Or ganic-mat ter vitrinite reflectance vari abil ity in the Outer Carpathians, Po land:
re la tion ship to tec tonic evo lu tion
Magdalena ZIELIÑSKA1, *
1 Uni ver sity of Silesia, Fac ulty of Earth Sci ences, Bêdziñska 60, 41-200 Sosnowiec, Po land
Zieliñska, M., 2017. Or ganic-mat ter vitrinite reflectance vari abil ity in the Outer Carpathians, Po land: re la tion ship to tec tonic evo lu tion. Geo log i cal Quar terly, 61 (1): 214–226, doi: 10.7306/gq.1338
Ran dom vitrinite reflectance of allochthonous plant ma te rial var ies through out all the flysch sed i men tary units of the Outer West ern Carpathians. The vitrinite reflectance of coalified phytogenic mat ter is vari able even within the same lithostratigraphic unit. There is no clear re la tion ship be tween ran dom vitrinite reflectance and stra tig ra phy (age of par tic u lar strata) within sur face sam ples. The typ i cal pat tern of in creas ing ran dom reflectance with depth in bore holes is un set tled by Rro “jumps” which oc cur within folds and overthrusts. How ever, this study re vealed a trend of in creas ing ran dom vitrinite reflectance from north to south in the area of the Magura Unit. A compressional re gime in volv ing phases of up lift and burial, vary ing from place to place in the flysch ba sin, was the main fac tor in flu enc ing coalification. The ini tial ma tu rity of or ganic mat ter trans ported to the ma rine en vi ron ment was a sec ond ary fac tor. A de gree of coalification had oc curred in the flysch sed i ments prior to the main stage of fold-and-thrust move ments as so ci ated with the phase of max i mum tec tonic sub si dence at the end of the Eocene. It is gen er ally as sumed that coalified plant ma te rial dis persed in sed i men tary rocks ex pe ri enced the same phys i cal and chem i cal changes as those in larger ac cu mu la tions of coal. Coalification of phytogenic ma te rial co eval with flysch in the Outer Carpathians cor re sponds to the in ter val from sub-bi tu mi nous to low-me dium-rank bi tu mi nous coal.
Key words: Outer Carpathians, or ganic mat ter, ther mal ma tu rity, vitrinite reflectance.
INTRODUCTION
The fo cus of cur rent re search on or ganic mat ter in the Carpathians is the as sess ment of its ther mal ma tu rity to iden tify ar eas pro spec tive for hy dro car bons. Most of this re search is cen tred in the east ern part of the Pol ish Outer Carpathians and on those flysch se quences that ex hibit the high est con tents of or ganic mat ter and have a high po ten tial for hy dro car bon gen - er a tion (Kuœmierek et al., 1995; Kotarba and Nagao, 2008;
Wiêc³aw et al., 2012). Geo chem i cal anal y ses al low ing to es ti - mate the amounts of or ganic car bon, types of or ganic ma te rial and their ma tu rity in the flysch for ma tions have been de ter - mined by, e.g. Kuœmierek (1990), Curtis et al. (2004), Lewan et al. (2006), Wójcik-Tabol (2006, 2015), Kotarba et al. (2007), Kosakowski et al. (2009) and Semyrka (2009). Menilite shales (e.g., Hempel, 1955; Kosakowski, 2013), long deemed to be of great im por tance in de ter min ing stem ar eas for hy dro car bon de pos its, are the key in ter est.
Coalified or ganic mat ter mainly of plant or i gin and ex hib it ing di verse mor pho log i cal forms is com mon in cer tain parts of flysch se quences. Its de gree of coalification ranges from sub-bi tu mi nous C to high-vol a tile B bi tu mi nous coal (e.g., Wag -
ner, 1980, 1992, 2011). Ex am i na tion, in the con text of geo log i - cal struc ture, of the de gree of coalification and of mor pho log i cal forms that char ac ter ize the coalified or ganic mat ter may sig nif i - cantly con trib ute to a better un der stand ing of coalification in the Al pine orog eny.
In this pa per, new ran dom vitrinite reflectance data are pre - sented and the causes of ran dom vitrinite reflectance vari abil ity in flysch sed i ments are dis cussed.
GEOLOGICAL SETTING
The Outer Carpathians be long to the Eu ro pean Al pine moun tain chain that ex tends from the Iron Gate of the Dan ube River in the west to Predeal Pass in Ro ma nia (e.g., Ksi¹¿kiewicz, 1977; Birkenmajer, 1986; Oszczypko, 1992, 2006; Œwierczewska and Tokarski, 1998). The Outer Carpathians are sub di vided into west ern and east ern parts (e.g., Oszczypko, 2004; Fig.1A). To the south, there is the Pieniny Klippen Belt form ing an orogenic su ture be tween the Outer and In ner Carpathians. The Outer Carpathians, also known as the Flysch Carpathians, com prise Me so zoic, Paleogene and Neo gene rock com plexes which, from the Late Eocene to Mid dle Mio cene, were tec toni cally de formed, sep a - rated from their base ment, and thrust tens of kilo metres north - wards onto the fore land (e.g., Ksi¹¿kiewicz, 1972; Birkenmajer, 1986; Oszczypko, 1992; Œl¹czka, 1996; Oszczypko and Oszczypko-Clowes, 2014). In front of the Outer Carpathians, folded molasse sed i ments oc cur (¯elaŸniewicz et al., 2011).
* E-mail: magdalena.zielinska@us.edu.pl
Received: April 12, 2016; accepted: July 5, 2016; first published online: December 29, 2016
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A num ber of struc tural units be long ing to the Flysch Carpathians oc cur within the study area (Fig. 1B). Start ing from the south, these are the Magura Unit, the group of Fore-Magura units and the Silesian and Subsilesian units (e.g., Golonka, 2007). The Fore-Magura units in clude the Fore-Magura Unit sensu stricto, and the Dukla and Grybów units oc cur ring in tec - tonic win dows (Fig. 1C). Be low the nappes, there are Mio cene for ma tions and the crys tal line base ment of the Eu ro pean Plat - form be long ing to the Brunovistulicum Up per Silesian Mas sif (also known as the Up per Silesian Block) and the Ma³opolska tec tonic block (Paul et al., 1996; ¯ytko, 1999; Cieszkowski et al., 2009; Bu³a et al., 2015; Fig. 1C).
Each nappe is a sep a rate tec tonic unit com posed mainly of turbiditic for ma tions. Prior to any orogenic tectonism, the nappe sed i ments were ac cu mu lated in a se ries of sed i men tary bas ins on the north ern mar gin of the Tethys Ocean (Ksi¹¿kiewicz, 1972; Tokarski, 1980; Oszczypko and Œl¹czka, 1985; Konon, 2001; Nemèok et al., 2001). The in di vid ual bas ins were sep a - rated by a se ries of sub ma rine up lifts and el e va tions. The most im por tant of these, the Subsilesian, Silesian and Czorsztyn ridges, were the main sources of clastic ma te rial de pos ited in the var i ous bas ins (Poprawa et al., 2002).
METHODS
FIELD STUDIES
The ba sic re search ma te rial con sisted of 205 flysch sam - ples com pris ing 170 sam ples gath ered at 85 sur face lo ca tions and 35 sam ples from 7 bore holes. The sur face sam ples came from nat u ral out crops and quar ries (see Fig. 1B). Core sam ples were col lected from bore holes: Tokarnia IG 1, Bystra IG 1, Obidowa IG 1, Nowy Targ PIG 1, £odygowice IG 1, G³ogoczów IG 1 and Porêba Wielka IG 1. The bore hole lo ca tions are shown on Fig ure 1D.
ORGANIC MATTER SAMPLES
Lump sam ples with pol ished sur face were pre pared from all col lected sam ples. In this study, all len tic u lar and lamellar ac cu - mu la tions of coal, plant de tri tus and dis persed or ganic mat ter were treated as pre served or ganic ma te rial dif fer ing only in size. Only coalified or ganic mat ter co eval with flysch sed i ments was se lected, no coal exotics in cluded.
VITRINITE REFLECTANCE
To de fine the de gree of or ganic-mat ter coalification, ran - dom vitrinite reflectance mea sure ments Rro
were car ried out.
Reflectance is the abil ity of pol ished sur faces of macerals of the vitrinite and huminite groups to re flect light. Mea sure ments of reflectance were made on sur faces of ulminite B/collotelinite in rocks con tain ing vitrinite (ISO 7404-5:2009) in par tially polar - ised light (1N) us ing an Opton Zeiss mi cro scope with Axioplan MPM 400 reflectometre, ac cord ing to the ICCP (In ter na tional Com mit tee for Coal and Or ganic Pe trol ogy, 1994) re quire - ments. Im mer sion oil with a re frac tive in dex of n = 1.518 at a tem per a ture of 20–22°C, and the ura nyl stan dard of 0.904%
were used. The num ber of sep a rate mea sure ments per sam - ple, rang ing from 71–145, de pended on the num ber of mea sur - ing points, i.e. the amount of coalified collotelinite/vitrinite forms.
The max i mum stan dard de vi a tion of the ran dom vitrinite reflectance mea sure ments was cal cu lated to be 0.06%.
RESULTS
VARIABILITY OF DEGREE OF COALIFICATION OF PLANT MATERIAL IN INDIVIDUAL STRUCTURAL UNITS – SURFACE SAMPLES
The de gree of coalification of allochthonous plant ma te rial var - ies through out the en tire pro file of the Outer West ern Carpathian for ma tions (Ap pen dix 1*). Or ganic mat ter ma tu rity var ies even be - tween sam ples from the same lithostratigraphic unit.
Reflectograms based on the mea sured Rr
o typ i cally ex hibit two or even three modal val ues (Fig. 2). The first peak is re lated to the oc cur rence of so-called dark vitrinite (vitrinite B) which low - ers the real value of Rro
in the sam ple. Dark vitrinite re flects sub-im preg na tion with resinite ma te rial or an or i gin from non-lignine ma rine plants or even par tial bitu mi ni sa tion of the plant ma te rial, e.g. in deep-sea con di tions (Newman and Newman, 1982). The sec ond peak should be re lated to collotelinite (vitrinite A). Usu ally, this peak is clearly sep a rated from the oth ers and is the dom i nant peak. With a stan dard reg is - tra tion for 1/2V= 0.05% (Stach et al., 1982), the two peaks link as one with a no tice able neg a tive skew ness (Syrek, 2009). Mea - sure ments made on pseudovitrinite, with petrographic fea tures sim i lar to collotelinite or vitrodetrinite, may re sult in a third peak.
Magura Unit. The de gree of coalification of or ganic ma te rial in the Magura Unit shows a gen er ally in creas ing trend to wards the south (Fig. 3). The high est Rr
o val ues char ac ter ize the area di rectly bor der ing the Pieniny Klippen Belt. Here, the Rro
val ues range from 0.71% in the Szczawnica For ma tion (Senonian–Paleocene) at Koœcienko nad Dunajcem (Kr, MS 43; ab bre vi a tion of sam ple lo ca tion and its sym bol for all text see Fig. 3 and Ap pen dix 1) to 0.81% in Maniowy (My, MS 109) and 0.82% in the Magura sand stones (Eocene–Oligocene) at Klikuszowa (Kl, MS 130) near Nowy Targ (Ta ble 1). The low est Rr
o val ues (0.40–0.45%; MS 96, 60, 06, 151) typ ify the north ern and cen tral-east ern parts of the nappe. Poprawa et al. (2002) have shown that, in the south ern part of the Magura Ba sin, the to tal thick ness of Cre ta ceous and Paleogene sed i ments was 3000–3500 m and 2300–2500 m in the north ern part in the study area. Sub si dence from the end of the Cre ta ceous to Early Mio cene may be at trib uted to flex ural bend ing of the base ment due to subduction, and to burial by the accretionary wedge (Poprawa et al., 2002).
The cen tral parts of the Magura Unit, where tec tonic win - dows are sit u ated, also fea ture high val ues of Rro
. In the Mszana Dolna (MG, MS 69, 87) tec tonic win dow, or ganic mat - ter in the Krosno Beds (Oligocene) of the Dukla Unit shows Rr
o
of 0.65–0.67%. In the Grybów Marl For ma tion (Mid dle/Up per Eocene) of the Grybów Unit in Koninki (Ko, MS 56) the value is 0.64%. In the Szczawa (Sz, MS 55) tec tonic win dow, the Rro
val ues of coalified mat ter in the Krosno Beds (Oligocene) of the Grybów Unit are 0.64%. In the Klêczany–Limanowa (Kc, MS 81) tec tonic win dow, the Rro
val ues of or ganic mat ter in the Krosno Beds (Oligocene) and Cergowa Beds of the Grybów Unit (Peszat, 1997) are as high as 0.76% (Ta ble 1).
In the en tire pro file of the Magura Unit (Ap pen dix 1), no cor - re la tion of Rro
with in di vid ual lithostratigraphic po si tion was noted. The great est di ver sity is seen in the Magura For ma tion (Lower Eocene–Oligocene) in which Rr
o val ues range from 0.40 to 0.82% (Ta ble 1).
* Supplementary data associated with this article can be found, in the online version, at doi: 10.7306/gq.1338
Fig. 2. Typical histograms of random vitrinite reflectance from selected samples
Fore-Magura Unit sensu stricto. Most of the six sam ples from the Fore-Magura Unit s.s., col lected in the ar eas of Istebna (Is), Kamesznica (Kam) and Przybêdza/Juraszów (Prz), are from the Oligocene Krosno Beds in which Rro
ranges from 0.42 to 0.45%; the de gree of coalification is uni form. In ter est ingly, sam ples of the older Jaworzynka For ma tion (MS 174; Lower Senonian) taken in Ciêcina (Ci) are char ac ter ized by Rro
val ues of 0.81%, and sam ples of the youn ger Oligocene Menilite beds (MS 187) from Przybêdza/Juraszów (Prz; Ta ble 1) by a value of 0.54%. A cor re la tion be tween Rro
val ues and strati graphic age may be in di cated. In this case, the dif fer ence in Rro
be tween the old est and the youn gest beds is ~0.3%, which is con sis tent with a trend of in creas ing Rr
o with depth of burial (Hilt’s law). Dif fer - en ti at ing the north ern and south ern part of the Fore-Magura Unit (Golonka et al., 2005; Golonka, 2007), it is no ta ble that the de gree of coalification is higher in the lithostratigraphic pro file of the south ern unit that has fea tures in com mon with Magura Unit for ma tions, whereas it is lower in the north ern part where li thol - ogy is sim i lar to the Silesian Unit.
Silesian Unit. The trend in the area of Silesian Unit is not as well vis i ble as in the Magura Unit; more di ver sity within Rr
o is ob served. A map of the dis tri bu tion of Rro
shows four ar eas with el e vated val ues (Fig. 3). In the west ern part of the Silesian Unit, the high est value of 0.73% was noted in the Istebna Beds (Senonian–Paleocene) in the area of Kamesznica (Kam, MS 178), val ues of 0.72% in the Godula Beds (Cenoman - ian–Senonian) in Szczyrk (Szcz, MS 131), and of 0.63% in the Cieszyn Lime stones For ma tion (Tithonian–Berriasian) in Leszna Górna (Lg, MS 119).
In the cen tral part of the unit, the high est Rro
val ues ap - peared in sam ples from the Lanckorona (Lan, MS 157, MS 183) area, namely 0.62% from the Lhoty For ma tion (Albian–Cenomanian), 0.69% from the Veøovice For ma tion (Barremian–Aptian), and 0.64% from an out crop of the Veøovice For ma tion in Krzywaczka (Kw, MS 142). The east ern part of the Silesian Unit has two zones of rel a tively high Rro
. The first in volves or ganic mat ter in the Istebna For ma tion (Senonian/Paleocene) from Zegartowice (Ze, MS 47) with Rro
val ues of 0.65%. The sec ond zone is near Ro¿nów Lake in Znamirowice (Zn, MS 53; Istebna For ma tion) and Kurów (Kó, MS 168; Cisownica Shale; Valanginian/Hauterivian) with Rro
val ues of 0.64% and 0.63%, re spec tively.
In the en tire pro file of the Silesian Unit, there is no cor re la - tion be tween or ganic mat ter ma tu rity and the age of par tic u lar lithostratigraphic beds. The great est di ver sity of Rro
is vis i ble within the Godula (Cenomanian–Senonian), Istebna (Senonian–Paleocene) and Krosno (Oligocene) for ma tions.
The low est and high est val ues in these for ma tions dif fer by 0.20%, 0.33% and 0.17%, re spec tively.
Subsilesian Unit. Sam ples were col lected from the ¯ywiec (¯w) tec tonic win dow and the tec toni cally dis turbed Lanckorona–¯egocina area (Fig. 3).
The ¯egocina Marls (Senonian) gave the high est value (0.63%) of Rro
of all tested Subsilesian sam ples, and the Menilite For ma tion (Oligocene), the low est (0.46%; Ta ble 1).
Gen er ally, the de gree of coalification in the Subsilesian Unit is rather uni form (see Ap pen dix 1). The ex cep tional Rro
value of 0.63% from the ¯egocina Marls may re flect the fact that the marls com prise re-de pos ited blocks of Frydek-type marls from the lime stone plat form and oc cur in an area of tec tonic melanges (Jugowiec-Nazarkiewicz and Jankowski, 2001).
VARIABILITY OF DEGREE OF COALIFICATION OF ORGANIC MATERIAL IN BOREHOLES
In the south ern most bore hole of Nowy Targ PIG 1, Rro
in - creases with depth (Fig. 4), at tain ing a value of 0.61% at a depth of 100 m, 0.63% at 800 m, and 0.67% at ~2150 m. This small in crease in Rro
oc curs en tirely within the Malcov Beds (Magura For ma tion). A greater in crease to 0.75% is ev i dent at
~2500 m in the older Szczawnica For ma tion.
Three struc tural units were en coun tered in the Obidowa IG 1 bore hole (Fig. 4): the Magura Unit down to 2666 m, and the Grybów Unit at ~2800 m, which passes at ~3300 m into the Obidowa–S³opnice Unit that con tin ues down to 4570.5 m. The sta tus of the Obidowa–S³opnice Unit is prob lem atic. It is Fig. 3. Map of surface samples with random vitrinite reflectance variability within study area
Other explanations as in Figure 1B
T a b l e 1 Vitrinite reflectance of or ganic mat ter in the OWC for ma tions and beds
Other ex pla na tions as in Fig ure 1B
modnar fo seliforp htpeD .4 .giFetinirtivdeiduts seloherob ni ecnatcelfer
deemed to be a west ern fa cies ex ten sion of the Dukla Unit (Burtan et al., 1992) and even as a part of the Skole Unit (¯ytko and Malata, 2001). For lithostratigraphic rea sons, a link age to the Dukla Unit is fa voured here.
In gen eral, Rro
val ues in crease with depth from 0.76% in the Inoceramian Beds of the Magura Unit to 1.02% in the Inoceramian (Obidowa) Beds of the Dukla Unit. De vi a tions from the trend are ev i dent in youn ger beds of other struc tural units in the overthrust area.
Sam ples from the Porêba Wielka IG 1 bore hole rep re sent the Dukla Unit flysch for ma tions from the Mszana Dolna tec - tonic win dow (Fig. 4). The rocks were de pos ited in rel a tively shal low wa ter (Jugowiec-Nazarkiewicz and Jankowski, 2001).
Silty zones, more sus cep ti ble to com pres sion, show greater in - cli na tions. The youn gest sed i ments, the Krosno For ma tion, were drilled to a depth of 1500 m. The Rro
value of or ganic mat - ter in the up per part of the Krosno For ma tion at a depth of 200 m is 0.82%. Rr
o val ues of or ganic mat ter in lower part of Krosno sed i ments range from 0.79% at ~500 m to 0.86% at 1100 m.
The Rro
value ob tained from the Menilite For ma tion at 1420–1423 m is 0.86%, and from the Inoceramian Beds (Ropianka For ma tion) at 1744–1747 m – 0.97%. Rr
o val ues in - crease with depth.
In the Tokarnia IG 1 bore hole, sed i ments from the Magura and Silesian units were sam pled (Fig. 4). The Rro
of or ganic mat ter in the Magura For ma tion at the low est depth in pro file is 0.59%. An in crease to 0.76% with in creas ing depth is ob served in the Hi ero - glyphic Beds. Be low, a de crease to 0.68% is re lated to the re ap - pear ance of the Magura For ma tion, most likely in a fold.
At 2044 m depth, the Inoceramian Beds from the older Magura Unit are thrust over the Krosno For ma tion from the youn ger Silesian Unit. The ran dom vitrinite reflectance for the Krosno For ma tion (Oligocene) is 0.79%, lower by 0.08% than for the over ly ing beds (0.88% in Eocene shales). Or ganic mat - ter in deeper sed i ments shows a slight in crease in Rro
to 0.84%.
Be low, it de creases (0.67%) in marly shales that prob a bly rep - re sent the Cisownica shale. In this in stance, the de crease may be re lated to a tec tonic un con formity be tween the Oligocene Krosno For ma tion and the Lower Cre ta ceous shales.
Sed i ments in the Bystra IG 1 bore hole show the great est lithostratigraphic vari abil ity of all in the bore holes (Fig. 4). Fold - ing is im por tant; al ter nat ing older and youn ger ho ri zons are of - ten en coun tered in pro files of known lithostratigraphic units.
There, where the Fore-Magura Unit is thrust over the Magura Unit, the Rro
of or ganic mat ter mea sured in the Inoceramian Beds (Up per Senonian) is 0.82%, whereas near the overthrust of the Fore-Magura Unit onto the Silesian Unit, the value is 0.86% in the Krosno For ma tion (Oligocene). De creases in Rro
to 0.68% were noted in the Krosno Beds in the overthrust of the Silesian Unit on the Subsilesian Unit, and to 0.60% in tec tonic brec cia in the overthrust of the Subsilesian Unit on the Silesian Unit (0.60%). The vari a tion (“jumps”) in Rro
in the pro file seems to re flect nu mer ous fold-type tec tonic struc tures and could in di - cate that or ganic mat ter in the flysch sed i ments had reached fi - nal ma tu rity prior to fi nal thrust ing. Oth er wise, “jumps” could not be vis i ble within tec tonic struc tures.
Sed i ments from the £odygowice IG 1 bore hole rep re sent both the Silesian Unit and the Subsilesian Unit. Be low, autochthonous Mio cene rocks and crys tal line base ment were drilled (Fig. 4). Rro
val ues of or ganic mat ter in the Silesian Unit in crease with depth. The low est value of Rro
(0.74%) was mea - sured in the Krosno For ma tion (Oligocene), the high est (1.19%) in the Grodziszcze For ma tion (Hauterivian–Aptian, Subsilesian Unit). In the overthrust area, a dis tinct de crease of Rro
to 0.83%, ev i dent in the Grodziszcze For ma tion, may re flect small-scale, thrust-re lated lihological com plex ity be tween struc tural units.
The north ern most bore hole of G³ogoczów IG 1 pen e trates flysch for ma tions to a depth of 652.5 m. The flysch for ma tions com prise the Silesian Unit (to 601 m depth) and the Subsilesian Unit (to 652.5 m). They are both tec toni cally dis turbed. Within the Silesian Unit, the Grodziszcze For ma tion (Hauterivian/Bar - remian) passes down into the Lhoty For ma tion (Albian) and the Up per Istebna For ma tion (Paleocene). The tec toni cally mixed for ma tions of the Subsilesian Unit might be termed a tec tonic brec cia (Fig. 4). Re versed beds in the Silesian Unit re flect sig - nif i cant fold ing and overthrusting. These rocks may be long to the north ern mar gin of the Flysch Carpathians where in ter nal units are thrust over highly-tectonized rocks of the Subsilesian Unit. Sam pling was not pos si ble here. In this core, the Rro
value in creases from 0.48% in the Up per Visean Shales to 0.65% in Lower Visean car bon ate for ma tions, and 0.85% in De vo nian for ma tions. Or ganic mat ter in Mis sis sip pian rocks at a depth of
~1500 m is char ac ter ized by a rel a tively low de gree of coalification.
DISCUSSION
COMPARISONS WITH ORGANIC MATERIAL IN COEVAL SEDIMENTS ELSEWHERE,BASED ON Rro
DATA
De grees of coalification of or ganic mat ter in the Outer Carpathians re late to the sed i men tary and tec tonic his tory of the host rocks. To gain a more com plete in sight, com par i sons are made to the east ern part of the Carpathians in Po land, the Podhale Flysch, the Carpathians out side Po land, and the Alps.
The name Outer West ern Carpathians (OWC) re fers to the study area.
EASTERN CARPATHIANS IN POLAND
Rel e vant stud ies in the East ern Carpathians in volve mainly thick com plexes of Lower Cre ta ceous shale se ries, Up per Cre ta - ceous–Lower Oligocene silty sed i ments, and the Oligocene Krosno For ma tion (Matyasik, 1994; Semyrka, 2009). The fo cus of these stud ies was the hy dro car bon po ten tial of the named for ma - tions, as the east ern Outer Carpathians are more fa vour ably pre - dis posed to de velop ef fec tive oil sys tems (Kuœmierek, 2004). The lithostratigraphic sim i lar ity of the flysch for ma tions in the East ern and Outer West ern Carpathians, and pub lished vitrinite reflectance data, in vite a com par i son to be made.
The great est amount of data on or ganic mat ter coalification is avail able for the Menilite Shales. Kosakowski et al. (2009) doc u mented the low (from 0.35 to 0.40%) de gree of coalification in the Menilite For ma tion of the Dukla, Silesian and Skole units; the low est Rro
val ues (0.30%) were noted in the north west ern part of the Skole Unit, and the high est (up to 0.67%) in the Dukla Unit in the south east ern part of the area.
The in creas ing de gree of coalification to wards in ter nal units of the Carpathians con firms ear lier find ings by Kruge et al. (1996) and Besserau et al. (1997).
Uni formly low (<0.50%) val ues of Rro
char ac ter iz ing the Menilite Shales in hib ited es ti ma tion of gra di ent vari abil ity in sur - face sam ples (Kuœmierek, 1995). Those sam ples col lected from sig nif i cantly eroded el e va tion zones did not help. The older rocks pro vided more var ied and more use ful val ues. The fact that Rr
o curves for the mar ginal zones of the East ern Carpathian ba sin were mainly steeper than those for the cen tral zones re flected, ac cord ing to Kuœmierek (1990, 1995), the more sta ble tec tonic re gime of the mar ginal zones, and a de lay in the pro cess of burial that aided the es ti ma tion of max i mal
palaeo-heat flows. In ad di tion, depth pro files of Rro
val ues in Oligocene for ma tions from the Dwernik-3 and Sêkowa-Gorlice bore holes (East ern Outer Carpathians) are com pat i ble with the trend of in creas ing de gree of coalification with in creas ing depth.
In some bore holes, up per beds are char ac ter ized by higher Rro
val ues than are lower beds in the pro file. This is a dis tin guish ing fea ture of highly-folded com plexes and re versed strati graphic se ries as well as of nor mally-de pos ited se ries of the Magura Nappe fore ground or in its tec tonic win dows. Ad di tion ally, in very deep bore holes (e.g., KuŸmina-1 in the Bieszczady Mts.) that pen e trated the base ment, a low er ing of Rro
in thrust slices of Up per Cre ta ceous rocks in the lower parts of the pro file was pre vi ously noted (Borys et al., 1989; Semyrka, 2009). De - creases in Rr
o is a con se quence of deep tec tonic slip page of the East Eu ro pean Plat form with the re sult that for ma tions now di - rectly in con tact with the base ment oc cur at depths ex ceed ing those at which their pre-tec tonic Rro
val ues were es tab lished (Kuœmierek, 1990, 1995).
Sim i lar pat terns of dif fer ences in ran dom vitrinite reflectance char ac ter ize the OWC area. Firstly, low val ues of Rro
(0.40–0.53%) from the Menilite For ma tion con firm the re - sults of Kuœmierek (1995) and Kosakowski et al., (2009). Sec - ondly, some bore hole pro files pro vide fur ther sim i lar ev i dence.
In the Tokarnia IG 1 bore hole, higher Rro
val ues in the up per part of the pro file are due to strati graphic in ver sion and, in the
Porêba Wielka IG 1 bore hole, to thrust slic ing of the older Krosno For ma tion. In the G³ogoczów IG 1, £odygowice IG 1 and Tokarnia IG 1 bore holes that pen e trated the base ment, Rro
de - creases at the con tact of the flysch se ries with the base ment.
Fi nally, Rro
curves in the Nowy Targ PIG 1 and Obidowa IG 1 bore holes in the mar ginal zone of the Magura Unit (Fig. 5) are steeper than in other pro files.
Higher val ues of Rro
in the Magura Unit tec tonic win dows are rep re sented by val ues from the Mszana Dolna, Klêczany and Szczawa sam ple lo ca tions which sed i ments be long to the Fore-Magura Unit. Oligocene for ma tions, ex posed in cen tral zones, are char ac ter ized by higher Rro
than the older, sur round - ing rocks. Such anom a lies are at trib ut able to de vel op ment of du plexes in the base ment of the Magura Nappe in the fi nal stage of its overthrusting onto the Carpathian Foredeep (Œwierczewska and Tokarski, 1998; Œwierczewska, 2005). Ac - cord ing to Œwierczewska (2005), heat ing re lated to tec tonic burial was the main fac tor that in flu enced the Magura Unit strata. Such con di tions were es tab lished dur ing ac cre tion.
The sim i lar i ties in the Rro
pat terns of the west ern and east ern parts of the Outer Carpathians seem to re flect con sis tently sim i - lar causes; both parts were sub ject to sim i lar fluc tu a tions dur ing the syn- and post-orogenic stages of up lift and sub si dence in the flysch sub-bas ins. Dif fer ences may be due to vari a tions in sub-ba sin depths, de grees of sub si dence, and late tectonism.
Fig. 5. Comparison of random vitrinte reflectance data in boreholes profiles in N–S cross-section
PODHALE FLYSCH
Vari a tions in the de gree of coalification in the Podhale Flysch are sim i lar to those en coun tered in the OWC. How ever, the rank changes in the Podhale Flysch have not been fully de - scribed yet. Ear lier work has fo cused on, e.g. mac ro scopic de - scrip tion and sed i men ta tion of or ganic ma te rial. In their study of the ther mal his tory of the Tatra Mts, Poprawa et al. (2004) used sam ples from the Podhale Flysch; typ i cal Rro
val ues ranged from 0.85 to 1.3%. Marynowski and Gawêda (2005), in a com - par a tive anal y sis of biomarkers and Rr
o in the Podhale Flysch Paleogene rocks, found that Rro
in creases to wards the SE, per - pen dic u lar to the main fault zones. The high est val ues were re - corded in the Zakopane IG 1 bore hole (2.37–2.42%) and the Bukowina Tatrzañska IG 1 bore hole (1.09–1.14%), and the low - est in the Chocho³ów PIG 1 bore hole (0.78–1.02%). Later, the diagenesis, sub si dence and ther mal his tory of the Podhale Flysch were dis cussed (Kêpinska, 2006; Œrodoñ et al., 2006;
Œrodoñ, 2008). Wag ner (2010, 2011) at tempted to ex plain pos - si ble causes for the dif fer ences in or ganic mat ter rank, us ing Rro
data from sur face sam ples. He re ported an in crease in Rro
from the north-west (0.49%) to wards the south-east (1.00%). These val ues cor re spond to bi tu mi nous coal D and C (PN-ISO 11760:2007/DIS 11760).
Ac cord ing to pre vi ous re search, dif fer ences in Rro
val ues do not re late to the stra tig ra phy of the Podhale Flysch, but rather to the depth of burial of the sed i ments and later tec tonic up lifts (Savian Phase). Fur ther more, the changes in Rro
val ues track the con tents of crys tal line illite in silty rocks (Œrodoñ, 2008).
Crys tal line illite con tents in di cate a clear trend of in creas ing tem per a ture with depth of burial to wards the SW. Wag ner (2010, 2011) es ti mated the prob a ble sed i ment burial depths in the re gion, as sum ing the val ues of palaeothermal gra di ent in the range of 30–40°C/km. Us ing the mea sured Rro
, he cal cu - lated the depths from 3.2 km (gra di ent 30°C/km) to 2.7 km (gra - di ent 40°C/km) in the north west ern part, and ~5 km (30°C/km) or ~4 km (40°C/km) in the south-east. These es ti mates sug gest a flysch thick ness greater than pres ent-day thick nesses by
~2.8 km in the north-west and ~2.2 km in the south-east.
Both the OWC and the Podhale Flysch show a sim i lar in - crease in Rro
to wards the S and SE. Dif fer ences are mainly ev i - dent in the ranges of Rro
val ues both in sur face and bore hole sam ples in these ar eas. Sur face val ues in the ranges of 0.49–1.00% (Wag ner, 2010, 2011) and 0.85–1.30% (Poprawa et al., 2004) from the Podhale Flysch are in con trast with the val ues of 0.40–0.82% in flysch from the OWC, as re ported above. Rr
o val ues from bore hole sam ples in the Podhale Flysch reach the max i mum val ues of 2.37–2.42% in the Zakopane IG 1, whereas, in the south ern most bore holes of Nowy Targ PIG 1 and Obidowa IG 1 in the OWC, the val ues are as low as
~1.00%.
The Podhale Flysch ba sin was not sub jected to fold-and-thrust tec tonic move ments, but did ex pe ri ence ver ti cal tec tonic move ments re lated to the up lift ing of the Tatra Mas sif, sug gest ing that coalification in the Podhale sed i ments was re - lated to sub si dence and burial linked to re gional tec ton ics (Birkenmajer, 1988). Vari a tions in coalification in the OWC also re flect sub si dence and burial in an area that was also sub jected to syn-orogenic tec tonic up lift and thrust ing. Poprawa et al.
(2002) sug gested that ba sin-floor to pog ra phy was rel e vant there.
CARPATHIAN OROGEN AND THE ALPS
Not sur pris ingly, many sim i lar ex pla na tions have been pro - posed to ex plain vari a tions in ran dom vitrinite reflectance in the
Alps and the Carpathians. Schuller (2004), deal ing with the evo lu tion of the Up per Cre ta ceous sed i men tary ba sin in the Apuseni Mts. (Ro ma nia), con cluded that depth pro files show ing abrupt “jumps” in Rro
val ues were a con se quence of post-sed i - men tary tec tonic ac tiv ity re sult ing in nu mer ous strati graphic un - con formi ties. Schuller (2004) also noted in stances of in creased Rro
val ues in the up per parts of flysch pro files, caused by thrust - ing within the nappes. The low er ing was not a con se quence of strati graphic in ver sion, but in di cates that the main stage of coalification was com pleted be fore the fi nal stage of thrust ing and fold ing (Hufnagel et al., 1981; Ja cob et al., 1982; Wag ner et al., 1986). Fur ther more, val ues of Rro
do not cor re late with strati graphic po si tion within a given struc tural unit, in di cat ing that coalification likely oc curred dur ing postdepositional events (Kuckelhorn and Hiltmann, 1992). Ad di tion ally, sur face sam - ples re veal a trend of in creas ing Rro
to wards the south and south-east (Ja cob et al., 1982; Wag ner et al., 1986).
Soták et al. (2001) sim i larly ar gued that the changes in Rr o
are not re lated to the depth and stra tig ra phy of the Paleogene sec tion in the Cen tral Carpathian Ba sin of north east ern Slovakia. Soták et al. (2001) ex plained the val ues of Rro
(0.70%) char ac ter iz ing both the Up per Oligocene for ma tions and Lower Oligocene de pos its at a depth of 2000 m as due to Late Oligocene sub si dence re lated to the ac cu mu la tion of molasse in an intermountain ba sin and to load-driven bend ing of the base ment. The bend ing pos si bly led to higher heat flow in the Up per Oligocene de pos its.
In the east ern part of the Slovakian ba sin, Soták et al.
(1995) ob tained high ther mal ma tu rity of or ganic mat ter in Eocene sed i ments. Vitrinite reflectance val ues (Rmin 3.37%, Rmax 5.57%) show a sub-greenshist meta mor phism grade as a re sult of hin ter land ex ten sion re lated to intra-plate ac cre tion.
Belkin et al. (2010), in dis cuss ing Rro
vari a tions in Oligocene bi tu mi nous coal in the Petroºani Ba sin (Ro ma nia), con cluded that high-rank coal was due to the mi gra tion of hy dro ther mal flu - ids. Rro
val ues, in creas ing from NE to SW there, ac cord with the di rec tion of thrust ing and trend per pen dic u lar to ma jor strike-slip faults (Sperner et al., 2002). Strike-slip faults are typ i - cal for the In ner and South ern Carpathians, dis tin guish ing them from the Outer and East ern Carpathians where thrusts pre vail (e.g., Marko et al., 1991; Nemèok, 1993; Kovãè et al., 1994;
Fodor, 1995; Decker and Perreson, 1996). Re gional changes in Rro
, con trolled by burial re lated to ex ten sion and to in tru sive vol - ca nism in the South ern Alps, were em pha sized by Zattin et al.
(2006). Peaks of max i mum tem per a ture and max i mum sub si - dence do not over lap, but are re lated to the oc cur rence of suc - ces sive vol ca nic in tru sions. Mählmann (2001) de scribed thrust-re lated “jumps” in Rro
val ues in depth pro files of nappes in the cen tral part of the Alps (Swit zer land) and noted that el e - vated Rr
o val ues are as so ci ated with mi gra tion of hy dro ther mal flu ids (~270°C) along faults and thrusts. Mählmann (1995, 1996) had ear lier emphasised the sig nif i cant role of heat ing and its du ra tion on coalification in the Alps of east ern Swit zer land.
Reinhardt (1991) de scribed the vari abil ity of Rr
o val ues in nappes of the east ern Apennines. He in ter preted signs of graphitisation in ar eas with the great est es ti mated tem per a - tures (~300°C; Rmax 4–7%) as due to the fact that large rock units were first bur ied to a depth of ~5 km be fore be ing rap idly thrust over large dis tances. In the south ern Alps of Aus tria, Rantitsch (1992, 1997) used Rro
val ues (2.0–2.8%; semi-an - thra cite) to show that clastic rocks had been sub jected to hy dro - ther mal ac tiv ity (350–400°C) re lated to plutonic ac tiv ity in an Oligocene fault zone, the Peri-Adri atic Lin ea ment. In ad di tion, Rro
val ues in crease from south to north, i.e. from footwall to hang ing wall. In the Peri-Adri atic Lin ea ment, Sachsenhofer (1992, 2001) at trib uted Rr
o anom a lies in coal-bear ing for ma -
tions to vol ca nic ac tiv ity; Rro
val ues in the vi cin ity of vol ca nic cen tres range from 1.00–1.30%, whereas, in rocks sev eral kilo - metres dis tant, the val ues are <0.40%. Dunkl et al. (1998) dis - puted Rantitsch’s and Sachsenhofer’s find ings, ar gu ing that not all the anom a lies are vol ca nic-re lated. Syn-rift for ma tions in the hang ing wall of the fault zone show Rr
o val ues of 0.67–1.04%, which they at trib ute to burial of the hang ing wall to a depth of
~1500 m dur ing the fi nal rift ing phase of the Pannonian Ba sin (Tari and Horváth, 1995).
In di ca tions of Mio cene vol ca nism re lated to the fold ing of nappes have been noted in the Paleogene of the Magura Nappe and Pieniny Klippen Belt in the West ern Flysch Carpathians (Birkenmajer, 1979). This opens the pos si bil ity that heat ing and hy dro ther mal ac tiv ity re lated to Mio cene vol ca nism ef fected coalification in the Magura Flysch. Though the pres ent re search in cluded sam ples from re gions of an de site oc cur rence, i.e.
Maniowy (0.82%) and Kroœcienko nad Dunajcem (0.60–0.71%), none were col lected from, e.g. con tact zones of dikes with flysch.
Though the trend of south ward-in creas ing Rro
in the Magura Nappe might sug gest a link with Mio cene vol ca nism, in creases in Rro
(1.00–1.30%) as re ported by Rantitsch (1992, 1997) and Sachsenhofer (1992) are not seen. In the south ern part of the Outer Carpathians, coalification of or ganic mat ter could not be at trib uted to vol ca nism. The ob vi ous Rro
anom a lies in the Silesian Unit are also clearly un re lated to vol ca nism.
CONCLUSIONS
In the OWC, de grees of vitrinite coalification in sur face rocks re veal no re la tion ship with ages of lithostratigraphic for - ma tions due to their re gional dis tri bu tion (oc cur rences). Or - ganic mat ter in the Oligocene rocks of lower units in tec tonic win dows, e.g. Magura Unit, can show higher de grees of coalification than sim i lar or ganic mat ter in older for ma tions of up per units. Fur ther more, sam ples both from the Cre ta ceous (Lanckorona MS 183; Szczyrk MS 131) and Paleogene for ma - tions (Kamesznica MS 178; Zegartowice MS 47; Znamirowice MS 53) may all de fine ar eas of higher de grees of coalification (Rr
o = 0.63%-0.73%) in the Silesian Unit, de spite the age dif fer - ence. In a re gional ap proach, vari a tions in the de gree of coalification shown by sur face sam ples pro vide prob lem at i cal re sults, as large hor i zon tal thrusts, tec tonic slic ing within nappes, and ero sion dis rupt the strati graphic con ti nu ity of the
flysch for ma tions. The rec og ni tion of clear trends is in hib ited, how ever, in the south ern part of the Magura Unit; an in crease in or ganic mat ter rank is ev i dent. The in creas ing de gree of coalification in the south ern part of the Magura Unit is not in flu - enced by the strati graphic po si tion, but may be at trib uted to flex - ural bend ing of the base ment due to subduction and deeper sub si dence re lated to accretionary prism pres sure. Isolines of Rro
il lus trate the pat tern of the main fold struc tures. In the west - ern part of the Outer Carpathians, the Magura Nappe is char ac - ter ized by nu mer ous SW–NE syn clines and anticlines. Rr
o val - ues fol low a sim i lar course. Fur ther east in the nappe, a block-faulted struc ture pre vails.
The re la tion ship of in creas ing Rro
with depth is ob served in bore holes. There is a cor re la tion be tween the coalification de - gree and the age of flysch for ma tions; the older the for ma tion, the higher the value of Rro
. In the Nowy Targ PIG 1, Porêba Wielka IG 1, G³ogoczów IG 1 and the lower sec tion of Obidowa IG 1 bore holes, tec toni cally un dis turbed in ter vals show an age- and depth-re lated in crease in Rro
val ues. In other bore holes, the vari a tion in Rro
with depth (“jumps”) is un der lined by overthrusts be tween nappes.
The be gin ning of coalification was pre- and syn-orogenic and the fi nal stages pre ceded the main fold ing and thrust ing be - cause:
1. The de gree of or ganic mat ter coalification in the bore - holes de pends on the depth and strati graphic po si tion.
Vari abil ity in Rro
de ter mines thrust and fold sur faces among the struc tural units;
2. In the Magura Unit, ar eas with the high est Rro
val ues match ar eas of the high est subduction-re lated sub si - dence. Ther mal ma tu rity of or ganic mat ter oc curred at time of ac cre tion of the Magura wedge;
3. Anom a lous de grees of coalification, de vi at ing from the S-SE trend in the struc tural units, re flect the to pog ra phy of the sub-ba sin floor.
Ac knowl edge ments. This study was sup ported by Stat u - tory Funds of AGH Uni ver sity no. 11.11.140.562. The au thor is grate ful to Prof. J. Soták, Dr. P. Wójcik-Tabol and an anon y - mous re viewer for their help ful re marks. The au thor is also in - debted to P.S. Kennan, Uni ver sity Col lege Dub lin, for im prov ing the Eng lish text. Spe cial thanks are to Prof. T. Peryt for his ed i - to rial work.
REFERENCES
Belkin, E.H., Tewalt, S., Hower, J.C., Stucker, J.D., O’Keefe, J.M., Tatu Calin, A., Buia, G., 2010. Pe trog ra phy and geo - chem is try of Oligocene bi tu mi nous coal from the Jiu Val ley, Petrosani ba sin (south ern Carpathian Moun tains), Ro ma nia. In - ter na tional Jour nal of Coal Ge ol ogy, 82: 68–80.
Besserau, G., Roure, E., Kotarba, A., Kuœmierek, J., Strzetelski, W., 1997. Struc ture and hy dro car bon hab i tat of the Pol ish Carpathians. Mémoires du Muséum Na tional d’Histoire Naturelle, Paris, 170: 343–373.
Birkenmajer, K., 1979. Przewodnik geologiczny po pieniñskim pasie ska³kowym (in Pol ish). Wyd. Geol., Warszawa.
Birkenmajer, K., 1986. Stages of struc tural evo lu tion of the Pieniny Klippen Belt, Carpathians. Studia Geologica Polonica, 88:
7–32.
Birkenmajer, K., 1988. Ex otic Andrusov Ridge: its role in plate-tec - tonic evo lu tion of the units of the Magura Nappe, Krynica Sub - unit, Carpathians. Annales Societatis Geologorum Poloniae, 59:
145–181.
Borys, Z., Cisek, B., Czernicki, J., 1989. Nowe perspektywy poszukiwañ z³ó¿ wêglowodorów w piaskowcach dolnej kredy jednostki skolskiej w Karpatach (in Pol ish). Nafta, 10–12:
142–147.
Bu³a, Z., Habryn, R., Jachowicz-Zdanowska, M., ¯aba, J., 2015.
The Pre cam brian and Lower Pa leo zoic of the Brunovistulicum (east ern part of the Up per Silesian Block, South ern Po land) – the state of the art. Geo log i cal Quar terly, 59 (1): 123–134.
Burtan, J., Cieszkowski, M., Mastella, L., Paul, Z., 1992. Okno tektoniczne Mszany Dolnej (in Pol ish) In: Przewodnik LXIII Zjazdu PTG, Koninki, 17–19 wrzeœnia 1992: 76–80.
Cieszkowski, M., Golonka, J., Krobicki, M., Œl¹czka, A.
Waœkowska-Oliwa, A., Wendorff, M., 2009. Olistolites in the Silesian unit and their re la tion ship with the phases of de vel op - ment of the Silesian ba sin (in Pol ish with Eng lish sum mary).
Kwartalnik AGH Geologia, 35: 13–21.
Curtis, J.B., Kotarba, M.J., Lewan, M.D., Wiêc³aw, D., 2004.
Oil/source rock cor re la tion in the Pol ish Flysch Carpathian and Me so zoic base ment and or ganic fa cies of the Oligocene Menilite Shales: in sights from hy drous py rol y sis ex per i ments.
Or ganic Geo chem is try, 35: 1573–1596.
Decker, H., Perreson, H., 1996. Ter tiary ki ne mat ics in the Al - pine-Carpathian-Pannonian sys tem: links be tween thrust ing, trans form fautling and crustal ex ten sion. EAGE Spe cial Pub li ca - tions, Geo log i cal So ci ety, 5: 17–21.
Dunkl, I., Grasemann, B., Frisch, W. 1998. Ther mal ef fects of ex - hu ma tion of a meta mor phic core com plex on hang ing wall syn-rift sed i ments – an ex am ple from the Rechnitz Win dow, East ern Alps. Tectonophysics, 297: 31–50.
Fodor, L., 1995. From transpression to transtension:
Oligocene-Mio cene struc tural evo lu tion of the Vi enna ba sin and the East-Al pine-West ern Carpathian junc tion. Tectonophysics, 242: 151–182.
Golonka, J., 2007. Tektonika polskich Karpat fliszowych pomiêdzy Bielskiem-Bia³¹ a Nowym Targiem (in Pol ish). Kwartalnik AGH Geologia, 33: 29–38.
Golonka, J., Krobicki, M., Matyszkiewicz, J., Olszewska, B., Œl¹czka, A., S³omka, T., 2005. Geodynamice of ridges and de - vel op ment of car bon ate plat forms within the Outer Carpathian realm in Po land. Slo vak Geo log i cal Mag a zine, 11: 5–16.
Hempel, I., 1955. Bed rock oil Carpathians (in Pol ish with Eng lish sum mary). Przegl¹d Geologiczny, 3: 468–473.
Hufnagel, H., Kuckelkorn, K., Wehner, H., Hildebrand, G., 1981.
In ter pre ta tion des Bohrprofils Vorderriss 1 aufgrund organogeochemischer und geophysikalischer Untersuchungen.
Geologica Bavarica, 81: 123–143.
In ter na tional Com mit tee for Coal and Or ganic Pe trol ogy (ICCP), 1998. The new vitrinite clas si fi ca tion (ICCP Sys tem 1994): Fuel, 77: 349–358.
Ja cob, H., Kuckelkorn, M., Mûller, M., 1982. Inkohlung und Tektonik im Bereich der gefalteten Molasse. Erdöl Kohle, 35:
510–518.
Jugowiec-Nazarkiewicz, M., Jankowski, L., 2001. Nannoplankton biostratigraphy of the ¯egocina marls: an as pect of geo logic set - ting of the Lanckorona-¯egocina Zone (in Pol ish with Eng lish sum mary). Przegl¹d Geologiczny, 49: 1186–1190.
Kêpinska, B., 2006. Ther mal and hy dro ther mal con di tions of the Podhale geo ther mal sys tem. Studia, Rozprawy, Monografie IGSMiE PAN w Krakowie, 135: 1–112.
Konon, A., 2001. Tec ton ics of the Beskid Wyspowy moun tains (Outer Carpathians, Po land). Geo log i cal Quar terly, 45 (2):
179–204.
Kosakowski, P., 2013. 1D mod el ling of hy dro car bon gen er a tion and ex pul sion from Oligocene Menilite source rocks in the San and Stryi rivers re gion (Pol ish and Ukrai nian Carpathians). Geo - log i cal Quar terly, 57 (2): 307–324.
Kosakowski, P., Wiêc³aw, D., Kotarba, M., 2009. Source rock char ac ter is tic of the se lected flysch de pos its in the transfrontier area of the Pol ish Outer Carpathians. Kwartalnik AGH Geologia, 35: 155–190.
Kotarba, M., Nagao, K., 2008. Com po si tion and or i gin of nat u ral gases ac cu mu lated in the Pol ish and Ukrai nian parts of the Carpathian re gion: gas eous hy dro car bons, no ble, gases, car - bon di ox ide and ni tro gen. Chem i cal Ge ol ogy, 255: 426–438.
Kotarba, M.J., Wiêc³¹w, D., Koltun, YV., Marynowski, L., Kuœmierek, J., Dudok, I.V., 2007. Or ganic geo chem i cal study and ge netic cor re la tion of nat u ral gas, oil and Menilite source rocks in the area be tween San and Stryi rivers (Pol ish and Ukrai - nian Carpathians). Or ganic Geo chem is try, 38: 1431–1456.
Kovaè, M., Kral, J., Marton, M., Plasienka, D., Uher, P., 1994. Al - pine up lift his tory of the Cen tral West ern Carpathians: geo - chron ol ogi cal, paleomagnetic, sed i men tary and struc tural data.
Geologica Carpathica, 45: 83–96.
Kruge, M.A., Mastalerz, M., Solecki, A., Stankiewicz, B.A., 1996.
Or ganic geo chem is try and pe trol ogy of oil source rocks, Carpathian overthrust re gion, south east ern Po land – im pli ca - tion for pe tro leum gen er a tion. Or ganic Geo chem is try, 24:
897–912.
Ksi¹¿kiewicz, M., 1972. Budowa geologiczna Polski (in Pol ish).
Tektonika. Wyd. Geol., Warszawa.
Ksi¹¿kiewicz, M., 1977. Tec ton ics of the Carpathians. In: Ge ol ogy of Po land (ed. W. Po¿aryski), Tec ton ics, 4: 476–604. Wyd.
Geol., Warszawa.
Kuckelkorn, K.F., Hiltmann, W., 1992. New ma tu rity in ter pre ta tion of Al pine overthrusting, Ba varia, Ger many. EAPG Spe cial Pub li - ca tion, 2: 177–184.
Kuœmierek, J., 1990. Geodynamics out line of the Cen tral Carpathian Pe tro leum ba sin (in Pol ish with Eng lish sum mary).
Prace Geologiczne, 135: 1–69
Kuœmierek, J., 1995. Evo lu tion and hy dro car bon po ten tial of Pol ish Carpathians (in Pol ish with Eng lish sum mary). Prace Geologiczne, 138: 1–92.
Kuœmierek, J., 2004. Pe tro leum sys tems: pri mary hy dro car bon po - ten tial and pro spec tive re sources of oil and nat u ral gas (in Pol - ish with Eng lish sum mary). Gospodarka Surowcami Mineralnymi, 20: 27–53.
Lewan, M.D., Kotarba, M.J., Curtis, J.B., Wiêc³aw, D., Kosakowski, P., 2006. Oil-gen er a tion ki net ics for or ganic fa - cies Type II and IIS kerogen in the Menilite Shales of the Pol ish Carpathians. Geochimica et Cosmochimica Acta, 70:
3351–3368.
Mählmann, R.F., 1995. The pat tern of diagenesis and meta mor - phism by vitrinite reflectance and illite crystallinity in Mittelbunden and in the Oberhalbstein. Part 1. The re la tion ship to stockwork tec ton ics. Schweizerische Mineralogische und Petrographishe Mitteilungen, 75: 85–122.
Mählmann, R.F., 1996. The pat tern of diagenesis and meta mor - phism by vitrinite reflectance and illite crystallinity in Mittelbunden and in the Oberhalbstein. Part 2. Cor re la tion of coal pet ro graph i cal and of min er al og i cal pa ram e ters.
Schweizerische Mineralogische und Petrographishe Mitteilungen, 76: 23–46.
Mählmann, R.F., 2001. Cor re la tion of very low grade data to cal i - brate a ther mal ma tu rity model in a nappe tec tonic set ting, a case study from the Alps. Tectonophysics, 334: 1–33.
Marko, F., Fodor, L., Kováè, M., 1991. Mio cene strike-slip fault ing and block roration in BrezovskÅ Karpaty Mts. (West ern Carpathians). Mineralia Slovaca, 23: 189–200.
Marynowski, L., Gawêda, A., 2005. Cor re la tion be tween biomarkers and ther mal ma tu rity of the or ganic mat ter from the Paleogene sed i men tary rocks of the Podhale Trough. Min er al - og i cal So ci ety of Po land, Spe cial Pa pers, 25: 329–332.
Matyasik, I., 1994. Geo chem is try of Menilite and Inoceramian Beds in Skole Unit. Nafta-Gaz, 6: 234–244.
Nemèok, M., 1993. Tran si tion from con ver gence to es cape: field ev - i dence from the West Carpathians. Tectonophysics, 217:
117–142.
Nemèok, M., Nemèok, J., Wojtaszek, M., Ludhova, L., Klecker, R.A., Sercombe, W.J., Cieszkowski, M., Paul, Z., Cow ard, M.P., Œl¹czka, A., 2001. Re con struc tion of Cre ta ceous rifts in - cor po rated in the Outer West Carpathian wedge by bal anc ing.
Ma rine and Pe tro leum Ge ol ogy, 18: 39–64.
Newman, J., Newman, N.A., 1982. Reflectance anom a lies in Pike River coals: ev i dence of vari abil ity in vitrinite type with im pli ca - tion for mat u ra tion stud ies and “Suggate rank”. New Zeland Jour nal Ge ol ogy and Geo phys ics, 25: 31–45.
Oszczypko, N., 1992. Magura ba sin de vel op ment in the Up per Cre - ta ceous and Paleogene (in Pol ish with Eng lish sum mary).
Przegl¹d Geologiczny, 40: 397–404.
Oszczypko, N., 2004. The struc tural po si tion and tectonosedi - mentary evo lu tion of the Pol ish Outer Carpathians. Przegl¹d Geologiczny, 52: 780–791.
Oszczypko, N., 2006. Late Ju ras sic–Mio cene evo lu tion of the Outer Carpathian fold-and-thrust belt and its foredeep ba sin (West ern Carpathians, Po land). Geo log i cal Quar terly, 50 (1):
169–194.
Oszczypko, N., Œl¹czka, A., 1985. An at tempt to palinspastic re - con struc tion of Neo gene bas ins in the Carpathian foredeep.
Annales Societatis Geologorum Poloniae, 55: 55–75.
Paul, Z., Ry³ko, W.,Tomaœ, A., 1996. The in flu ence of con sol i dated base ment on flysch dis tri bu tion in the Pol ish West ern Carpathians (in Pol ish with Eng lish sum mary). Przegl¹d Geologiczny, 44: 489–494.
Peszat, C., 1997. Petrographic tex ture and phys i cal prop er ties of thick-bed ded Cergowa sand stones (Fx, Ta) in Grybów unit in Klêczany near Nowy S¹cz (in Pol ish with Eng lish sum mary).
Gospodarka Surowcami Mineralnymi, 15: 137–163.
Poprawa, P., Malata, T., Oszczypko, N., 2002. Tec tonic evo lu tion of sed i men tary bas ins of the Pol ish part of the Outer Carpathians based on the sub si dence anal y sis (in Pol ish with Eng lish sum mary). Przegl¹d Geologiczny, 50: 1092–1108.
Poprawa, P., Malata, T., Pécskay, Z., Banaœ, M., Skulich, J., Paszkowski, M., Kusiak, M., 2004. Geo chron ol ogy of crys tal - line base ment ofthe west ern Outer Carpathians’ sed i ment source ar eas – pre lim i nary data. Prace Specjalne Polskiego Towarzystwa Mineralogicznego, 24: 329–332.
Rantitsch, G., 1992. Reflexionsmessungen an Graptolithen im Silur und Unterdevon der Karnischen Alpen. Jahrbuch der Geologischen Bundesanstalt, 135: 299–316.
Rantitsch, G., 1997. Ther mal his tory of the Carnic Alps (South ern Alps, Aus tria) and its paleogeographic im pli ca tions.
Tectonophysics, 272: 213–232.
Reinhardt, M., 1991. Vitrinite reflectance, illite crystalinity and tec - ton ics: re sults from the North ern Appenines (It aly). Or ganic Geo chem is try, 17: 175–184.
Sachsenhofer, R.F., 1992. Coalification and ther mal his to ries of Ter tiary bas ins in re la tion to late Alpidic evo lu tion of the East ern Alps. Geologische Rundschau, 81: 291–308.
Sachsenhofer, R.F., 2001. Syn- and postcollisional heat flow in the Tertiaty East ern Alps. In ter na tional Jour nal of Earth Sci ences, 90: 579–592.
Schuller, V., 2004. Evo lu tion and geodynamic sig nif i cance of the Up per Cre ta ceous Gosau ba sin in the Apuseni Moun tains (Ro - ma nia). Tübinger Geowissenschaftliche Arbeiten, A 70: 1–122.
Semyrka, G., 2009. Vitrinite reflectance and kerogen types in East - ern Carpathians bore holes (in Pol ish with Eng lish sum mary).
Kwartalnik AGH Geologia, 35: 49–59.
Sikora, W., Borys³awski, A., Cieszkowski, M., Gucik, S., Jasionowicz, J., 1980. Przekrój geologiczny Kraków-Za - kopane (in Pol ish). Wyd. Geol., Warszawa.
Soták, J., Biroò A., Kotulová, J., Rudinec, R., Spišak, J., 1995.
Geo log i cal struc ture of the East Slo vak ba sin base ment in the light of facts and re gional tec tonic con text. Mineralia Slovaca, 27: 1–8.
Soták, J., Pereszlenyi, M., Marschalko, R., Milicka, J., Starek, D., 2001. Sedimentology and hy dro car bon hab i tat of the sub ma - rine-fan de pos its of the Cen tral Carpathian Paleogene ba sin (NE Slovakia). Ma rine and Pe tro leum Ge ol ogy, 18: 87–114.
Sperner, B., Ratschbacher, L., Nemèok, M., 2002. Intreplay be - tween subduction re treat and lat eral ex tru sion: tec tonic of the West ern Carpathians. Tec ton ics, 21: 1–24.
Stach, E., Makowsky, M.T., Teichmuller, M., Tay lor, G.H., Chandra, D., Teichmuller, R., 1982. Stach’s Text book of Coal Pe trol ogy: 77–98. Borntraeger, Berlin.
Œl¹czka, A., 1996. O tworzeniu siê Karpat Zewnêtrznych (in Pol ish).
Sprawozdanie z Posiedzenia Pañstwowej Akademii Umiejêtnoœci, 59: 79–80.
Œrodoñ, J., 2008. Diagenetic his tory of the Podhale flysch ba sin.
Geoturystyka, 2: 45–50.
Œrodoñ, J., Kotarba, M., Biron, A., Such, P., Clauer, N., Wójtowicz, A., 2006. Diagenetic his tory of the Podhale-Orava ba sin and the un der ly ing Tatra sed i men tary struc tural units (West ern Carpathians): ev i dence form XRD and K-Ar of illite-smectite. Clay Min er als, 41: 747–770.
Œwierczewska, A., 2005. The in ter play of ther mal and struc tural his to ries of the Magura Nappe (Outer Carpathians) in Po land and Slovakia. Mineralogia Polonica, 36: 91–144.
Œwierczewska, A., Tokarski, A.K., 1998. De for ma tions bands and the his tory of hold ing in the Magura Nappe West ern Outer Carpathians, Po land. Tectonophysics, 297: 73–90.
Syrek, M., 2009. De gree of coalification dis persed or ganic mat ter in Magura Unit and tec tonic win dows (Outer Carpathians) (in Pol - ish with Eng lish sum mary). Materia³y konferencyjne IV Krakowskiej Konferencji M³odych Uczonych, 17–19 wrzeœnia 2009: 195–202. https://www.researchgate.net/pub li ca - tion/280315286_Stopien_uweglenia_rozproszonego_materialu _organicznego_w_jednostce_magurskiej_i_strefie_okiennej_K arpaty_Zewnetrzne
Tari, G., Horvát, F., 1995. Over view of the Al pine evo lu tion of the Pannonian ba sin. In: Hun gary, Extensional Col lapse of the Al - pine Orogene and Hy dro car bon Pros pects in the Base ment and Ba sin Fill of the West ern Pannonian Ba sin (eds. F. Horvath, G.
Tari and C. Bokor): 7–19, AAPG In ter na tional Con fer ence and Ex hi bi tion, Nice, Guide book to fieldtrip no. 6, Hun gary.
Tokarski, A.K., 1980. Dy nam ics of outer Carpathian Ter tiary oro - gen esis. Pub li ca tions of Institue of Ge og ra phy Pol ish Acad emy of Sci ences, A8: 129–141.
Wag ner, L., Kuckelkorn, K., Hiltmann, W., 1986. Neue Ergebnisse zur alpinen Gebirgsbildung Oberösterreichs aus der Bohrung Oberhofen 1- Stratigraphie, Fazies, Maturität und Tektonik.
Erdöl, Erdgas, Kohle 102: 12–19.
Wag ner, M., 1980. Coal-bear ing sed i ments from the Magura Unit (in Pol ish with Eng lish sum mary). Annales Societatis Geologorum Poloniae, 50: 99–117.
Wag ner, M., 1992. Pet ro log i cal re search of Carpathians coal oc cur - rences as a source for hy dro car bons (in Pol ish with Eng lish sum mary). Gospodarka Surowcami Mineralnymi, 8: 803–817.
Wag ner, M., 2010. Pet ro logic re sults of coal oc cur rences from the Podhale flysch sed i ments (in Pol ish with Eng lish sum mary).
Przegl¹d Górniczy: 116–119.
Wag ner, M., 2011. Pet ro logic stud ies and diagenetic his tory of coaly mat ter in the Podhale flysch sed i ments, South ern Po land.
Annales Societatis Geologorum Poloniae, 81: 173–183.
Wiêc³aw, D., Kotarba, M., Kowalski, A., Koltun, Y., 2012. Or i gin and ma tu rity of oils in the Ukrai nian Carpathians and their Me so - zoic base ment. Geo log i cal Quar terly, 56 (1): 158–168.
Wójcik-Tabol, P., 2006. Or ganic car bon ac cu mu la tion events in the mid-Createcous rocks of the Pieniny Klippen Belt (Pol ish Carpathians) – a pet ro log i cal and geo chem i cal ap proach. Geo - log i cal Quar terly, 50 (4): 419–436.
Wójcik-Tabol, P., 2015. Depositional re dox of the Grybów suc ces - sion (Oligocene, Pol ish Carpathians) in the light of pet ro log i cal and geo chem i cal in di ces. Geo log i cal Quar terly, 59 (4):
603–614.
Zattin, M., Cuman, A., Fantoni, R., Mar tin, S., Scotti, P., Stefani, C., 2006. Cool ing dur ing burial: the ther mal re cord in the sed i - ments of the Do lo mite re gion (Cen tral Alps, It aly).
Tectonophysics, 414: 191–202.
¯elaŸniewicz, A., Aleksandrowski, P., Bu³a, Z., Karnkowski, P.H., Konon, A., Oszczypko, N., Œl¹czka, A., ¯aba, J., ¯ytko, K., 2011. Regionalizacja tektoniczna Polski (in Pol ish). Komitet Nauk Geologicznych PAN, Wroc³aw.
¯ytko, K., 1999. Cor re la tion of the main struc tural units of the West - ern and East ern Carpathians (in Pol ish with Eng lish sum mary).
Prace Pañstwowego Instytutu Geologicznego, 168: 25–44.
¯ytko, K., Malata, T., 2001. Palaeogeographic po si tion of the Obidowa-Slopnice unit in the Outer Carpathian ba sin (SE Po - land) (in Pol ish with Eng lish sum mary). Przegl¹d Geologiczny, 49: 425–430.
PN-ISO-11760:2007/DIS 11760 – Clas si fi ca tion of Coals.
ISO 7404-5:2009 – Part 5 – Method of de ter min ing mi cro scop i cally the reflectance of vitrinite.
