Annales Societatis Geologorum Poloniae (2011), vol. 81: 173–183.

PETRO LOG IC STUDIES AND DIAGENETIC HISTORY OF COALY MATTER IN THE PODHALE FLYSCH SEDI MENTS, SOUTH ERN

Mar ian WAG NER

AGH Uni ver sity of Sci ence and Technol ogy, Fac ulty of Ge ol ogy, Geo phys ics and En vi ron men tal Pro tec tion, Al. Mickiewicza 30, 30-059 Kraków, Poland, e-mail:wagner@ge ol.agh.edu.pl

Wagner, M., 2011. Pet ro logic stud ies of diagenetic his tory of coaly matter in the Podhale Flysch sed i ments, south ern Po land. Annales Societatis Geologorum Poloniae, 81: 173–183.

Ab stract: Common occur rences of terrigenic or ganic mat ter (both dis semi nated and ac cu mulated in lay ers) in sed i mentary rocks were ob served. The flysch sed i ments in the Podhale Trough and in other parts of the Carpathians are in ad e quately re cog nised from coal pet ro logic point of view. Studies were car ried out in the east ern (2008) and west ern part (2009) of the Podhale Trough. Sam ples were col lected from the ex po sures. Petrographic studies in cluded mi cro scopic ob ser va tions of pol ished sec tions as well as mean random reflectance measure ments of vitrinite (colotellinite) were done. In the Podhale Flysch, coalified or ganic mat ter is rep re sented mostly by vitrinite and, in mi cro scopic scale, mainly by collotellinite. The com mon oc currence of coaly matter is revealed. It is well–visi ble in sandstones and mudstones, usually as the bed ding planes. The amounts of coaly matter in clay miner als and car bon ates are small. Organic matter hosted in the Podhale Flysch strata rep resents diver si fied coalification ranks measured as ran dom reflectance of vitrinite (colotellinite), which falls into the range from 0.49 to 1.00%. Such val ues are typ i cal for low- to me dium ranks of bi tu minous coal. Mea sure ments of reflectance pro vided new data suit able for eval u a tion of ther mal history of rocks in the Podhale Trough. The changes of vitrinite (colotellinite) mean reflectance of organic matter from the Podhale Flysch are rele vant to the contents of crys talline illite – the recently applied geothermometer of diagenetic (katagenetic) transfor ma tions of clay miner als. If the thermal palaeogra- dient is known, ran dom changes of reflectance of vitrinite can be used for es ti mations of both the max i mum thick ness of the Podhale Flysch dur ing de po sition and its later amount of ero sion. It ap pears that esti mation of ma- x i mum thickness of the Podhale Flysch (i.e., depositional thick ness af ter com pac tion) and the amount of ero sion are al most identi cal with the esti ma tions based upon the illitization of clay miner als.

Key words: terrigenic or ganic mat ter, ran dom reflectance of vitrininite, the Podhale Flysch, Po land.

Manu script re ceived 8 June 2011, ac cepted 3 November 2011

INTRODUCTION

Com mon occur rence of terrigenic or ganic matter (both The flysch sedi m ents in the Podhale Trough and in dis sem i nated and ac cu mu lated in lay ers) in sed i men tary other parts of the Carpathians, although suffi cie ntly re cog- rocks togethe r with the de velop m ent of modern, fast petro- nised from the geolog i cal point of view, reveal many con - graphic methods of coalification rank measure m ents result trover sie s and uncertaintities concern ing their geotectonic in wide appli cati on of such petrographic obser va ti ons and posi ti on. Studies of vitrinite coalification provide new in- mea sure ments in var i ous re search pro jects, e.g. of geotecto- ter pre ta tive op por tu ni ties, hence, rocks from the East ern nic his tory of par tic u lar re gions. and West ern Carpathians, from the Tatra Mts., from the In the Podhale Flysch sedi m ents, coalified organic mat- Pieniny Klippen Belt and from the Podhale Trough are re- ter is rep re sented mostly by vitrinite. Mea sure ments of vitri- cently in ten sively in ves ti gated. The lat ter de pos its are par - nite mean reflectance (Ro) en able the sci en tists to solve many ticu lar ly useful due to suggest ed low degree of their tec - tec tonic problem s in both the orogenic belts and the plat- tonic trans for ma tion (de spite their sig nif i cant thick ness – forms as this pa ram e ter car ries in for ma tion on coalification several thousands of metres) and the posi ti on betwee n the as a functi on of sedi m ent burial within the Earth crust, coeval two young- Alpine orogens: the Pieniny Klippen Belt and with depo si ti on and with later orogenic ac tivit y. the Tatra Mts. 174 M. WAGNER

Fig. 1. Geo log i cal sketch map of the Podhale Trough with lithostra tig ra phy of the Podhale Palaeogene Flysch and gen eral cross-sec tion (A – A ) through the Podhale Trough (af ter Cho- waniec, 1989; Chowaniec & Kêpiñska, 2003. In: Krobicki & Go- lonka, 2008; slightly modi fied)

Fig. 3. Lithostratigraphic col umn of the Podhale Flysch in the impor tant parts of the Podhale Trough (af ter Geld, 2000, also Krobicki & Golonka, 2008, modi fied)

In the northwest ern part of the Podhale region. i.e., in the Orawa porti on of the Nowy Targ–Orawa Trough a part Fig. 2. Lithostratigraphic cross sec tion (A – A, Fig. 1) of the of the Podhale Flysch succes sion is uncon form ably covered west ern part of the Podhale Trough (af ter Gedl, 2000. In: Krobicki by the Neogene (Miocene -Pliocene ) intramontane molas - & Golonka, 2008). PKB – Pieniny Klippen Belt ses. This suite com prises huge allu vial fans, several hun - dreds of metres thick (maxi m um thickness – 1,300 m), which have been de pos ited since the Early Mio cene, af ter the upli ft of the Tatra Mas sif and the folding of the Podhale Even the pre lim i nary re sults re veal com pli cated diage- Flysch. Their char acter istic feature is the pres ence of coaly netic his tory of the Podhale Flysch refle cted in signif i cant matter (Ko³con & Wagner, 1991). dif fer ences in coalification of con tained or ganic matter. The Podhale Flysch include s four lithostratigraphic units (Gedl, 2000; Ry³ko, 2004): the Szaflary beds, the Za- kopane beds, the Chocho³ów beds and the Ostrysz beds. GEO LOG I CAL SET TING The oldest unit – the Szaflary beds (Fig. 3) – occurs in OF THE PODHALE FLYSCH the northern part of the Podhale Trough but it is absent from the southern part, at the contac t with the Eocene limestone s. The Palaeogene sedi m ents of the Podhale Trough are These are mostly sandstone s in the lower part (about 300 m divided into two lithostratigraphic units. The older unit thick), sandstone s and shales (about 200 m thick) or sandsto- comprises shal low-ma rine car bon ates tra di tion ally named nes and conglom erate s in the upper part with the dom inance ”the Num muli tic Eocene”. It is fol lowed by the younger, of mudstones and claystones over sandstone s (Fig. 4). The flysch unit named ”the Podhale Flysch” (see, e.g., Watycha, sandstone s are fine-grained and thin-bedded (0.1–3.0 m). In 1959; Mastella, 1975). the upper part of the succes sion, among claystones, the si lici- The imm edi ate base ment of the Podhale Flysch con sists fied shales of menilite type oc cur. of Eocene car bon ates which are in tec tonic con tact with the Both the conglom erate s and the sandstone s of the High–Tatric and Sub-Tatric serie s, and which form the Szaflary beds contai n limestone grains derive d from the northern margin of the Tatra Mts. (Fig. 1, 2). Pieniny Klippen Belt whereas the flysch strata in clude full The Eocene carbon ate s of total thickness about 150 m tur bid ity se quences iden ti fied as prox i mal flysch. Com mon are exposed only along the northern margin of the Tatra com ponent of the Szaflary beds is plant detri tus and even a Mts. whereas the youn ger, Oligocene flysch strata, which few-centim etres-thick coal layers. fill the Podhale Trough crop out at num erous sites betwee n Scarce foraminifers iden tified in the Szaflary beds point the Tatra Mts. and the Pieniny Klippen Belt. out to Late Eocene age, but dinocysts observe d in the youn - COALY MAT TER IN THE PODHALE FLYSCH 175

Fig. 4. Sedimentological fea tures of the Podhale Flysch. A – Thin-bed ded Szaflary beds (Nowe Bystre vil lage); B – Folded Szaflary beds in the con tact zone with the Pieniny Klippen Belt (Szaflary vil lage); C – Lower Chocho³ów beds in the Bia³y Dunajec River (near Bia³y Dunajec vil lage); D – Break-thrust of Brzegi beds (Jurgów vil lage); E – Thin-bed ded Up per Chocho³ów beds (Kojsówka vil lage); F – black shales of beds (Zakopane-Olcza vil lage) 176 M. WAGNER

ger part in di cate the Early Oligocene (Watycha, 1976; Gedl, from 0 to 10°). Only in nar row zones of the Pieniny Klippen 2000). Belt and, lo cally, close to the edge of the Tatra Mas sif, the The Zakopane beds, known from the southern and Podhale Flysch strata do dip at high angle (even verti cally), northern parts of the Podhale Trough (Figs 1–3), are dom i- with some overthrusting from the south (close to the Tatra nated by clayey shales. Basing on the frequency of shale oc- Mts.) and from the north (border zone of the Pieniny Klip- currence , the lower, shale-dom inate d and the upper, pen Belt). sandstone-shale-dom inate d parts were disti nguishe d, of total The tectoni c pat tern of the Podhale Synclinorium in- thickness up to 300 m. The lower part include s dark (Fig. 4), cludes par allel zones of somewhat dif fer ent struc tures. clayey and cal car eous shales with rare in ter cala tions of fine- From the north these are: grained sandstone s (up to 10 centi metres thick), local ly grad- – the contac t zone with the Pieniny Klippen Belt – this ing into dolomites. The upper part com prises rhythm ical ly is a tectonic con tact, the Numm u litic Eocene strata are ab - interbedded, fine-grained sandstone s and dark-grey, clayey sent, dips of flysch beds are steep with com mon overthrusts shales with rare do lo mite lenses. and overturns caused by num erous faults. The width of this In the Zakopane beds, typ ical turbidites are scarce and zone is vari able, usu ally a few kilo metres, occur in strata repre sent ing the upper Bouma se quences. – the bor der flexure of the Pieniny Klippen Belt, 450– Coaly de tri tus is less abundant in com pari son to the Szaflary 600 m wide, with steep dips of flysch beds and num erous beds. The thickness of the Zakopane beds is esti mated as faults downthrowing the rocks towards the south, 300– 500 m (loc. cit). The foraminiferal as semblage in di - – the zone of low dip angles which, in the eastern part, cates a Late Eocene-Early Oligocene age and it is sim ilar to is a wide brachyanticline cut by num erous, small faults, fauna of the Krosno beds in the Outer Carpathians, whereas – the axial zone with low dip angles and num erous, lo - the dinocysts point out to the Early Oligocene. cal folds, The Chocho³ów beds conform ably rest upon the Zako- More over, the border zone with the Tatra Massif can be pane beds. Two mem bers were disti nguishe d: the lower one dis tin guished, of tec tonic fea tures sim i lar to those bor der ing (800–1,000 m thick) com posed of sandstone s and conglom - the Pieniny Klippen Belt, i.e. vari able dip angles , northward erate s, and the upper one (650 m thick) com posed of shales dipping, micro-overt hrusts and num erous, small faults and sandstone s, and named “the Brzegi beds” (Fig. 4). The downthrowing the rocks to the north. boundary betwee n the Chocho³ów and Zakopane beds is Accord ing to Mastella (1975), the princi pal tectoni c pat - conven ti onall y placed where thick sandstone lay ers appear tern of the Podhale Synclinorium origi nate s from the Savian in the top por tion of the Zakopane beds. The Chocho³ów phase of the Alpine orogeny . It was control led by verti cal beds fill the centra l part of the Podhale Trough (Figs 1, 2). movem ents of base ment blocks and the result ing two-stage Their li thol ogy is dom inate d by fine- and medium -grained up lift of the Tatra Mas sif and the Pieniny Klippen Belt. At sand stones with rare con glom er ates, the lat ter con tain ing the first stage, the ver tical move ments of base ment blocks de tri tal ma te rial eroded from the Tatric sed i men tary se ries. took place togethe r with the form ati on of paral lel dislo ca ti ons The upper part (i.e., the Brzegi beds) comprises shales and whereas at the sec ond stage the merid io nal faults were sandstone s with thin lay ers of greenish mudstones and clay- formed. The up lift of the Tatra Mas sif was most in ten sive in stones, someti mes highly cal care ous. Sandstone s of the the southern part of the massif in Slovakia, along the eastern Chocho³ów beds are thin – or medium -bedded, with graded segm ent of the Tatra Fault, whereas along the northern bor- bedding. The Chocho³ów beds are cat ego riz ed as so-called der of the Tatras the ver tical move ments were less pro - nor mal flysch orig i nat ing from den sity cur rents (Roniewicz, nounced. In the northern part of the Podhale Trough, the up- 1979). The age of the Chocho³ów beds is palaeontologically lift of the Pieniny Klippen Belt was very in ten sive, as re - dated as the Early Oligocene (Dudziak, 1986). vealed by the contac t zone and the border flexure. The youngest mem ber of the Podhale Flysch is named the Ostrysz beds. Li thol ogy is dom inate d by sandstone s. Poor expo sures cause the general lack of palaeontological METH ODS AND MA TE RI ALS TEST docu m enta ti on known only from the vi cinit y of the Ostrysz Hill (Fig. 1). From the lithological point of view the Ostrysz De tailed field stud ies were car ried out in the east ern beds can be re garded as local , sandstone -dom inate d vari ety (2008) and western part (2009) of the Podhale Trough, from of the Chocho³ów beds. The thickness of this mem ber rea- the Czarny Dunajec River to wards the east ern state bor der, ches 300 m but its topm ost part was presum ably rem oved by and from the main Pieniny Fault close to Szaflary vil lage erosion (Watycha, 1976). The age of the Ostrysz beds was (Figs 1, 7) to the tectoni c edge of the Tatra Mts. (the Cho- de ter mined as the Early/Late Oligocene (Fig. 3). In Slo- cho³owska and the Bia³y Valleys). Samples were collected vakia, where this topm ost part was preserve d, the age corre - from the ex po sures. Ad di tion ally, the ar chi val sam ples were sponds to the Late Oligocene break (Gross et al., 1980). analy sed, taken from expo sures of the Zakopane beds in The tecton ics of the Podhale Flysch disti nctly differs Guba³ówka and Butorowy Hill near Zakopane town. from the other parts of the Carpathian orogen. These sedi - Petrographic stud ies in cluded mi cro scopic ob ser va tions ments occupy a vast synclinorium on both sides of the Tatra of polishe d sec tions under the refle cted light (standard, Mas sif. In the Pol ish part (i.e. in the Podhale area) their tec- white and flu o res cent, blue) as well as mean ran dom reflec- tonic pat tern is sim ple. The sedi m ents rest on site and form tance measure ments of vitrinite (colotellinite) in accor dance an asym metric synclinorium of steeply dipping northern with the ICCP (In ter na tional Com mit tee for Coal and Or- limb. General dip angle is low (up to 15°, in centra l part ganic Pe trol ogy) re quire ments. COALY MAT TER IN THE PODHALE FLYSCH 177

RE SULTS Among of disperse d coaly matter in these rocks, vitri- nite forms two va ri et ies: dark (vitrinite A) and light (vitri- Forms of oc cur rence and petrog ra phy of coaly mat ter nite B). Av er age size of iso metric vitrinite grains in dis sem- Even very general obser va ti ons of the Podhale Flysch inate d coaly matter falls into the range from 5 to 30 µm; al - sed im ents re veal the comm on occur rence of coaly matter. It though, as menti oned above, large (up to 0.3 mm), elon - is well visi ble in sandstone s and mudstones, usuall y at the gated, poorly rounded or angu lar grains of colotellinite were bedding planes. In claystones and carbon ate s the amounts noti ced in sandstone s. of coaly matter are lower. Taking into ac count the forms of occur rence and the Vitrinite reflectograms size of par ticles, the fol low ing types were dis tin guished (Fig. 5): Vitrinite reflectograms of rocks from the Podhale – coal laminae of vari able thick nesses (from a frac tion Flysch show two differ ent peaks (marked as Ro I and Ro II) of a milli metre to about 5 cm, but 0.1–1.0 mm, in aver age); within the range of val ues typ ical for vitrinite. Both are – dis semi nated coal detri tus of vari able size (fine and shifted towards the higher val ues with the increa sing coali- medium -grained), encoun ter ed as dark lenses or streaks, fication of or ganic matter. These are: mainly at the bedding planes of fine-grained sedi m ents – Ro I peak: for low est coalification reflectance val ues (plant debris). It is ac com panied by fine musco vit e flakes. are from 0.38 to 0.44%, with the increa sing coalification In claystones and carbon ate s the coal detri tus is dis sem i- peak values shifted to 0.49% for medium rank and to 0.88% nated in the layers as an ac ces sory compo nent. for the highest rank, Ac cu mula tions of coaly mat ter are mostly thin, elon - – Ro II peak: for low est coalification reflectance val ues gated lenses of coal. Such forms were observe d mostly in are from 0.43 to 0.53%, for medium rank of coal these shift thin-bedded sandstone s and mudstones with disti nct, flat or to 0.57% and to 0.98% for the highest rank. cross-lam i na tion. Some times, ac cu mu la tion of laminae (15– The main peak of colotellinite reflectogram marked as 45 vol.%) perm its to include such sedi m ents to coaly rocks. RoII dom inate s the recorded plots. Measured total values In the expo sures such rocks are eas ily identi fiable due to fall into the range from 0.49 to 1.00% (Table 1). dark-grey color. Micro scopic stud ies re vealed that these peak val ues re - Both the lay ers and lenses of coaly matter are composed sult ex clu sively from the pres ence of dif fer ent colotellinite of vitrinite. This maceral is black, with black streak and phases. glassy luster. Its typi cal fea tures are dense con trac tion cracks, The first peak of ran dom reflectance (Ro I) undoubt edly which result in cube cleavage. Un der the micro scope , the belongs to the so– called “dark vitrinite”. This phase forms prin ci pal compo nent of vitrinite lenses is colotellinite (colli- thin laminae and fine lenses. In the reflectograms record ed nite), which forms two va ri et ies: colotellinite of typ ical op ti - at the scale compa ra ble with the stan dard de vi ation (DRo = cal proper ti es (vitrinite A, for exam ple Fig. 6B–D) and 0.03%), the Ro I peak forms an isolat ed maxi m um shifted darker colotellinite (vitrinite B – Fig. 6F) of some what to wards lower reflectance whereas at the stan dard re cord lower mean reflectance, which forms ex tended, thin lenses. (DRo = 0.05 %, i.e. half stage Ro) the maxi m um does not ap- Both va ri et ies show dis tinctly dif fer ent reflectance. In dar- pear but causes neg ative skew ness. ker laminae ir reg u lar, mi cro scopic-size net work of lighter This peak is al ways lower by 0.06-0.10%, in aver age, va ri ety was ob served. from the main maxi m um recorded in the abso lut e scale. The Rare compo nent of such vitrinite ag gre gates is tellinite, presence of both peaks re flects petrographic diver sit y of al most al ways im preg nated with resinite or bituminite (Fig. vitrinite and re sults from the oc cur rence of liptinites within 6A), fusinite (Fig. 6E) and clay miner als . the dark vitrinite, pre sumably with resinite or bituminite, A typical ac compa ny ing mineral in coal laminae is py- which form sub mi cro scopic mix ture im preg nate colotelli- rite, usuall y observe d as framboids and distri buted as more nite. Such ori gin of dark vitrinite was proposed by Newman or less dis tinct streaks in colotellinite (Fig. 6A–D, F). Lo - and Newman (1982). Addi ti onall y, the pres ence of bitumi- cally, pyrite oc cu pies the in ter nal parts of tellinite cells nite seems to be indi cat ed by large amounts of framboidal and/or scarce microfossils. Apart from pyrite , fine crystal s py rite within the colotellinite, which points out to re duc ing of covel lite and bornite were observe d. depositional envi ron m ent. The ori gin of the Podhale Flysch The dis sem i nated coaly mat ter en coun tered in claysto- strongly fa cil itated the for mation of dark telocollinite as nes and sandy mudstones is a coaly detri tus of dom inat ing these sedi m ents were de posit ed in the shelf zone, within the <0.1 mm fracti on with rare larger grains, up to 0.3 mm range of so – called nor mal shales of the euxinic envi ron - across. Larger ac cu mu la tions of coal de tri tus were typ i cally ment (Morris, 1979). observe d in dark-grey, coaly sandstone s and mudstones as Main peak of colotellinite reflectogram marked as RoII well as in some claystones where they form coal laminae in - dom inate s in the recorded plots. Some sam ples show posi - ter calated with clayey laminae. Such mudstones and clay- tive skewness of this peak, which result s from the presence stones re veal flat lam i na tion orig i nat ing from sed i men ta tion of limited ar eas of colotellinite of some what higher of densit y flows in the dis tal part of abyssal plane. reflectance (up to 0.05%) surround ing framboidal pyrit e ag- The dissem inate d coaly matter is com posed mostly of gre gates. Such variabil ity can be ne glected in fi nal in ter pre - vitrinite (colotellinite) and inertinite (inertodetrinite). Rare ta tion. com ponents are larger fragm ents of fusinite, funginite and Anal ysis of dif fer ences be tween the record ed peaks of resinite. mode rate reflectance leads to the con clu sion that dark 178 M. WAGNER

Ta ble 1 vitrinite peak should be suc cessfull y treated globall y in RoII peak from final evalu a ti on of this param eter in the studied Char ac ter is tic fea tures of more im por tant reflectograms samples (Ta ble 1). The dif fer ence in re sults var ies from from the Podhale Flysch strata – recorded peaks of random 0.03 to 0.07%, with aver age value of 0.05%. vitrinite reflectance. Stage I (2008) and Stage II (2009) The precise de ter mina tion of vitrinite reflectance in

o sam ples from the Podhale Flysch is parti cu lar ly im portant R total due to gener all y low and medium ranks of organic matter , (RoI + Range stdv Sample Location n RoII) [%] [%] which, ac cord ing to re cent prin ci ples, is cat e go rized as bi tu - [%] minous coal D and C (see ISO 11760:2002) or, al ter na- T-13 Trybsz 0.51 0.42–0.64 0.0338 104 tively, as para- and orthobituminous coal (see ECE-UN/EN- BT-11 Trybsz-Bia³ka 0.55 0.48–0.63 0.02 128 ERGY 50:2002). Includ ing the dark vitrinite into the evalu - a tions, the re sult ing mean vitrinite reflectances of stud ied BT-1 Bia³ka-Budzowie 0.67 0.60–0.81 0.0399 126 coals and dissem inate d organic matter fall into the range BD-3 Bia³y Dunajec 3 0.55 0.43–0.66 0.0315 95 from 0.49-0.50 to 1.00 % (Ta ble 1). Sim ple identi fica ti on BN-4/2 Bia³y Dunajec 2 0.56 0.41–0.66 0.0294 100 feature s indi cat e that the rank of or ganic matter in the Pod- BD-102 Bia³y Dunajec 1 0.52 0.41–0.64 0.0192 95 hale Flysch corre sponds to bitu m inous coal. Moreover, P-5a 1 0.61 0.52–0.68 0.0216 90 mean reflectance val ues for or ganic matter from the Sub- P-6/2 Poronin 2 0.64 0.53–0.75 0.0243 115 Tatric Se ries (Poprawa et al., 2004) and the Pieniny Klippen MS-24 £apsze Wy¿ne 0.58 0.52–0.68 0.0136 90 Belt (Wagner, 1996), togethe r with those from the Podhale Z-1 0.55 0.42–0.69 0.0323 115 Flysch, seem to re flect a se quence of geotectonic events. However, it is worthy to note that al though nat ural Z-1-1 Zakopane Olcza 0.56 0.46–0.66 0.025 100 boundari es are only rarely sharp, the form al approach to all Z-1-2 0.56 0.45–0.68 0.0255 90 geolog i cal boundari es (includ ing the coal rank) is an im por- J-3 0.63 0.52–0.74 0.0347 105 Jurgów tant and nec es sary tool in cat e go ri za tion of phe nom ena, J-3/1 0.81 0.74–0.88 0.0138 70 which is useful in gener a ti on of coher ent schemes in nature . B-1 Brzegi-Kucówka 0.73 0.62–0.87 0.0425 90 B-3 Brzegi 0.75 0.64–0.87 0.0415 90 M-8a/1 Palenica Pañszcz. 0.77 0.64–0.87 0.0228 90 DIS CUS SION AND CONLUSIONS M-8 0.79 0.68–0.90 0.0252 70 Regional changes in vitrinite coalification rank MG-10a 0.93 0.88–1.04 0.0255 80 Or ganic matter hosted in the Podhale Flysch strata re - MG-9 Ma³e Ciche 0.95 0.88–1.04 0.0189 75 veals di ver sified coalification ranks measured as mean ref- MG-11a 1 0.92–1.16 0.0208 100 lectance of vitrinite (colotellinite), which falls into the range L-13a Lichejówka 0.77 0.64–0.92 0.2225 150 from 0.49 to 1.00%. Such values are typi cal of low- to me- Ker-1 Butorowy Wierch 0.57 0.46–0.60 0.0305 100 dium ranks of bi tum inous coal. Choch 1 0.51 0.41–0.64 0.0234 100 The coalification pat tern re corded in structural map Chocho³ów Choch 2 0.52 0.47–0.61 0.0176 100 clearly demon strates the in crease of coalification from the W-1 0.57 0.51–0.68 0.0442 90 northwest (Chocho³ów area – sam ples marked as K and Ch Witów W-5 0.55 0.50–0.69 0.07 90 – Ta ble 1; Fig. 7) to wards the south east (Ma³e Ciche area – sam ples marked as MC). More over, coalification does not Koj 1/1 Kojsówka 0.66 0.56–0.76 0.0514 80 depend on strati gra phy (Fig. 7). The best-recog nise d area Chocho³owska SW-4 0.55 0.47–0.68 0.05 80 Valley (con sid er ing the sam pling den sity) is lo cated be tween Bia³y Dunajec (BD), Bia³ka Tatrzañska (BT), Ma³e Ciche and Bi 1 Bia³y Valley 0.72 0.63–0.80 0.0045 85 Jurgów (J) village s, where regu lar and signif i cant changes R-4 Ratu³ów 0.54 0.55–0.62 0.036 80 in mean reflectance were observe d from 0.51 to 1.00% (the M-1 Ratu³ów-Mulice 0.58 0.51–0.67 0.0372 100 latter found in the Ma³e Ciche area). NB-1 Stare Bystre 0.49 0.46–0.51 0.0375 85 Such a patter n clearly points out to the highest parts of NB-2 Nowe Bystre 0.54 0.49–0.64 0.0322 100 the Tatra Mas sif, i.e. towards the £omnica (Lomnicky štit) A-2 Noski 0.6 0.51–0.72 0.0472 100 and Kie¿marski peaks (Kežmarsky štit) where, presum ably, OW Opalony Wierch 0.61 0.50–0.66 0.03 100 the highest am pli tudes of verti cal movem ents have oc - St-1 Z¹b - Stochy 0.6 0.51–0.68 0.0467 100 curred. The low est val ues of mean reflectance Ro in the organic SG-1 Skrzypne Grn 0.53 0.49–0.60 0.0398 100 matter from the Podhale Flysch (about 0.5%) were found D-2 Dzianisz 0.57 0.46–0.68 0.0547 100 close to the boundary with the Pieniny Klippen Belt and in o R to tal = RI+RII– random vitrinite reflectance includ ing the dark vitrinite; the vi cinit y of Chocho³ów. Range – measur ing range of ran dom vitrinite reflectance; n – quantity of mea sure ments; stdv – stan dard de vi a tion Val ues of mean reflectance of vitrinite from the north - ern part of the Podhale Trough differ deci sive ly from those measured in the Pieniny Klippen Belt: about 0.93-0.95% in the Aalenian and Bajocian sed im ents from the Szlachtowa and the Czorsztyn form ati ons (the Skrzypne Form ati on), COALY MAT TER IN THE PODHALE FLYSCH 179

Fig. 5. Types of morpho log i cal forms of coaly matter of the Podhale Flysch sed i ments: A – coaly de tri tus laminae (Lower Chocho³ów beds from Chocho³ów vil lage); B – coal laminae from coaly tis sue of fossil wood (Szaflary beds, Trybsz vil lage); C – coalbed from Up per Chocho³ów beds (Kojsówka vil lage); D – coal laminae with ex ter nal moulds of bark and roots of coaly wood ( Szaflary beds, M³yn vil - lage); E – dispersed or ganic mat ter (de tri tus) near nat u ral moulds of flute and cres cent marks (Ratu³ów vil lage) 180 M. WAGNER

Fig. 6. Micro pho to graphs of coal laminae and coal frag ments (pieces) from the Podhale Flysch: A – tellinite impreg nated of gelinite (sam ple MG-9; B – tellinite (sam ple R-4); C – ir reg u lar lenses of telocollinite in sand stones from Brzegi area (samples B-1, B-3); D – telocollinite impreg nated on py rite in coal piece (sample BD-3); E – fusinite and semifusinite in sand stone from the Chocho³owska Val ley area (sam ple SW-3); F – Framboidal py rite in coal piece (sam ple Z-1). All reflected light, oil im mersion COALY MAT TER IN THE PODHALE FLYSCH 181

Fig. 8. Map of illite diagenetic changes in clayey shales, K-Ar Fig. 7. Sketch-map of changes in mean random reflectance of datings of illite-smectite in bentonites and fission tracks of apa tite vitrinite (colotellinite) of coal and coaly matter from the Podhale in the Podhale Trough (af ter Œrodoñ 2008, mod i fied). 1– isolines Flysch. 1 – samples; 2 – isolines of total random re flectivity (RoI + of illitization degree (%S); 2 – lines mark the limit of kaolinite, RoII) – spac ing 0.05% (RoI + RoII); 3 – border of the Tatra Mts which dis ap pears due to diagenesis; 3 – bor der of the Tatra Mts; 4 and the Pieniny Klippen Belt; 4 – state bound ary – state bound ary of Poland; 5 – re sults of K-Ar datings from bentonites (Ma) and 1.00 to 1.05% in other succes sions from the Pieniny in the Podhale Trough are di versi fie d. Basing upon the re- Mts. (unpub li shed data). More over, these values differ also sults of litho logi c and tectogenetic studies proposed re cent from those found in sedi m ents from the High- and Sub- thickness of the southern part of Podhale Flysch to be about Tatric serie s (from 0.90 to 1.80%; Poprawa et al., 2004). 4 km. Watycha (1968) found somewhat over 3 kilom etres The changes of vitrinite (colotellinite) mean reflectance for the same part of the flysch suc ces sion whereas Mastella of organic matter from the Podhale Flysch are consis tent and Mizerski (1978) esti mated the thickness in the south- with the con tents of crys tal line illite – the re cently ap plied west ern part of the flysch as 2.2 km. Studies of Kêpiñska geothermometer of diagenetic (katagenetic) trans for mations (2006) reveal ed that the thickness of flysch sedi m ents in the of clay miner als (Fig. 8). centra l part of the Podhale Trough (Poronin area) might This map shows disti nct, increa sing trend of burial tem - have been 4–5 km at the amount of erosion of 2–3 kilome- pera ture s of sedi m ents towards the southeas tern part of the tres, whereas erosion in the vi cinit y of Zakopane amoun- Podhale area. The K-Ar datings of maxi m um burial (from ted to ca. 4 km and in Chocho³ów to 1.3–1.5 km. Accord ing 15.8 to 18.6 Ma) enable s the author to corre lat e this proces s to Œrodoñ (2008), at the therm al palaeogradient close to the with the Savic phase of Alpine orogeny (Œrodoñ, 2006, recent (?) value (21±2°C/km), depositional thickness of 2008). flysch in the western part of the Podhale area reached 5– Measure ments of mean reflectance pro vided new data 6 km whereas the amount of erosion was 3.1–3.6 km (Fig. 8). suit able for eval ua ti on of therm al history of rocks in the However, Kêpiñska (2006) studied Palaeogene sedi - Podhale Trough. Con sid er ing the world lit er a ture deal ing ments and found that therm al palaeogradient dur ing depo si - with the influ ence of geolog i cal factors on coalification of tion of the Podhale Flysch was higher (mean: 30-40°C/km) organic matter , the opinion of Sweeney and Burnham than the recent val ues. As the heat source was placed in the (1990) must be taken into account that dur ing coalification base ment rocks of the Tatra suc ces sions, it can be as sumed period of about 10 Ma the maxi m um burial tem pera ture can that the palaeogradient was rel atively con stant be fore the be es tim ated at about 90°C for vitrinite mean reflectance Savic phase of Al pine orogeny (Oligocene/Miocene ). If the 0.49–0.51% and about 140°C for vitrinite mean reflectance subsi dence was the only im portant burial mecha nism (and, 1.00%. Sim i lar tem per a tures can be ob tained from di a grams si mul ta neously, the only fac tor de ter min ing the ob served after Bostick (1979): 90°C for Ro = 0.50% and 155–160°C coalification of organic matter ), the burial depth in the for Ro = 1.00%. Accord ing to the IGCP scheme, also the northwestern part of the Podhale Trough (Chocho³ów area) overall pressure during coalification can be esti mated: for should vary from about 3.2 km (at ther mal palaeogradient lig nite-bi tu mi nous coal tran si tion (Ro = 0.50%) pressure 30°C/km) to 2.7 km (at ther mal palaeogradient 40°C/km) can be from 107 to 108 hPa whereas for bitu m inous D/bi tu- and the total thickness of flysch should be about 2.8 km mi nous C tran si tion (Ro = 1.00%) the pressure might have higher (i.e., recent thickness of the Podhale Flysch se - amounted up to 30×1010 hPa. quence). In the southwest ern part of the trough (Jurgów, If the ther mal palaeogradient is known, these values can Ma³e Ciche ar eas), at the mean reflectance about 1.00% be used for esti mati ons of both the maxi m um thicknesse s of (which cor re sponds to max i mum burial tem per a ture of 155– the Podhale Flysch during depo si ti on and its later amount of 160°C), the burial depth should be about 5 km (therm al erosion. Esti mati ons of the thickness of flysch suc ces sions palaeogradient 30°C/km) or 4 km (therm al palaeogradient 182 M. WAGNER

40°C/km), and maxi m um thickness of flysch strata might tional Con gress of Car bon if er ous Stra tig ra phy and Ge ol ogy, have been 6–7 km (recent thickness of flysch about 2.2 km, Ur bana, Il li nois. p. 24. af ter Mastella & Mizerski, 1978). Chowaniec, J., 1989. Hydrogeologiczne warunki zasilania i It appears that esti mati on of the maxi m um thickness of przep³ywu wód podziemnych w utworach trzeciorzêdowych the Podhale Flysch strata (i.e., depositional thickness after Podhala miêdzy Zakopanem a Bia³ym Dunajcem. (In Polish). Unpub lished Ph.D The sis. Centralne Archiwum Geologiczne com pacti on) and the amount of erosion, both based upon the PIG, Warszawa: 1–144. mean reflectance of colotellinite, are alm ost iden tical with Chowaniec, J. & Kêpiñska, B., 2003. Podhale geo ther mal sys tem the es tima tion s based upon the illitization of clay min er als. – se lected issues. In: Golonka, J. Lewandowski, M. (eds) Ge - Consid er ing the depositional condi ti ons and, first of all, ol ogy, geo phys ics, geothermics and deep struc ture of the the later tec tonic his tory of the Podhale Flysch, it seems West Carpathians and their base ment. Pub li ca tion of the In- likely that esti mati ons present ed above bear an error, which stitute of Geophys ics Polish Academy of Sciences, M-28 result s from the follow ing reasons: (363): 13–23. – during the Savic phase of Al pine orogeny (Late Day-Strirrat, R. J. Alpin, A. C., Œrodoñ, J. & Van der Pluijm, B. Oligocene-Chattian) flysch and its base ment com posed of A., 2008. Diagenetic re ori en ta tion of phyllosilicate min er als High- and Sub-Tatric se ries were subject ed to strong block in Paleogene mudstones of the Podhale Ba sin, south ern Po - tec ton ics (see, e.g., Mastella, 1975), mostly subsi dence , due land. Clay and Clay Min er als, 56 (1): 100–111. to con ti nent-con ti nent col li sion be tween the Czorsztyn and Dudziak, J., 1986. Stratygrafia fliszu podhalañskiego (paleogen) na podstawie nannoplanktonu wapiennego. (In Pol ish, Eng - Andrusov ridges. This proces s has conti nued during the lish summary). Studia Geologica Polonica, 102: 159–176. later phases of Al pine movem ents, starting from the Styrian Gedl, P., 2000. Biostratigraphy and paleoenvironment of te Pod- phase (Middle Miocene -Langhian) and caused folding of hale Paleogene (In ner Carpathians, Po land) in the light of the Podhale Flysch and upli ft of the Tatra massif. Such geo- palynological studies, part I. Studia Geologica Polonica, 117: tec tonic proces ses result ed in de posi ti on of molasse, which 69–154. filled the recent Orawa De pression as about 1,300-m- thick Gross, P., Köhler, E., Papšova, J. & Snopková, P., 1980. Geologia al lu vial fans (Mid dle Mio cene–Plio cene) (Watycha, 1976) a stratigrafia sedimentov Centralnokárpackeho paleogénu. (In with the seams of soft brown coal (Ko³con & Wagner Slo vak). In: Geologia Liptovskej Kotliny. Geologický Ústav 1991); D. Štúra. Bratislava: 22–72. – this molasse might have covered the whole area of the Kêpiñska, B., 2006. Ther mal and hy dro ther mal con di tions of the Podhale Trough, sim i larly to Pleis to cene-Ho lo cene al lu vial Podhale geo ther mal sys tem. (In Pol ish, Eng lish summary ). fans which docu m ent the conti nu ous upli ft of the Tatra mas- Studia, Rozprawy, Monografie IGSMiE PAN w Kra- kowie, 135: 1–112. sif; Ko³con, I. & Wagner, M., 1991. Wêgiel brunatny z osadów neo- – brown coal (metalignite) recent ly exposed in the out - genu Kotliny Orawsko-Nowotarskiej – studium petrolo- crops of the Orava Neogene succes sion indi cat es that under giczne. (In Polish, Eng lish summary ). Kwartalnik Geolo- the “cool” geother mal gradi ent (<50°C/km) observe d in giczny, 35: 305–322. many coal de posit s the overbur den thickness had to be over Krobicki, M. & Golonka, J., 2008. Podhale Paleogene Flysch as 400 m but less than 1,000 m (Stach et al., 1978), maybe geotourictic at trac tive re gion – first look to its unique geo log - about 700 m, i cal val ues. Geoturystyka - Geotourism, 2 (13): 25–44. – conse quentl y, the amount of erosion of the Podhale Mastella, L., 1975. Flysch tecton ics in the eastern part of the Flysch should be reduced by this value, at least in the area of Podhale Ba sin. (In Pol ish, Eng lish summary ). Rocznik Pols- Chocho³ów where these sedi m ents have been partly pre- kiego Towarzytwa Geologicznego, 45: 361–401. served (vicin it y of Czarny Dunajec-Chy¿ne). Mastella, L. & Mizerski, W., 1978. Uwagi o budowie geologicznej In order to il lustra te changes in the diagenetic and kata- SW czêœci Podhala. (In Polish). Przegl¹d Geologiczny, 10: geneti c his tory of the Podhale Flysch, the studies reporte d 494–499. Morris, K., 1979. 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