Wójcik- Tabol, P. & Œl¹czka, A., 2009. Prove nance and dia gene sis of sili ci clas tic and or ganic ma te rial in the Al bian–Tu ro nian sedi ments (Silesian Nappe, Lanck orona, Outer Car pa thi ans, Poland): pre limi nary stud ies. An nales So cie ta tis Ge olo go rum Po lo niae, 79: 53–66.
Ab stract: The prove nance and dia gene sis of the sili ci clas tic and hemipe la gic sedi ments of three lithos tra tigraphic units: Lhoty For ma tion, Bar na siówka Ra dio lar ian Shale For ma tion (BRSF) and Varie gated Shales from Lanck o-rona area, Pol ish Outer Car pa thi ans, was ap proached by means of pet ro logi cal and geo chemi cal analy sis of the rep re sen ta tive sam ples. Data show that stud ied suc ces sion was mainly de rived from two sources: 1. a domi nant ter ri ge nous fine- grained com po nents have af fin ity with av er age up per con ti nen tal crust (bas ing on min eral de tri tus, K2O/Rb ra tio and Y/Ni vs. Cr/V ra tios) and 2. bio genic si li ceous ma te rial and mac er als. Com po si tion var ies up sec tion and ac counts for changes in the de tri tal sup ply due to eustatic sea- level changes. Or ganic pe trol ogy shows pres ence of or ganic de tri tus within the Lhoty Fm and domi nance of marine- derived mac er als in the BRSF. Chemi cal and pet ro logi cal fea tures im ply a pro gres sive deep en ing of the ba sin. The stud ied suc ces sion was dia ge neti cally al tered (e.g. co ali fi ca tion of bi tu minite, il li ti sa tion of smec tite and py ri ti sa tion).
Key words: or ganic and in or ganic geo chem is try, Al bian–Tu ro nian, Sile sian Nappe, Outer Car pa thi ans, Poland. Manu script re ceived 1 October 2007, ac ceepted 16 April 2009
IN TRO DUC TION
The Outer Carpathian bas ins were sit u ated dur ing Cre -ta ceous times be tween the con verg ing Eu ro pean con ti nent and the In ner Carpathian plate (Oszczypko, 1999; Golonka
et al. 2000, 2008b). Dur ing its open ing and postrift sub si
-dence (Late Ju ras sic–Early Cre ta ceous), the Silesian Ba sin was filled with cal car e ous turbidites fol lowed by siliciclas-tic turbidites and hemipelagic shales (Oszczypko 2004). The siliciclastic and biogenic ma te ri als were sup plied from two main sources: the Eu ro pean Plat form and the Silesian Cor dil lera (e.g., Wieser, 1948; Burtan et al., 1984; B¹k, 2007b).
Dur ing the Al bian–Ce no ma nian (Gedl, 2001; B¹k et
al., 2005, Golonka et al., 2008b) tur bid ite com plexes of the
Lhoty For ma tion were de pos ited in the ax ial part of the ba -sin. A low and de creas ing rate of sedi men ta tion (20–40 m/My) was char ac ter is tic for the Sile sian Ba sin (Po prawa et
al., 2002). The Lhoty For ma tion deposition took place dur
-ing rela tively low sea level and was con trolled by a post- rift ther mal sub si dence (Po prawa et al., 2002; Nemèok et al., 2001). The Bar na siówka Ra dio lar ian Shale For ma tion (BRSF) is de vel oped as the green ra dio lar ian shales and ra
dio larites, in ter ca lated with black shales con tain ing ben to -nites and ferro-manganiferous con cre tions and lay ers (Ksi¹¿kiewicz 1951; Koszarski & Œl¹czka, 1973; B¹k et al., 2001; B¹k, 2006, 2007a–d). The BRSF was de pos ited dur -ing the Late Cenomanian–Early Tu ro nian un der high- stand sea level con di tion (B¹k, 2007a). It is over lain by the Tu ro -nian Varie gated Shales (VS) that rep re sent a prod uct of deep- sea hemipe la gic sedi men ta tion (Kosz ar ski & Œl¹czka, 1973). The hy dro ther mal ac tiv ity could de velop dur ing the Al bian maxi mal ex ten sion of con ti nen tal crust and lasted at least through the Tu ro nian (Bur tan & Turnau- Morawska, 1978; Gucwa & Wie ser, 1978; Geroch et al., 1985; B¹k, 2006, 2007a–d).
The pres ent pa per shows re sults of min era logi cal and geo chemi cal in ves ti ga tion of hemipe la gic sedi ments to in di -cate the prove nance of the min eral and or ganic de tri tus and dia ge netic changes of the sedi ment. Pe lagic sedi ment for -ma tion is af fected by many pro cesses, in clud ing de tri tal sup ply from con ti nen tal ar eas as well as hy dro ther mal and bio logi cal ac tiv ity, and dia gene sis (Ches ter, 1990). Chemi cal rec ords of the en vi ron mental changes across the Ce no
-ma nian–Tu ro nian tran si tion in the Pol ish Car pa thi ans were pre sented ear lier by B¹k (2006, 2007a–d). The main ob jec tives of this study is pres en ta tion of new data with cor re la -tion to that pre vi ous.
GEO LOG I CAL SETTING
The Pol ish Car pa thi ans are part of the great arc of mountains stretch ing for more than 1300 km. The Pol ish part of the Outer Car pa thi ans con sists of stacked nap pes and thrust- sheets, such as the Sub sile sian, Sile sian, Skole, Dukla and Ma gura Nap pes (Fig. 1; Ksi¹¿kiewicz, 1977).
The pre sented pa per con cerns the sed i ments of the Sile- sian Nappe, which were de pos ited in the Subsilesian–Sile-sian Ba sin (Severinic-Moldavidic sensu Œl¹czka, 2006) from Late Albian to Early Turonian (Ksi¹¿kiewicz, 1962). The sam ples rep re sent siliciclastic and hemipelagic sed i ments of three lithostratigraphic units: turbiditic Lhoty For -ma tion (sensu Golonka et al., 2008a, pre vi ously known as Lgota Beds, e.g. Bieda et al., 1963), Barnasiówka Radiola-rian Shale For ma tion (BRSF; sensu B¹k et al., 2001) and Var ie gated Shales.
The sec tion stud ied is lo cated in west ern part of the Sile sian Nappe, within the Lanck orona Foot hills, about 30 km south- west from Kraków (Fig. 1). The main out crop is
situ ated in the banks of a small creek, a right tribu tary of the Ce dron stream. This sec tion is small and strongly folded. The stud ied suc ces sion ap pears in re verse or der and con -tains nu mer ous tec tonic hia tuses.
The old est sedi ments ex posed in the north ern part of stud ied sec tion be long to the Bar na siówka Ra dio lar ian Shale For ma tion. They are rep re sented by black and green, si li ceous shales (Fig. 2E) with in ter ca la tions of ben to nites and fer ro man ga nese ho ri zons (up to 5 cm thick) (Figs 2C, D; 5A). The thick ness of these strata amounts to about 5 m. Fur ther, up wards the suc ces sion a com plex of red and green ish grey thin- and medium- bedded si li ceous shales with thin in ter ca la tions of glau co nitic sand stones and green -ish cherts is ex posed (Fig. 2A, B). This part is about 3.8 m thick and be longs to the Up per Cre ta ceous Varie gated Shales.
When go ing to wards the south, up ward the hill, the old quar ries of the Mid dle and Up per Lhoty For ma tion oc cur. The Mid dle Lhoty For ma tion con sists mostly of thin- and medium- bedded si li ceous dark- grey sand stones. They are in ter be ded with black, grey and spotty, lightly- calcareous shales (Fig. 3A–D). The up per di vi sion of the Lhoty For ma -tion, named the Mikuszowice Chert Mem ber (Szajno cha, 1884 in Golonka et al. 2008b; Bieda et al., 1963) is rep re sented by me dium and thick bedded (about 50 cm) sand -stones with blu ish cherts in the mid dle and up per parts of lay ers in ter ca lated with grey and black shales (Fig. 4A, B).
Fig. 1. Lo ca tion of the stud ied area at the back ground of main geo log i cal units: A. Sim pli fied tec tonic scheme of the Al pine orogens; PKB – Pieniny Klippen Belt (af ter Kovaè et al., 1998, mod i fied); B. Cen tral part of Pol ish Carpathians (af ter ¯ytko et al., 1989); C. De -tailed di vi sion of the Silesian and Subsilesian units in the Lanckorona re gion (af ter Ksi¹¿kiewicz, 1977)
Fig. 2. Lithological log of the Lanckorona sec tion. Var ie gated Shales: A. Red and green ish-grey, thin- and me dium-bed ded si li ceous shales with glauconitic sand stone (Snd); B. Se quence of green-grey shales interbedded by quartzitic sand stone; Barnasiówka Radiolarian Shale For ma tion: C. Ben ton ite (BT) in ter ca la tion within none-cal car e ous black and green shales; D. Or ganic-rich shales and radiolarites with Mn-Fe ho ri zon (Mn); E. Si li ceous black and green shales with in ter ca la tion of volcanoclastic lay ers
MA TE RI ALS AND METH ODS
Mi cro struc tures and or ganic pet ro logi cal in di ces in 15 sam ples us ing mi cro scopic ob ser va tion (Ni con ECLIPSE, E 600 POL; trans mit ted and re flected light) were examined.
The sam ples were stud ied by X- ray dif frac tion (XRD) both as bulk rocks and in <0.2 µm frac tions sepa rated from these rocks. The pe li tic frac tions <0.2 µm were sepa rated us ing the com plete Jack son (1975) pro ce dure, ap plied in or -der to dis solve car bon ates and re move or ganic mat ter and iron ox ides. They were stud ied as ori ented prepa ra tions, sedi mented on glass slides, both in air- dry and eth yl ene gly col satu rated form. A Phil ips dif frac to me ter, equipped with a Cu lamp, and a mono chro ma tor were used.
The iden ti fi ca tion of clay min er als fol lowed the method out lined by Moore and Rey nolds (1997). Mixed-layer il lite- smec tite and smec tite were iden ti fied in gly co lated prepa ra tions us ing the po si tions of ap pro pri ate pairs of ba sal re flec -tions (Œro doñ, 1980, 1984; Dudek & Œro doñ, 1996).
The amounts of ma jor ox ides were de ter mined in 15 sam ples us ing an in duc tively cou pled plasma – op ti cal emis sion spec trome try (ICP OES). Trace element were de ter mined by the in duc tively cou pled plasma – mass spec -tros copy (ICP- MS) us ing a Perkin El mer Elan 6000 ICP at the ACME Ana lyti cal Labo ra to ries, LTD, in Van cou ver, Can ada.
The en rich ment fac tors (EF) for ma jor and trace el e -ments rel a tive to the Post-Archean Aus tra lian Shale (PAAS, Tay lor & McLennan, 1985) were used in the dis cus sion. The val ues of en rich ment fac tor are cal cu lated as fol lows (* ac cord ing to Tay lor & McLennan (1985):
(ele ment con tent/Al con tent) sam ple /(ele ment con tent / Al con tent) PAAS*
RE SULTS
MIN ER AL OGY AND PE TROL OGY
The XRD pat terns of whole- rock analysed sam ples show that, in gen eral, they (Lhoty For ma tion, BRSF and Varie gated Shales) are rich in quartz, as so ci ated with clay min er als, and con tain small amounts of feld spar. Cal cite is pres ent in the Lhoty For ma tion sam ples and rarer within shales of the BRSF, ab sent in the Varie gated Shales.
Up ward the suc ces sion, from the Mid dle Lhoty For ma tion through the Varie gated Shales, the quartz con tent in -creases. The clay min eral com po si tion var ies slightly and con sists mainly of il lite and mixed lay ers il lite/smec tite (I/S). The con tent of il litic lay ers in the I/S range be tween 10 and 60%. The Lhoty Fm. siltstones contain the low est amounts of smec tite, while the clayey shales of the BRSF are en riched in it. The high est amounts of smec tite oc cur within the vol cano clas tic lay ers in the BRSF (about 80%). Kao lin ite is the as so ci at ing clay min eral in the shales of the Mid dle Lhoty Fm. Up ward the sec tion, kao lin ite con tent de creases. It fi nally dis ap pears in the lower part of the Varie -gated Shales. Chlo rite has been rec og nized in mi nor amount within the Mid dle Lhoty For ma tion only.
Ob ser va tions of thin- section of green- grey shales (within both: Lhoty For ma tion and BRSF) re veal the wavy-and par al lel lami na tion (Fig. 5D). The ichno fos sils are also noted (Fig. 5B). The bur rows are en riched in or ganic mat ter, which is usu ally as so ci ated with py rite. Py rite oc curs as mas sive, an he dral grains. Ra dio laria and sponge spic ules have been there of ten rec og nised. Tests are ori ented par al lel to the bed ding. The sin gle grains of glau co nite, quartz, mica and or ganic de tri tus (cell structured mac er als, e.g. semi fus -inite) are dis persed within ar gil la ceous ma trix.
Fig. 3. The Mid dle Lhoty For ma tion; A–D. Thin- and me dium-bed ded si li ceous dark-grey sand stone interbedded with black, grey and spotty, low-cal car e ous shales
The par al lel lami na tion oc curs within black shales (within both: Lhoty For ma tion and BRSF). It is em pha sised by abun dant or ganic mat ter (Fig. 5C) rep re sented by a dark, amor phous sub stance and ter res trial de tri tus (Fig. 5E–H). The sam ples in clude very rare ra dio lar ian tests as the only bi otic com po nent. Py rite oc curs as very thin fram boids and crys tals. The size of both var ies from 5 to 12 µm, where pre -domi nately 8 – 10 µm in di ame ter (Fig. 5E, H).
The man ganif er ous ho ri zon, 2–5 cm thick oc curs within the si li ceous shales of the BRSF. It over lies the pack age of black and green clayey shales with ben to nite in ter ca -la tion. The Mn- Fe -layer con tains many con cen tri cally zoned nod ules that are less than 3 cm in size. The nod ules are built of green ish core and outer black rim (Fig. 6A). The section im ages ex hibit the pres ence of nu mer ous rhom bo he -dric pseu do morphs (50 µm in size on av er age) dis persed within sil ica (cryp to crys tal line chal ced ony) ad mixed with clay min er als ma trix (Fig. 6B). In the in ter nal part of the nod ules, sil ica adopts rhom bo he dral shape whereas rhom -bo he dra of the outer crust are in filled by the Fe and Mn oxy- hydroxides (Fig. 6C, E). The pseu do morphs from the ex ter nal part of the nod ules con tain mas sive ag gre gates of py rite (Fig. 6D).
The stud ied Varie gated Shales over ly ing the BRSF are rep re sented by si li ceous red and green shales with bedded sand stones. The shales are clayey, bar ren of de tri -tus. The fine- grained in ter ca la tions con sist of quartz, mica, feld spars and glau co nite. Some sand stone lay ers are en -riched in Fe- Mn oxy- hydroxides.
GEO CHEM IS TRY
The rel a tively low amounts of the ma jor ox ides (Fe2O3
and MnO, MgO, CaO, TiO2, Na2O, K2O) have been
determined in the sam ples stud ied (Tab. 1). Their amounts are lower (oc ca sion ally sim i lar) than that in PAAS. Only SiO2 con tents are well above the SiO2 con tent of PAAS
(62.8 wt. %; Tay lor & McLennan, 1985). The amount of sil -ica in the se lected sam ples of the BRSF and Var ie gated Shales is higher than in oth ers. The manganiferous sam ple (LC 4BG), de spite its low SiO2 con tent (43.82 wt. %) has a
high SiO2 (2.83) en rich ment fac tor (EF) be cause of low
Al2O3 content (4.66 wt. %).
In the SiO2 vs. Al2O3 di a gram (Fig. 7), the stud ied sam
-ples dis play neg a tive cor re la tion be tween these ox ides. The ma jor ity of sam ples show sim i lar SiO2/Al2O3 ra tio (5 in av
-er age, with out manganif-erous sam ples). They are lo cated in a small field ap prox i mately along one trendline. The ex cep tion is FeMn sam ple (LC 4BG) that is out of gen eral di -rec tion due to low con tent of SiO2 and Al2O3.
MnO, P2O5, Y, La, Ce
The dis tri bu tions of these el e ments are ir reg u lar (Tab. 1; Fig. 8). The Lhoty For ma tion seem to be more en riched in up per part than in lower – it might be con nected with li -thol ogy. The most en riched sam ples from the Up per Lhoty For ma tion con tain abundant detritus.
In gen eral, itrum con tents vary be tween 13.2 and 39 ppm in the sam ples stud ied, whereas in the PAAS it yields 27 ppm. There fore, (EF)Y val ues vary from 0.65 to 5.87.
The manganiferous sam ple (LC 4BG) is the most en riched in Y. The high Y con cen tra tion was also noted in the Mn-rich sand stone of the Var ie gated Shales (LC 1).
The La con tents dif fer within nar row range; they equal to 30 ppm in av er age, with max i mum in the volcanoclastic sam ples (LC BT). Nev er the less, the high est val ues of en -rich ment fac tor are noted in the LC 1 and LC 4BG sam ples (EF are 2.58 and 3.36).
The ab so lute con tents of ce rium are low with a small rise in the Mn-rich LC 4BG and ?volcanoclastic (LC BT) sam ples from the BRSF. The en rich ment fac tor va ri ety shows sim i lar pat tern like La and Y. Their val ues do not ex -ceed unity, ex cept of the LC 4 BG and LC 1, where EF amounts to 3 and 6.37 re spec tively. Worth to note that el e -va tion of the EF -val ues in both sam ples is af fected by low per cent age of Al2O3.
The en rich ment of Y, La and Ce cor re lates with in -creas ing con cen tra tions of MnO and P2O5. The BRSF and
Var ie gated Shales are en riched of MnO and P2O5 ob vi
-ously. The high est con tent of ox ides char ac ter ises the LC 4BG and LC 1 sam ple. The LC 4B and LC 3 sam ples ex -hibit the moderate enrichment.
Fig. 4. The Up per Lhoty For ma tion; A, B. Me dium- and thick-bed ded sand stones with blu ish cherts
K2O and large ion lithophile trace el e ments: Rb, Pb
The per cent age of K2O and Rb var ies in broad ex tent.
Most of sam ples are just be low PAAS. There fore, the sam -ples have en rich ment fac tors be low unity (Fig. 9). The ?volcanoclastic sed i ments of the BRSF con tain the high est amounts of K2O and Rb and dis play the stron gest sim i lar ity
to PAAS. In con trast, the manganiferous LC 4BG and LC 1 sam ples rep re sent the poor est sed i ment. They seem to be rel a tively en riched in K2O and Rb (EF >1), but it is a re sult
of low Al2O3 con tent. In gen eral, the K2O con tents cor re
-late with Rb (r2 equals 0.9) and K2O/Rb ra tio is con stant – it
amounts to 0.02, like PAAS (Fig. 12).
The lead dis tri bu tion through the sec tion is ir reg u lar. Ex cept of black shale, un der ly ing Mn ho ri zon from the BRSF, the Pb con tents are rather low. Coo per and va na dium con tents fol low this pat tern. The en rich ment fac tor for Pb, Cu and V ex ceed the high est val ues in the same sam ples (LC 4B and LC 4BG).
More over, cor re la tion be tween Pb, Cu, V fre quency and con cen tra tion of or ganic mat ter (OM) and S has been recognized (Fig. 10). The sam ples en riched of OM and/or S con tain higher amounts of metals.
Fe2O3, MgO, and S-re lated trace el e ments: Ag, As, Cd, Co, Cu, Mo, Ni, Se, V, Zn
The av er age amounts of MgO are low in the Lhoty For -ma tion and higher in the up per part of the sec tion. Within the BRSF and Var ie gated Shales, the amounts of MgO dif -fer be tween 0.8 and 2.56%. The mangani-ferous sam ples (LC 4 BG and LC 1) con tain the low est amount of MgO, while in the volcanoclastics (LC BT and LC 5G) per cent age of MgO is the high est. Fi nally, the en rich ment fac tor closes to unity in the Lhoty For ma tion and slightly passes 1 in the up per part of the sec tion (BRSF and Var ie gated Shales; Fig. 10).
The dis tri bu tion of the ab so lute con tent and en rich ment fac tors for Fe2O3 is anal o gous. The val ues in crease up ward
to spike in the manganiferous sam ple (EF is 4.8) and de -crease again be low 1 in up per BRSF/Var ie gated Shales.
The ab so lute con tents of S-re lated el e ments vary along the sec tion er ratically. The Lhoty For ma tion sam ples are poor in S and con tain small amounts of Ni, Co, Zn, Mo as well. Their en rich ment fac tor does not ex ceed unity (Fig. 10). Va na dium con tents are close to these for PAAS. Only copper con cen tra tions are higher with respect to PAAS.
Fig. 5. Mid dle part of the Barnasiówka Radiolarian Shale For ma tion in the Lanckorona sec tion; A. Non-cal car e ous black and green shales with yel low ish volcanoclastic layer; B. Ichnofossils within green shales (LC 5 G sam ple, TL, II nicols); C. Microfacies of par al -lel-lam i nated black si li ceous shale in clud ing detritic grains (LC 5B sam ple, TL, II nicols); D. Par al lel lam i na tion and pas sage from green to black shales (LC 5G sam ple, TL, II nicols); E–H. Or ganic par ti cle – vitrinite maceral (OM), py rite (PY; LC 5B sam ple, RL)
The sam ples from the BRSF are sig nif i cantly en riched in V, Co, Ni, Cu, Zn and Mo (Se, As, Cd). This for ma tion con sists of OM-rich black shales, where trace el e ment might be trapped by OM and S. The en rich ment in Co, Ni, (Ag, Cd) was noted in the manganiferous sam ple LC 4BG, bar ren of S (Fig. 10). The en rich ment in Co, Mo, Zn, Ni, As, Se oc cur ring in the ben ton ite sam ple (LC BT) cor re lates with presence of S.
In the Var ie gated Shales, con tents of trace el e ments and S di min ish again. They re sem ble sam ples of the Lhoty For -ma tion.
TiO2 and high strength field trace el e ments: Zr, Nb, Th and Ga
Ab so lute con tents of TiO2 in the sam ples stud ied are
gen er ally lower than those for PAAS, thus en rich ment fac -tors for TiO2 are usu ally be low unity (Fig. 11). In de tail, the
Lhoty For ma tion sam ples con sist of higher amounts of TiO2
that de crease up ward the suc ces sion. Sur pris ing is the peak for LC BT. The min i mal per cent age was noted in the manganiferous sam ples of the BRSF (LC 4BG) and VS (LC 1). The sec ond one is sand stone im pov er ished of Al2O3,
thus it shows rel a tively high EF about 1. The be hav iour of
TiO2 is sim i lar to Nb and Th, and partly cor re lates with zir
-con. The LC 1 sam ple is ex tremely en riched due to both high amount of Zr and low amount Al2O3.
Fig. 6. The ferro manga nese ho ri zon over ly ing the or ganic-rich fa cies within the Barnasiówka Radiolarian Shale For ma tion in the Lanckorona sec tion; sam ple LC 4 BG; A. Frag ment of a small-sized el lip soi dal Fe-Mn nod ule con tain ing green core and black, outer rim; B. In ter nal core con sist ing of sil ica and pseudo morphs af ter car bon ate crys tals (PC); ma trix com posed of clay min er als ad mixed with sil ica (Q/CM), TL; C–E. Outer rim of nod ule in clud ing FeMn oxy, hy drox ide (ox Mn) pseudo morphs af ter car bon ates, TL; D. Pseudo -morphs con tain ing py rite (py)
Fig. 7. SiO2 vs. Al2O3 re la tions in the stud ied sam ples from the Lanckorona area. LC 4 BG sam ple of BRSF is dis placed from the curves due to low amounts of ox ides and high con tent of MnO
The Ga pat tern is more ir reg u lar (Fig. 11). The high est en rich ment (EF=6.34) is mea sured in the manganiferous shale, whereas the rest of sam ples dis play en rich ment factor just above 1.
DIS CUS SION
PROV E NANCE OF THE MIN ERAL AND OR GANIC DE TRI TUS
The most im por tant prob lem is to sep a rate the de tri tal ma te rial from the prod ucts of diagenesis and or ganic sup ply. The shales in the turbidite suc ces sion (Lhoty For ma -tion) con tain a rel a tively small amount of or ganic mat ter
rep re sent ing mainly land-orig i nated vitrinite macerals. Glauconite and quartz grains are the sec ond most fre quent and un ques tion able type of re de pos ited ma te rial. The sort -ing and ad di tion of biogenic sil ica may sig nif i cantly af fect the SiO2/Al2O3 ra tio, which is used as prov e nance in ter pre
-ta tion (Ros ter & Grapes, 1990). A value of Si/Al ra tio of about 3 is con sid ered to be an av er age ra tio for terrigenous sed i ments. Val ues greater than 3 are thought to be due to an “ex cess” sil ica sup ply, prob a bly of biogenic or i gin (Ar thur & PremoliSilva, 1982). Ex cept of ?ben ton ite (LC BT sam -ple), the stud ied sam ples dis play val ues of Si/Al ra tio higher than 3. Ex tremely high ra tio was es ti mated for sili ceous LC 1 sam ple of the Var ie gated Shales and Mn-rich LC 4 BG
Ta ble 1
Ma jor and trace el e ment chem is try for the Albian–Lower Turonian sed i ments from the Lanckorona area, Silesian Nappe
Element SiO2 Al2O3 Fe2O3 MgO CaO Na2O K2O TiO2 P2O5 MnO S Th U V Zr Y La Ce
Samples % % % % % % % % % % % ppm ppm ppm ppm ppm ppm ppm LCL 1 64.84 12.58 3.26 1.3 4.08 0.22 2.7 0.64 0.09 0.03 <0.01 10.1 3.1 120 125.9 16.3 28.6 45.8 LC L 2 69.8 14.2 2.65 1.07 0.93 0.2 2.37 0.54 0.06 0.01 <0.01 11.4 2 101 83.9 13.2 23.9 46 LCL 3 69.84 14.59 2.56 1.14 0.72 0.21 2.42 0.57 0.05 0.02 0.01 11.3 2.1 97 98.3 14.8 25 51.7 LC 7 64 18 3.2 1.23 0.5 0.3 3.4 0.71 0.07 0.03 0.03 13.2 2.4 119 122.6 16.7 28 57.5 LC 6 66.17 16.3 3.9 1.3 0.5 0.3 3.03 0.6 0.08 0.04 0.01 13.2 1.9 114 99.9 17.1 24.5 52.7 LC 5B 70.48 11.52 3.41 1.75 0.73 0.23 2.46 0.42 0.13 0.04 0.43 8.6 3.1 196 61.9 23.8 24.4 59.1 LC 5G 60.8 16.56 5.07 2.56 0.78 0.28 3.63 0.59 0.1 0.04 0.47 13.1 4 175 82.9 21.1 31.4 73.7 LC 5M 67.4 12.26 4.75 1.79 0.49 0.23 2.7 0.45 0.13 0.03 1.25 10 4 263 66.9 24.4 27.5 64.6 LC 4BG 43.82 4.66 7.67 0.72 0.28 0.08 1.41 0.15 0.21 26.6 0.01 3.3 2.9 134 25.6 39 31.4 125.3 LC 4B 65.4 13.54 4.75 1.99 0.71 0.21 3.22 0.5 0.18 0.27 0.01 11.5 2.4 705 71.3 33.7 34.9 74.2 LC BT 55.23 19.9 5.04 2.5 0.77 0.28 4.05 0.78 0.09 0.05 0.31 16.5 4.8 207 108.4 26.3 39.2 87.4 LC 3G 68.23 11.01 2.53 1.57 3.22 0.18 2.39 0.44 0.09 0.13 0.01 8.6 1.8 78 80.1 19.8 27.2 64.6 LC 3B 69.54 12.9 3.35 1.89 0.8 0.24 2.83 0.51 0.09 0.07 0.01 8.7 1.8 137 73.5 20 26.5 60.8 LC 2B 69.49 12.74 2.91 1.77 0.78 0.22 2.64 0.52 0.07 0.08 0.01 10.1 1.7 93 77.6 14.8 25.7 49.5 LC 1 83.06 5.59 2.96 0.82 0.68 0.56 1.04 0.31 0.21 0.7 0.01 8.6 2.4 42 262.7 35 29 72.7 Element Ba Co Ga Nb Rb Ba Mo Cu Pb Zn Ni As Cd Ag Se Cr Samples ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm LCL 1 313.8 10.4 12.8 13.6 109.1 313.8 0.4 55.2 14.5 45 33.1 4.7 0.1 <0.1 <0.5 90 LC L 2 244.5 6.6 17.1 10.9 94.2 244.5 0.4 100.2 20.3 42 20 3.7 <0.1 <0.1 0.5 70 LCL 3 241.3 6.2 16.7 11.1 97.4 241.3 0.2 100 17.2 44 18.5 1.7 <0.1 0.1 <0.5 70 LC 7 364.7 6.4 3.7 14.7 142.2 364.7 0.1 52.2 18.2 36 19.8 32 0.1 0.1 <0.5 82 LC 6 259.3 11.4 19.8 14.1 119.6 259.3 0.2 129.5 25.2 62 50.8 5.1 0.9 0.1 <0.5 82 LC 5B 275.6 12.4 17.7 7.7 101.7 275.6 1.7 151.9 20 240 52.8 10.1 2 0.8 4 100 LC 5G 293.7 24.7 24.7 12.3 160.7 293.7 0.4 92 24.1 193 89.7 16.9 0.6 <0.1 1.3 90 LC 5M 316.1 18.1 19 9.2 122.8 316.1 10.6 182 25.8 1346 59.6 28.4 4.3 1.2 12.7 110 LC 4BG 3098.9 91.7 31.2 2.7 65.2 3098.9 12.6 290.1 53.8 663 238.3 8.7 4.2 14.5 0.8 30 LC 4B 343.1 20.1 19 10.1 130.9 343.1 0.3 818.8 123 35 46.9 0.8 0.1 0.3 1 110 LC BT 321.5 25.5 23 16.8 168.9 321.5 1.9 123.2 25.2 448 147.5 16.4 0.9 <0.1 6.2 110 LC 3G 316 11 16.9 10.1 117.4 316 <0.1 95.2 10 58 31.9 2.4 <0.1 <0.1 <0.5 70 LC 3B 255.3 20.9 14.8 9 106.5 255.3 <0.1 113.9 22.9 86 36.7 2.7 0.1 0.3 <0.5 80 LC 2B 290.8 22.2 16.2 10.5 111.8 290.8 0.1 57.2 13.8 49 34.8 8.5 <0.1 <0.1 <0.5 70 LC 1 306.8 8.3 7.2 5.7 43.6 306.8 0.9 14.9 10.5 32 23.5 2.2 0.1 <0.1 <0.5 40
sam ple. The higher neg a tive cor re la tion may be the ef fect of pre dom i nance of biogenic sil ica, di luted by terrigenous par -ti cles as was ear lier sug gested by B¹k (2007a, b) for the BRSF in the Silesian, Subsilesian and Skole units. The pres -ence of siliceous tests and detritic quartz in the studied samples was confirmed by thin section observation.
Bas ing on the ab so lute con tents, the sil ica is as so ci ated with the high est amounts of TiO2, Nb, Th and Zr. The con
-cen tra tions of TiO2, Zr, Nb, Th and Ga, con sid ered to be im
mo bile el e ments, vary mostly as a func tion of biogenic di lu -tion in ma rine sed i ments and thus are in ter preted to be largely de tri tal (Plank & Langmuir, 1998).
With respect to PAAS, the stud ied ma te rial is poor in TiO2, Nb and Zr. Two sam ples only (LC 6, LC 1) are en
-riched in TiO2, Nb and Zr that cor re late with en hanced fre
-quency of de tri tal quartz. The amounts of Th and Ga in the stud ied sam ples are sim i lar to PAAS. Ad di tion ally, the manganiferous LC 4BG sam ple is ex tremely en riched in Ga. Most of sam ples dis play en rich ment fac tor just above 1, tes ti fy ing to the small supply of detrital material.
Ac cord ing to B¹k (2007b), an in crease in fine de tri tal in put to the Carpathian ba sin oc curred dur ing lat est Ceno-manian. It is marked by pos i tive ex cur sions of Al/(Al+ Fe+Mn) and Rb/Al pro files (Machhlour et al.,1994; Wehausen & Brumsack, 1998). The flu vial in put was dom i -nat ing, while the ae olian in put might have been neg li gi ble, as ex pressed by the low ra tio of Ti/Al (Wehausen & Brum-sack, 1998). The share of land-de rived siliciclastic ma te rial was fairly con stant dur ing the Cenomanian–Turonian Boun -dary (CTB) in ter val.
Plank and Langmuir (1998) have showed strong cor re -la tion be tween trace el e ments, in clud ing al ka lis (K, Rb) and
Fig. 8. PAAS-nor mal ised con cen tra tions of SiO2, MnO, P2O5, Y, La, Ce in the stud ied sam ples. Dashed line cor re sponds to PAAS (Tay lor & McLennan, 1985)
Fig. 9. PAAS-nor mal ised con cen tra tions of K2O and large ion lithophile trace el e ments: Rb, Pb in the stud ied sam ples. Dashed line cor re sponds to PAAS (Tay lor & McLennan, 1985)
li thol ogy, and that their ra tios are pre dom i nantly due to con -ti nen tal in put. Con tri bu -tions from vol ca nic sources can be es ti mated us ing the K2O/Rb ra tio (Fig. 12). Low K2O/Rb
ratios are typ i cal of weath ered sources (McLennan et al., 1990), whereas high K2O/Rb ra tios are char ac ter is tic of
sediments rich in volcanoclastics or sed i ments that have been al tered due to K metasomatism (Plank & Languir, 1998). The in ves ti gated sam ples have the K2O/Rb ra tio
sim i lar to de tri tus de rived from the up per continental crust (Chester, 1990; Fig. 12).
The con ti nen tal af fin ity of the stud ied sam ples can be tested us ing the Y/Ni and Cr/V el e men tal ra tios, which are used to iden tify mafic sources (Hiscott, 1984). The stud ied sam ples are very sim i lar to PAAS (Fig. 13). How ever, a mafic-ultra mafic con tri bu tion can be ex cluded. Andreozzi
et al. (1997) have pro posed a di a gram bas ing on the con
tents of some tran si tion met als (V, Ni, Cr) and im mo bile el -e m-ents (Zr and Ti) to dis crim i nat-e a pos si bl-e volcanoclastic or terrigenous con tri bu tion. The sam ples in ves ti gated plot within the terrigenous field (Fig. 14).
These data cor re spond with ear lier par a digm that siliciclastic par ti cles were sup plied to the Outer Carpathian bas -ins from the Eu ro pean Plat form (e.g., Wieser, 1948; Burtan
et al., 1984; B¹k, 2007 b).
The high con tent of sil ica may in di cate rel a tive in crease in or ganic pro duc tiv ity in the lat est Cenomanian–ear li est Turonian times. The nu mer ous radiolarianrich lay ers prob -a bly re flect upwelling cir cu l-a tion -at the m-ar gin of the C-ar- Car-pathian Ba sin (B¹k, 2006, 2007 a, b). The abun dance of radio lar ians is linked to the ma rine organic matter en rich-ment.
The amor phous macerals in the black shales of the BRSF were iden ti fied as colovitrinite and al tered
bitu-Fig. 10. PAAS-nor mal ised con cen tra tions of Fe2O3, MgO, and trace el e ments: V, Ni, Cu, Zn in the stud ied sam ples. Dashed line cor re sponds to PAAS (Tay lor & McLennan, 1985)
Fig. 11. PAAS-nor mal ised con cen tra tions of TiO2 and high strength field trace el e ments: Zr, Nb, Th and Ga in the stud ied sam ples. Dashed line cor re sponds to PAAS (Tay lor & McLennan, 1985)
minite. The source ma te rial of bituminite is pre dom i nantly phytoplanctonic and bac te rial. To lower ex tent the bitumi-nite is de rived from zoo plank ton, cyanobacteria and other or ganic ma te rial (In ter na tional Com mit tee for Coal Pe trol -ogy, ICCP, 1993; Tyson, 1995).
The changed pro por tion of land to ma rine or ganic mat ter was di rectly re sulted by eustatic sea level rise, with max -i mum -in the ear l-i est Turon-ian (Jacqu-in et al., 1998). Th-is event has caused a de crease in sup ply of siliciclastic ma te rial to the Tethyan mar ginal bas ins and could pro mote in -creased nu tri ent sup ply to sur face wa ters that would have sup ported in creased pro duc tiv ity in epicontinental seas and mar ginal deep bas ins (cf. B¹k, 2007c).
The black shales of the BRSF dis play high con cen tra tion of Cd, Zn, V, Mo, Ag, As. An ex pla na tion of this phe -nom e non could be ma rine-or i gin of the or ganic mat ter. Biophile el e ments are ab sorbed by or gan isms and scav enged to sed i ment by or ganic mat ter. Cd, Ag and Se cor re -late with nu tri ent el e ments in sea-wa ter and can ac cu mu -late in the sed i ment pri mar ily bound to or ganic car bon (Ndung’u et al., 2001; Bruland, 1980). The black shales of
the Bonarelli-equiv a lent level analysed by B¹k (2007 a, b, c) re veal high val ues of the As/Al ra tio. The author pos tu lated that part of or ganic mat ter could be of al gaeder i va -tion. Ar senic is ab sorbed by plank tonic or gan isms (mainly by al gae) and ac cu mu lated within organic matter (France-sconi & Edmonds, 1998 in B¹k, 2007 c).
Cd and Ag as sul phideform ing met als can form the sta -ble sulphides (Jacobs et al., 1985). The stud ied sam ples are S en riched as well. It is pos si ble, that Sre lated traceel e ments could be in cor po rated into sed i ment dur ing pre cip i ta -tion of sulphides.
The min eral com po si tion of the stud ied clay ma te rial is cor re la tive with other Cre ta ceous sam ples. Rob ert and Chamley (1982) sug gest that the clay-min eral com po si tion of the Cre ta ceous oce anic sed i ments is rather a func tion of the pri mary source in put. These au thors came to the con clu sion that illite and chlorite were de tri tal in or i gin and in di
-cate the pe ri ods of in tense phys i cal ero sion, whilst smectite might ev i dence cli ma tic con di tion or vol ca nic ac tiv ity suit -able for neoformation of clay min er als (Chamley, 1989). In Spain, the Early Cre ta ceous suc ces sion are rich in kaolinite and illite. High amount of kaolinite sug gests that the de posit was formed un der warm, wet con di tion fa vour able to chem -i cal wather-ing of ac-id-ic rocks. To wards the top, the amount of smectite in creases grad u ally. The in crease in smectite indicates influence of the Cenomanian transgression (Chamley, 1989).
Fig. 12. K2O vs. Rb di a gram. The val ues of K2O/Rb ra tio in the stud ied sam ples are sim i lar to that of the PAAS (McLennan et al., 1990)
Fig. 13. Cr/V vs. Y/Ni di a gram. Ultra mafic sources have low Y/Ni and high Cr/V ra tio, con trary to gra nitic where Y/Ni is high and low Cr/V ra tio. Sam ples are dis trib uted close to the PAAS end-mem ber
Fig. 14. Dis crim i na tion di a gram (Andeozzi et al.,1997) show ing that the sam ples are mostly de rived from terrigenous sup ply
Clay min eral com po si tion of the in ves ti gated sam ples sug gests that the Lhoty For ma tion is en riched in illite and kaolinite, prob a bly terrigenous-de rived, whereas the shales of the BRSF con sist mainly of smectite-rich phases. Mineral com po si tion of the bentonites in the CTB in ter val suc ces -sion has been stud ied by Koszarski et al. (1962), Burtan & Turnau-Morawska (1978), and B¹k (2006). They ex hibit analogous pe trol ogy and de scribe the same igneous pro-vinces.
Hoffman and Hower (1979) have pro posed smectite per cent age in illite-smectite in shales to be a palaeogeother-mometer. They con cluded the on set of illitisation at 60°C, there fore high share of smectite in the in ves ti gated illite – smectite might in di cate a low-tem per a ture diagenesis.
DIAGENESIS
The diagenetic pro cesses have af fected the sed i ment stud ied. They are ev i denced by al ter ation of or ganic mat ter, as well as geo chem i cal (re la tion be tween REE, Mn, P2O5)
and min er al og i cal (py rite and clay min er als, ferro manga -nese nodules) imprints.
Dur ing diagenesis, the bituminite ma te rial be comes thin banded or fine grained and in creas ingly vitrinite-like (meta- bituminite af ter Teichmüller & Ottenjann, 1977 and micri-nite af ter ICCP, 1993). The metabitumimicri-nite might be more ac cu rate for the characterization of the coalification res i -dues of bituminite. Such macerals were in ter preted by Stasiuk (1993) as prod ucts of deg ra da tion and mi cro bial al -ter na tion of ma rine or ganic mat -ter, both within the wa -ter column and the sediment.
The high REE con cen tra tions might be a com bined ef -fect of the oc cur rence of Mn-oxyhydroxides (MnO-rich sed i ments scav enge Ce4+) and fish de bris (high P2O5 sed i
-ments in herit neg a tive Ce anom a lies) in the ar eas of slow pe lagic sed i men ta tion (Plank & Langmuir, 1998; Reynard
et al., 1999). None of the above pro cesses have af fected the
ana lysed sed i ment. Con se quently, REE were re dis trib uted in sed i ments dur ing diagenesis (Ras mus sen, 1996; Ras mus -sen et al., 1998; Lev et al., 1998, 1999) and this over print is re lated with the pres ence of sec ond ary min er als, such as phosphates and sul phur min er als. It seems to be the most prob a ble ex pla na tion for LC 5B and LC 5M sam ples that are MnO de pleted but en riched in REE, P2O5 and S.
Diagenetic or i gin of the ferro manga nese nod ules was pre sented by B¹k (2006, 2007a–d). Some chem i cal in di ces of the FeMn lay ers were stud ied in de tail in the rep re sen ta -tive sec tions of the Subsilesian and Skole nappes. The first Fe-Mn layer dis plays fea tures of hy drog e nous to diage netic sed i ment, while the sec ond one has fea tures of hy dro ther -mal deposit (B¹k, 2007 c, d).
Py rite in the in ter nal part of rhomboedric pseudo morphs oc curs as mas sive, ir reg u lar ag gre gates. Large oc ta -he dral crys tals (av er age 20 µm in di am e ter) ap pear within the light-col oured sam ples. They pre cip i tated in sed i ments un der ly ing oxic wa ter col umn (diagenetic; Wignall & New -ton, 1998). Con trary to thin framboidal (up to 10 µm in diam eter) py rite within the black shales. Framboids that are on the av er age smaller and less vari able in size was formed
in the euxinic wa ter col umn (syngenetic; Raiswell & Ber-ner, 1985; Wignall & Newton, 1998).
CON CLU SIONS
The major and trace el e ment geo chem is try of the silici-clastic and hemipelagic sed i ments of three lithostratigraphic units: Lhoty For ma tion, Barnasiówka Radiolarian Shale For ma tion and Var ie gated Shales from Lanckorona area, Pol ish Outer Carpathians sug gests a largely con ti nen tal source. A biogenic si li ceous source is re cog nised for the por tion of the Lhoty For ma tion and the BRSF of the stud ied suc ces sion. The in put of ma rine or ganic mat ter into de pos its of the mid dle part of BRSF is very im por tant as well. There -fore, it can be con cluded that the sup ply of ma te rial to the clay rich lay ers of the Lhoty For ma tion, BRSF and Var ie gated Shales sam pled in the Lanckorona area are mainly de -rived from two ma jor in puts. The first is a dom i nant terri-genous fine-grained com po nent, hav ing af fin ity with the average up per con ti nen tal crust. The sec ond com po nent of the source is a ma rine-de rived biogenic material (silica and organic substances – metabituminite).
The stud ied sed i ment was diagenetically al tered. The fol low ing data are ev i denc ing these con clu sions: coalifi-cat ion of bituminite, low-tem per a ture illitisation of smec-tite, pre cip i ta tion of sec ond ary min er als such as phos phates and sulphides, for ma tion of ferromanganese nodules.
Ac knowl edge ments
Krzysztof B¹k (Ped a gog i cal Uni ver sity), Zbigniew Saw³o-wicz (Jagiellonian Uni ver sity) and Jan Golonka (AGH Uni ver sity of Sci ence and Tech nol ogy) are thanked for valu able dis cus sion and com ments on the manu script. Wojciech Narêbski (Mu seum of the Earth) is ac knowl edged for im prov ing the Eng lish and Leszek Chudzikiewicz (In sti tute of Geo log i cal Sci ences, Pol ish Acad emy of Sci ences, Kraków) for help with ed i to rial re marks. This work was fi nan cially sup ported by a grant of the Pol ish Min is try of Sci -en tific Re search and In for ma tion Tech nol ogy no. 2P04D 080 29.
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