a case of geological misinterpretation. Cretaceous Res., 29 (3): 535-549. BRALOWER T. J., SLITER W. V., ARTHUR M. A., LECKIE R. M., ALLARD D. and SCHLANGER S. O. (1993) - Dysoxic/anoxic epi- sodes in the Aptian/Albian (Early Cretaceous). In: The Mesozoic Pa- cific: Geology, Tect onics and Volcanism (eds. M. S. Pringle, W. W. Sager, W. V. Sliter and S. Stein). Am. Geoph. Union, Monograph, 73: 5-37. BRUMSACK H. J. (1980) - Geochemt stry of Cretaceous black shales from the Atlantic Ocean (DSDP Legs 11, 14, 36, 41). Chem. Geol., 31: 1-25. BRUMSACK H. J. (2006) - The trace metal content of recent organic car- bon-rich sediments: implications for Cretaceous black shale forma- tion. Palaeogeogr. Palaeoclimat. Palaeoecol., 232: 344-361. CHAMLEY H. (1989) - Clay sedimentology. Springer, Berlin. CONDIE K. C. (1991) - Another look at rare earth elements in shales. Geochim. Cosmochim. Acta, 55 (9): 2527-2531. COX R., LOW D. R. and CULLERS R. (1995) - The influence of sediment recycling and basement composition on evolution of mudrock chemis- try in the Southwestern United States. Geochim. Cosmochim. Acta, 59: 2919-2940. CULLERS R. L. (2000) - The geochemistry of shales, siltstones and sand- stones of Pennsylvanian-Permian age, Colorado, U.S.A.: implications for provenance and metamorphic studies. Lithos, 51: 305-327. FEDO C., NESBITT H. and YOUNG G. (1995) - Unraveling the effects of potassium metasomatism in sedimentary rocks and paleosols, with im- plications for paleoweathering conditions and provenance. Geology, 23: 921-924. GARCIA D., COEHLO J. and PERRIN M. (1991) - Fractionation between TiO2 and Zr as a measure of sorting within shale and sandstone series (northern Portugal). Europ. J. Miner., 3: 401-414. GOLONKA J. and RĄCZKOWSKI W. (1984a) - Objaśnienia do szczegłowej mapy geologicznej Polski w skali 1:50 000, ark. Piwniczna. Inst. Geol., Warszawa. GOLONKA J. and RĄCZKOWSKI W. (19846) - Szczegłowa mapa geologiczna Polski w skali, 1:50 000, ark. Piwniczna. Inst. Geol., Warszawa. GOLONKA J., OSZCZYPKO N. and ŚLĄCZKA A. (2000) - Late Carbon- iferous-Neogene geodynamic evotution and paleogeography of the circum-Carpathian region and adjacent areas. Ann. Soc. Geol. Pol., 70: 107-136. GOLONKA J., KROBICKI M., WAŚKOWSKA A., MATYASIK I., PAUKEN R., BOCHAROVA N. J., EDRICH M. and WILDHARBER J. (2009) - Source rock prediction value: world provinces during late Jurassic-Earliest Cretaceous times and position of West Carpathians in SRPV prediction. Ann. Soc. Geol. Pol., 79: 195-211. HOFMANN P., RICKEN W., SCHWARK L. and LEYTHAEUSER D. (2001) - Geochemical signature and related climatic-oceanographic processes for early Albian black shales: Site 417D, North At l ant ic Ocean. Cretaceous Res., 22: 243-257. HORWITZ L. (1929) - Sur la geologie de la Zone Pienine des Klippes (Carpates Polonaises). II Zjazd Geografów i Etnografów Słowiańskich, Pamiętnik, Kraków, 1: 321-326. HU X. M., JANSA L., WANG C. S., SARTI M., BAK K., WAGREICH M., MICHALIK J. and SOTAK J. (2005) - Upper Cretaceous oceanic red beds (CORBs) in the Tethys: occurrences, lithofacies, age, and envi- ronments. Cretaceous Res., 26: 3-20. JENKYNS H. C. (1980) - Cretaceous anoxic events: from continents to oceans. J. Geol. Soc., 137: 171-188. JIANG S. Y., JANSA L., SKUPIEN P., YANG J. H., VASICEK Z., HU X. and ZAO K. D. (2009) - Geochemistry of intercalated red and gray pe- lagic shales from the Mazak formation of Cenomanian age in Czech Re pub lic. Ep i sodes, 32: 3-12. KROBICKI M., GOLONKA J., LEWANDOWSKI M., MICHALIK M., OSZCZYPKO N., POPADYUK I. and SLABY E. (2004) - Volcanism of the Jurassic-Cretaceous triplejunction zone in the Eastern Carpathians. Geolines, 17: 124-161. KROBICKI M., OSZCZYPKO N., SALATA D. and GOLONKA J. (2008) - Intra-plate alkaline volcanism in the Pieniny Klippen Belt (Eastern Carpathians, Ukraine). In: SlovTec08. Proc. Excur. Guide (eds. Z. Németh and D. Plasienka): 73-74. State Geol. Inst. D. Stur, Bratislava. KSIĄŻKIEWICZ M., ed. (1962) - Geotogt cal attas of Pot and. Strati- graphic and facial problems. Fasc. 13 - Cretaceous and early Tertiary in the Polish External Carpathians. Inst. Geol., Warszawa. KSIĄŻKIEWICZ M. (1977) - The tectonics of the Carpathians. In: Geol- ogy of Poland: 476-620. Inst. Geol., Warszawa. KOVAC M., NAGYMAROSY A., OSZCZYPKO N., ŚLĄCZKA A., CSONTOS L., MARUNTEANU M., MATENCO L. and MARTON E. (1998) - Palinspastic re con struction of the Carpathian-Pannonian re- gion during the Miocene. In: Geodynamic Development of the West- ern Carpathias (ed. M. Rakus): 189-217. Slovak Geol. Surv., Bratislava. KRAWCZYK A. and SŁOMKA T. (1986) - Development and sedimento- logy of the Szlachtowa Formation (Jurassic) eastward from Szczawnica, Grajcarek Succession, Pieniny Klippen Belt. Stud. Geol. Pol., 88: 33-134. KRAWCZYK A. and SŁOMKA T. (1987) - Exotics from the Szlachtowa Formation of the Pieniny Klippen Belt, Carpathians. Stud. Geol. Pol., 92: 69-74. ŁOZIŃSKI J. (1956) - Les minéraux lourds des grès exotiques (jurassiques) de Bachowice (Karpates Occidentales) (in Poli sh with French summary). Rocz. Pol. Tow. Geol., 26 (1): 157-164. ŁOZIŃSKI J. (1959) - Les minéraux lourds des grès du Crétacé inférieur et moyen dans les Klippers des Pieniny (in Polish with French summary). Rocz. Pol. Tow. Geol., 29 (1): 119-125. 186 Patrycja Wójcik-Tabol and Nestor Oszczypko ŁOZIŃSKI J. (1966) - Les minéraux clastiques dans les grès flyscheux de la zone des klippes Piénines et des terrains avoisinantes (in Polish with French summary). Pr. Geol. Komis. Nauk Geol. PAN, 37: 1-72. McLENNAN S. M., HEMMING S., McDANIEL D. K. and HANSON G. N. (1993) - Geochemical approaches to sedimentation, provenance and tectonics. Geol. Soc. Am. Spec. Pap., 284: 21-40. NATH B. N., ROELANDTS I., SUDHAKAR M. and PLUEGER W. L. (1992) - Rare earth element patterns of the Central Indian Basin sedi- ments related to their lithology. Geoph. Res. Lett., 19: 1197-1200. NEUHUBER S. and WAGREICH M. (2011) - Geochemt stry of Creta- ceous Oceanic Red Beds - a synthesis. Sediment. Geol., 235: 72-78. NESBITT H. and YOUNG G. (1982) - Early Proterozoic climates and plate motions inferred from major element chemistry of lutites. Na- ture, 299: 715-717. NESBITT H., MARKOVICS G. and PRICE R. (1980) - Chemical pro- cesses affecting alkalis and alkaline earths during continental weather- ing. Geochim. Cosmochim. Acta, 44: 1659-1666. OSZCZYPKO N. (2004) - The structural position and tectonosedimentary evolution ofthe Polish Outer Carpathians. Prz. Geol., 8 (2): 780-791. OSZCZYPKO N. (2006) - Late Jurassic-Miocene evolution of the Outer Carpathian fold-and-thrust belt and its foredeep basin (Western Carpathians, Poland). Geol. Quart., 50 (1): 169-194. OSZCZYPKO N. and SALATA D. (2005) - Provenance analyses of the Late Cretaceous-Palaeocene deposits of the Magura Basin (Poltsh Western Carpathians) - evidence from the heavy minerals study. Acta Geol. Pol., 55 (3): 237-267. OSZCZYPKO N. and OSZCZYPKO-CLOWES M. (2009) - Stages in the Magura Basin: a case study of the Polish sector (Western Carpathians). Geodinam. Acta, 22 (1-3): 83-100. OSZCZYPKO N. and OSZCZYPKO-CLOWES M. (2010) - The Paleogene and Early Neogene strat igr aphy of the Beskid Sądecki Range and Lubovnianska Vrchovina (Magura Nappe, Western Carpathians). Acta Geol. Pol., 60: 317-348. OSZCZYPKO N., MALATA E., SVABENICKÂ L., GOLONKA J. and MARKO F. (2004) - Jurassic-Cretaceous controversies in the Western Carpathian Flysch, the “Black Flysch” case study. Cretaceous Res., 25 (1): 89-113. SCHLANGER S. O. and CITA M. B. (1982) - Nature and Origin of Creta- ceous Carbon-rich Facies. Acad. Press, London. SCHLANGER S. O. and JENKYNS H. C. (1976) - Cretaceous oceanic anoxic events: Causes and consequences. Geol. Mijn., 55: 179-184. SIKORA W. (1962) - Nowe dane o stratygrafii magurskiej w okolicy szczawnicy. Kwart. Geol., 6 (4): 805-806. SPISIAK J., BUCOVÄ J., PLASIENKA D. and MIKUS T. (2008) - Creta- ceous alkali volcanites in the Chmielova region (Vrsatec klippen area Pieniny Klippen Belt, Western Carpathians). In: SlovTec08. Proc. Excur. Guide (eds. Z. Nemeth and D. Plasienka): 124-125. State Geol. Inst. D. Stur, Bratislava. SPISIAK J., PLASIENKA D., BUCOVÄ J., MIKUS T. and UHER P. (2011) - Petrology and palaeotectonic setting of Cretaceous alkaline basaltic volcanism in the Pieniny Klippen Belt (Western Carpathians, Slovakia). Geol. Quart., 55 (1): 27-48. ŚLĄCZKA A. and KAMIŃSKI M. (1998) - A guidebook to excursions in the Polish Flysch Carpathians. Grzybowski Found. Spec. Publ., 6. TAYLOR S. R. and McLENNAN S. M. (1985) - The continental crust: its composition and evolution. Blackwell, Oxford. TURGEON S. and BRUMSACK H. J. (2006) - Anoxic vs dysoxic events reflected in sediment geochemistry during the Cenomanian-Turoni an Boundary Event (Cretaceous) in the Umbria-Marche Basin of central Italy. Chem. Geol., 234: 321-339. WANG C., HU X., HUANG Y. and WAGREICH M. (2011) - Cretaceous oceanic red beds as possible consequence of oceanic anoxic events. Sediment. Geol., 235 (1-2): 27-37. WINKLER W. and ŚLĄCZKA A. (1992) - Sediment dispersal and prove- nance in the Silesian, Dukla and Magura flysch nappes (Outer Carpathians, Poland). Geol Rundsch., 81: 371-382. WINKLER W. and ŚLĄCZKA A. (1994) - A geodynamic model for the Western Carpathians in Poland (Late Cretaceous-Paleogene). Geol. Carpath., 45: 71-82. WÓJCIK-TABOL P (2006) - Organic carbon accumulation events in the mid-Cretaceous rocks of the Pieniny Klippen Belt (Polish Carpathians)-apetrological and geochemical approach. Geol. Quart., 50 (4): 419-437. WÓJCIK-TABOL P. and ŚLĄCZKA A. (2009) - Provenance of siliciclastic and organic material based on geochemical indices in the Albian-Turonian sediments - preliminary studies from Lanckorona Area in the Silesian Nappe, Polish Outer Carpathians. Ann. Soc. Geol. Pol., 79: 53-66. WÓJCIK-TABOL P and OSZCZYPKO N. (2010) - Relationship between the ?Cretaceous “black shales”; and Cretaceous Oceanic Red Beds of the Grajcarek Succession - a geochemical approach (Pieniny Klippen Belt, West Carpathians, Pol and). Scientific Annals, School of Geol- ogy, Aristotle University of The saloniki, Proceedings XIX Congress of the Carpathian-Balkan Geological Association (CBGA2010), 100: 249-258.