Tec tonic dis crim i na tion of siliciclastic sed i men tary re cord of the north ern Tethyan mar gin at the end of the Tri as sic
Marek VÏAÈNÝ1, Jozef MICHALÍK1, * and Otília LINTNEROVÁ2
1 Slo vak Acad emy of Sci ences, Earth Sci ence In sti tute, Geo log i cal Di vi sion, Dúbravská cesta 9, P.O. BOX 106, 840 05 Bratislava, Slovakia
2 Comenius Uni ver sity in Bratislava, Fac ulty of Nat u ral Sci ences, De part ment of Ge ol ogy of Min eral De pos its, Mlynská dol - ina, Ilkovièova 6, 842 15 Bratislava, Slovakia
Vïaèný, M., Michalík, J., Lintnerová, O., 2019. Tec tonic dis crim i na tion of siliciclastic sed i men tary re cord of the north ern Tethyan mar gin at the end of the Tri as sic. Geo log i cal Quar terly, 63 (1): 30–38, doi: 10.7306/gq.1458
As so ci ate ed i tor: Joachim Szulc
Tec tonic set ting of both the up per most Tri as sic Tomanová and the low er most Ju ras sic Dudziniec for ma tions can be char ac - ter ized by a se ries of di ag nos tic dis crim i na tion di a grams. High-sil ica and low-sil ica multi-di men sional di a grams in di cate that the sed i ments could have been de pos ited in the con ti nen tal col li sion/rift set ting. Di a grams of K2O/Na2O ver sus SiO2, SiO2/Al2O3 ver sus K2O/Na2O and Th-Co-Zr/10 as well as Th-Sc-Zr/10 de ter mine an or i gin from the tec toni cally ac tive and/or pas sive con ti nen tal mar gin set ting. REE pa ram e ters in di cate pre dom i nantly a pas sive mar gin tec tonic set ting of the sed i - ments. The most prob a ble source of clastic ad mix ture in the Scythian to Domerian sed i ments in the Tatric Unit was sit u ated in a rem nant of the Variscan collisional orogen – the Vindelician High lands. Oc ca sional mon soonal rains oc cur ring in or bit - ally con trolled cy cles trans ported weath ered ma te rial from the source area down river val leys on the sea ward slopes of the Variscan Vindelician Moun tains to wards the Tethyan Sea. The in put of this ma te rial in flu enced also the mar ginal parts of the Fatricum (e.g., Vysoká or Havran units).
Key words: sedimentology, geodynamics, ma jor and trace el e ments, palaeo ge ogra phy.
INTRODUCTION
Geo graph ical set ting. The area un der study, where the Tomanová For ma tion crops out on the sur face, lies in the Tatra Moun tains on both sides of the Slovakia/Po land state bor der (Jach et al., 2014). The most fa mous lo cal i ties are sit u ated in the Tomanová Val ley (Èervený Úplaz ra vine un der Gory - czkowa Mt. – N 49°266’296”, E 19°947’626”) (see Michalík et al., 1976) and in the Czerwone Wierchy Mts. (Tomaniarski Twardy Uplaz, Czerwone ¯lebki; Fig. 1).
Geo log i cal set ting. The tectonostratigraphic Tomanová Unit is a part of the post-Variscan sed i men tary cover of the Tatric Superunit in the Cen tral West ern Carpathians (Fig. 2).
This cover has been par tially de tached from its crys tal line (mostly gra nitic) fundament and folded into sev eral folds and digi ta tions. The Tomanová Unit rep re sents one of the deeper struc tures and used to be con sid ered a para-autochthonous or even an “autochthonous” unit by for mer au thors.
Pre vi ous stud ies. The “Tomanowa beds” have been de - fined by Raciborski (1890) as a com plex of var ie gated and black fine clastic sed i ments with abun dant palustrine flora, form ing a char ac ter is tic Up per Tri as sic mem ber in the homo - nymous tectonostratigraphic unit. Uhlig (1897) parallelized the lower part of this com plex with the Carpathian Keuper and the up per part with the Li assic Gresten Beds. Kotañski (1959) con - sid ered the Tomanová “beds” to be of Late Norian to Early Rhaetian age. Radwañski (1968) re garded them as Rhaetian ma rine de pos its. Michalík et al. (1976, 1988) con firmed the lac - us trine/palustrine char ac ter of the Tomanová For ma tion by find ings of three di no saur foot prints and by the char ac ter of an ac com pa ny ing plant as so ci a tion. NiedŸwiedzki (2011) found sev eral other di no saur foot prints on the Pol ish side of the High Tatra Mts.
Rock re cord. The Up per Tri as sic se quence in the Tatric Superunit of the Cen tral West ern Carpathians con sists mostly of clastic rocks (Michalík, 1994). The Rhaetian Tomanová For - ma tion over ly ing the Norian Carpathian Keuper in the Èervený Úplaz sec tion is built of a cy clic parasequence of argillites and sand stones. Quartz, kaolinite and 2:1 Al dioctahedral phyllo - silicates rep re sent the ma jor, slightly diagenetically al tered min - eral phases. The kaolinite/dioctahedral 2:1 ra tio de creas ing up - ward the sec tion (from 4.3 to 0.5) sig nal izes vari abil ity in the weath er ing/ero sion in ten sity and chang ing wa ter sa lin ity. The over ly ing Ju ras sic se quence starts with the ma rine Dudziniec
* Corresponding author, e-mail: geolmich@savba.sk Received: April 11, 2018; accepted: November 9, 2018; first published online: March 22, 2019
For ma tion. It con sists of sandy lime stones to cal car e ous sand - stones (Lintnerová et al., 2013).
Geo chem is try. Ma jor and trace el e ment (LILE, HFSE, REE) com po si tion of sed i ment sup poses an uni form source com posed of fel sic rocks (Lintnerová et al., 2013). U, V and Eu were mo bi lized by ox y gen re duced con di tions, and the high Fe con tent re sulted in a for ma tion of sid er ite and berthierine. The C iso tope com po si tion in di cates a con ti nen tal char ac ter of the or - ganic mat ter. The rel a tive de crease in d13Corg val ues in the Dudziniec For ma tion car bon ates in di cates a ma rine type of or - ganic mat ter and, in prin ci ple, it doc u ments ma rine trans gres - sion (Lintnerová et al., 2013).
Sedimentology. The min er al og i cal ma tu rity of clastic grains has been reached by long and strong chem i cal weath - er ing of fel sic rocks. Kaolinite crusts of the in tensely weath -
ered el e vated ar eas were eroded and trans ported down the river val leys into the ba sin as sup ported by lithofacies, min eral ho mo ge ne ity of sed i ments, and by their chem i cal prop er ties.
The ra tio of kaolinite to dioctahedral 2:1 phyllosilicates in argillite points to changes in ero sion in ten sity and phys i cal dif - fer en ti a tion dur ing sed i men ta tion. An event char ac ter of sand - stone lay ers con tain ing mixed ae olian and flu vial quartz grains is un der lined by the tex tural im ma tu rity of sed i ment par ti cles (Lintnerová et al., 2013).
En vi ron ment and palaeoclimate. Al ter na tion of dry and hu mid pe ri ods was at tested by the sed i men tary tex tures and by the ma tu rity of quartz (ae olian ver sus flu vial) grains, con tent of or ganic mat ter and its char ac ter (Corg and d13Corg). Shales with a high kaolinite con tent (2:1 phyllosilicates ± chlorite) are typ i cal of the Rhaetian pluvialized cli mate (Michalík et al., 2010) com -
Fig. 1. Geo graph ical lo ca tion (lower left cor ner) and geo log i cal sit u a tion of the cen tral part of the Tatra Mts., with in di ca tion of out crops of the Tomanová and Dudziniec for ma - tions (red ar eas), which are sit u ated along both sides of the Slo vak-Pol ish bor der line (af - ter Bezák et al., 2011, adapted)
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pa ra ble to con di tions gov ern ing the en tire Eu ro pean con ti nent (Norian-Hettangian kaolinization pe riod). Authigenic sid er ite or berthierine in the up per part of the Tomanová For ma tion may also in di cate wet (or even brack ish) and re duc ing con di tions.
The sed i men tary rate (83 mm/ky ac cord ing to the cyclo stra - tigraphic anal y sis) has been de ter mined by the quan tity of pre - cip i ta tions. The pro duc tion and de cay of or ganic mat ter were con trolled by hu mid ity (Michalík et al., 2007, 2010). The palaeo - sol for ma tion, trans port of eroded ma te rial, and en hance ment of bioproductivity in a limnic ba sin were evoked by pe ri od i cal cli - ma tic changes – “megamonsoons” com ing from the Tethyan Do main in prob a bly 400-ky-long ec cen tric ity cy cles (Lintnerová et al., 2013).
The sed i men tary rate of the Hettangian Dudziniec For ma - tion at tained 25 mm/ky, and the fin ing-up ward parasequences pre served in the se quence are sim i lar to those of the Toma - nová For ma tion (Lintnerová et al., 2013). How ever, quite dif fer - ent min er al ogy of clays, re cy cled char ac ter of sil i cates, raised cal cite de tri tus, and car bon ate d18O (from –9 to –11‰ PDB) and d13C (from –25 to –28‰ PDB) val ues doc u ment me te oric re- equil i bra tion within the parasequences. Grad ual sta bi li za tion of ma rine biota is re corded by the ver ti cal dis tri bu tion and en vi - ron men tal sig nif i cance of ben thic foraminifera. Involutinids and spirillinids dom i nate in the lower part of the Dudziniec For ma - tion, endothyrinids gov ern its mid dle part, and nodosariids and Ammodiscus-type micro fauna oc cur in the up per part (Lintne - rová et al., 2013).
Palaeo ge ogra phy and palaeotectonics. Sandy and ar gil - la ceous ma te rial of the Tomanová For ma tion was orig i nated by me chan i cal and chem i cal weath er ing of the Vindelician High - lands. Mon soonal winds com ing from the Tethys had been los ing their wa ter con tent above the sea ward slopes of these old moun - tains un til they came to the dry Mid-Eu ro pean Ba sin (Feist- Burkhardt et al., 2008). These slopes were cut by oc ca sional river val leys (Berra et al., 2010). The grad ual sea level rise in the Tatric Zone was trig gered by the ther mal ex pan sion of the Cen - tral At lan tic Rift, be ing also af fected by the in put of ter res trial clastics via fresh wa ter and wind (Lintnerová et al., 2013).
METHODS
Nine shale sam ples from the Tomanová For ma tion as well as two cal car e ous sand stone and two sandy lime stone sam - ples from the Dudziniec For ma tion (all ob tained from and de - scribed in Lintnerová et al., 2013) were ana lysed for ma jor and trace el e ments at the Acme An a lyt i cal Lab o ra to ries (Van cou - ver) Ltd in Can ada. Geo chem i cal anal y ses were car ried out for whole rocks with out ex tract ing the clay frac tion. Two in stru men - ta tion tech niques, in duc tively cou pled plasma op ti cal emis sion spec trom e try and mass spec trom e try (ICP-OES/MS), were used for the geo chem i cal anal y ses. The an a lyt i cal pro ce dures were de scribed in de tail by Lintnerová et al. (2013) and are briefly sum ma rized be low. The pul ver ized rock sam ples were mixed with LiBO2/Li2B4O7 flux. Later, cru ci bles were fused in a fur nace. The cooled beads were then dis solved in ACS grade ni tric acid. Fi nally, these beads were ana lysed by ICP-OES/MS.
In this study, the ma jor and trace el e ment data from the stud ied sed i ments (Ta ble 1) were used to in fer the tec tonic set - ting of the sed i men tary ba sin with the help of var i ous di ag nos tic di a grams pro posed by Roser and Korsch (1986), Bhatia and Crook (1986), Verma and Armstrong-Altrin (2013). To ap ply the multi-di men sional tec tonic dis crim i na tion di a grams of Verma and Armstrong-Altrin (2013), the DF1 and DF2 func tion co or di - nates for the sam ples were cal cu lated from the re spec tive
equa tions. How ever, the chem i cal data were first ad justed to 100% on an an hy drous (LOI-free) ba sis.
In or der to fur ther de ter mine the tec tonic set ting of the sed i - ments, their most char ac ter is tic rare earth el e ment (REE) pa - ram e ters were com pared with those of greywackes of a known tec tonic set ting (Bhatia, 1985). The sum of all REE de ter mined (La–Lu) is de noted by SREE. The SLREE/SHREE is the ra tio of the sum of light REE (La–Sm) to the sum of heavy REE (Gd–Yb). The La/Yb ra tio is an in dex of the en rich ment of LREE over HREE, and it is called LaN/YbN when ex pressed as the chondrite-nor mal ized ra tio. Chondrite val ues were taken from Boynton (1984), since this type of chondrite is one of the most com monly used in sed i men tary rocks. The value of Eu/Eu* rep - re sents the ra tio of ac tual nor mal ized Eu to in ter po lated nor mal - ized Eu for no de ple tion or en rich ment.
Orig i nal bulk rock chem i cal anal y ses of the sam ples stud ied and ba sic char ac ter is tics of their chem i cal com po si tion were pro vided by Lintnerová et al. (2013). In ad di tion, chem is try was used as the proxy of source rock weath er ing, re work ing, prov e - nance and sed i men tary and cli ma tic con di tions. In this pa per, we eval u ated the same geo chem i cal data to com ple ment and ex tend the above-men tioned study. New, com pared to our pre - vi ous con tri bu tion, was the use of the set of the afore men tioned anal y ses for tec tonic dis crim i na tion of the source area of cla - stics. Thus, the pres ent study con trib utes to the in ter pre ta tion of geodynamic pat tern of the whole north ern Tethyan shore.
MINERAL COMPOSITION AND BURIAL HISTORY OF THE SEDIMENTS
The quan ti ta tive min eral com po si tion of the stud ied sed i - ments was in ter preted from XRD pat terns by Lintnerová et al.
(2013). The ma jor min eral phases in the Tomanová sam ples were rep re sented by quartz (15–70%), kaolinite (13–46%) and 2:1 Al dioctahedral phyllosilicates (5–39%). The fourth min eral phase in cluded berthierine and prob a bly Fe-chlorite (3–14%).
In ter est ingly, sid er ite was the dom i nant phase in sam ple CU13R (39%), ac com pa nied by other Fe min er als, goethite (11%) and he ma tite (4%). Goethite was also re corded in other sam ples, but typ i cally in amounts lower than 2%. Like wise, bi o - tite and K-feld spar were iden ti fied in the ma jor ity of sam ples, but their con tents did not ex ceed 3%. Al bite, oligoclase, do lo mite, ana tase, rutile and il men ite oc curred only in trace amounts (<1%). The ma jor min eral phases in the Dudziniec sam ples were rep re sented by quartz (14–71%) and 2:1 dioctahedral phyllosilicates (3–14%). These sam ples were also en riched in cal cite (24–79%), while chlorite (0–4%) and kaolinite (1%) were de ter mined only in trace amounts.
It is well known that as sem blages of clay min er als can elu ci - date burial his tory of sed i ments. The most im por tant phe nom e - non of burial his tory of shales in cludes con tin u ous illitization of smectite via in ter me di ate mixed-layer illite-smectite (Kisch, 1983). Al though Lintnerová et al. (2013) iden ti fied illitic illite - -smectite in the sam ples from the Tomanová For ma tion, which could be a stage of illitization re sult ing from a burial tem per a ture of about 180–200°C (Pollastro, 1993), they ex cluded the pos si - bil ity that the sed i ments ex pe ri enced late diagenesis. Their ar - gu men ta tion was based on the pres ence of berthierine which is a typ i cal min eral of very early diagenesis, since it is trans formed to chamosite at tem per a tures over 70°C (Hornibrook and Long - staffe, 1996). More over, the com mon pres ence of dis or dered kaolinite and the oc cur rence of de tri tal illite-smectite and chlorite in the stud ied sam ples are strong in di ca tions that the rocks were not mark edly trans formed af ter de po si tion. Fi nally,
also the d18O shift to more neg a tive val ues in sid er ite sug gests a rel a tive weak diagenetic al ter ation (Lintnerová et al., 2013).
Thus, the in ten sity of diagenetic change of the sed i ments was no ta bly low and hence these sed i ments are suit able for tec tonic set ting de duc tions based on geo chem i cal data.
RESULTS
Ma jor and trace el e ment data from the Tomanová and Dudziniec for ma tions were plot ted for tec tonic set ting dis crim i -
T a b l e 1 ICP-de ter mined ma jor and some trace el e ment abun dances for sed i ments of the Tomanová and Dudziniec for ma tions
Sam ple CU1 CU3 CU5 CU7 CU10
A CU13 CU13R CU13
R1 CU15 CU37 CU40 CU44 CU55
Ma jor el e ments [wt.%]
SiO2 57.24 62.94 56.33 54.73 58.61 63.02 23.77 43.12 51.5 75.55 20.71 70.74 63.54
TiO2 1.28 1.6 1.14 1.39 1.46 1.18 0.42 0.82 0.89 0.12 0.13 0.15 0.82
Al2O3 25.94 23.3 19.5 26.2 21.55 21.82 7.13 13.33 25.75 2.29 2.37 2.15 11.67
Fe2O3 2.08 1.07 2.95 4.06 6.44 2.56 48.31 24.3 5.65 1.42 1.14 1.02 2.35
MnO 0.01 0.01 0.01 0.01 0.02 0.01 0.51 0.18 0.01 0.08 0.1 0.03 0.03
MgO 0.49 0.38 0.23 0.65 0.65 0.75 0.98 1.92 0.81 0.15 0.73 0.22 0.98
CaO 0.05 0.1 0.03 0.19 0.09 0.13 0.19 0.77 0.32 10.79 39.55 13.41 7.66
Na2O 0.26 0.31 0.21 0.4 0.27 0.25 0.01 0.05 0.45 0.05 0.04 0.03 0.1
K2O 1.32 0.63 0.78 1.21 0.93 0.89 0.21 0.41 2.83 0.43 0.7 0.54 3.24
P2O5 0.03 0.03 0.04 0.04 0.03 0.02 0.02 0.03 0.03 0.01 0.03 0.02 0.07
LOI 11.2 9.5 18.6 11 9.8 9.2 18.4 15.9 11.6 9.1 34.4 11.6 9.3 Trace el e ments [ppm]
Co 8.7 8.8 2.7 8.7 26.7 11.5 25.3 18.3 11.8 1.2 1.8 2.3 7.4 Sc 20 18 17 21 20 16 11 20 7 1 2 2 8 Th 22.5 24.5 18.7 25.9 32.7 24.5 8.8 17 14.7 3.2 4.5 5.9 16.1 Zr 245 460 357 207 297 411 180 363 120 99 164 252 730
Rare earth el e ments [ppm]
La 48.9 41.5 70.8 88.1 71.8 34.7 18 23.5 39.5 8.5 13.7 16.5 45.4 Ce 102.6 96.2 154.2 165.5 187 72.5 40.5 51.8 79.5 14.7 27.5 32.4 90.8
Pr 10.88 10.7 16.5 17.45 19.97 9.74 4.32 6.03 9.87 1.77 3.13 3.72 9.81
Nd 41.3 37.5 58.1 61.5 73.1 41.3 16.4 25.1 37 5.5 11.4 15.2 34.8
Sm 7.09 6.01 10.1 10.54 12.67 9.01 3.39 4.61 7.17 1.28 2.22 2.71 5.92
Eu 1.27 1.08 1.97 1.91 2.31 2.5 1.93 1.49 1.28 0.2 0.35 0.26 0.76
Gd 6.17 5.72 9 8.18 9.04 8.27 3.69 4.6 5.42 1.02 1.67 2.06 4.98
Tb 1.07 1.19 1.6 1.38 1.47 1.31 0.73 0.94 0.89 0.13 0.26 0.29 0.77
Dy 6.15 7.22 8.41 7.44 7.71 7.18 4.41 5.92 4.93 0.95 1.36 1.61 4.69
Ho 1.23 1.58 1.68 1.51 1.59 1.46 1 1.35 0.99 0.15 0.26 0.27 0.93
Er 3.52 4.65 4.54 4.21 4.5 4.16 2.84 3.74 2.97 0.49 0.7 0.87 3.21
Tm 0.5 0.71 0.66 0.61 0.67 0.63 0.43 0.57 0.45 0.07 11 13 48
Yb 3.34 4.66 4.09 3.76 4.43 3.94 2.69 3.67 2.92 0.42 0.81 0.93 3.44
Lu 0.51 0.71 0.62 0.55 0.66 0.62 0.4 0.55 0.45 0.05 0.13 0.15 0.54
Sam ples CU1–15 are from the Tomanová For ma tion and sam ples CU37–55 are from the Dudziniec For ma tion; CU1 – black-grey argillite; CU3 – black-grey argillitic shale; CU5 – black-grey argillitic shale; CU7 – black-grey argillite with cop per col oured coat ings;
CU10A – or ange-weath er ing grey argillite with sid er ite sphaeroids; CU13, CU13R, CU13R1 – grey argillites with sid er ite bulbs; CU15 – black-grey argillite with cop per col oured coat ings; CU37 – grey cal car e ous sand stone; CU40 – black sandy biodetrital lime stone;
CU44 – shaly cal car e ous sand stone with bi valve shells; CU55 – dark grey sandy lime stone with quartz peb bles; geo chem i cal data were taken from Lintnerová et al. (2013)
na tion. The di a gram of K2O/Na2O ver sus SiO2 is shown in Fig - ure 3. The fields in this di a gram rep re sent oce anic is land arc mar gin (ARC), ac tive con ti nen tal mar gin (ACM) and pas sive mar gin (PM), as in di cated in Roser and Korsch (1986). In as - much as the chem is try of siliciclastic sed i ments is in flu enced by the grain size, Roser and Korsch (1986) plot ted sand-mud cou - plets for re cent sed i ments to test the va lid ity of their di a gram for sands and muds. Gen er ally, they re ported that sed i ments plot where ex pected. Ex cep tions are forearc sands that plot in the ARC field, whereas the as so ci ated muds plot in the ACM field.
Our sam ples fall pre dom i nantly in the ACM field with a con sid - er able over lap into the PM field.
Sim i larly, four plate tec tonic set tings, the arc (A1), evolved arc (A2), ac tive con ti nen tal mar gin (ACM) and pas sive mar gin (PM), have been rec og nized in the SiO2/Al2O3 ver sus K2O/Na2O dis crim i na tion di a gram of Roser and Korsch (1986) (Fig. 4). On this di a gram, the sam ples stud ied fall again within the ACM field with sub stan tial over lap of both the Tomanová and the Dudziniec sed i ments into the PM field.
Bhatia and Crook (1986) iden ti fied the chem i cal el e ments La, Th, Zr, Nb, Y, Sc, Co and Ti as the most use ful in dis crim i - nat ing be tween sed i ments from dif fer ent tec tonic set tings and rec og nized dis tinc tive fields for four en vi ron ments – oce anic is - land arc (A), con ti nen tal is land arc (B), ac tive con ti nen tal mar - gins (C) and pas sive mar gins (D) – on bivariate plots of La ver - sus Th, La/Y ver sus Sc/Cr, Ti/Zr ver sus La/Sc and trivariate plots of La-Th-Sc, Th-Sc-Zr/10 and Th-Co-Zr/10. Fig ure 5 shows the plots of Th-Co-Zr/10 and Th-Sc-Zr/10 for both the Toma nová and the Dudziniec for ma tions. All sam ples fall within the C and D fields, ex cept for two sam ples of Fe-rich mud - stones (CU13R and CU13R1) which are placed in the B field.
Fig ure 6 shows two discriminant func tion-based ma jor-el e - ment di a grams for the tec tonic dis crim i na tion of clastic sed i - ments for high-sil ica [(SiO2)ad justed = 63–95%] and low-sil ica [(SiO2)ad justed = 35–63%] rocks (af ter Verma and Armstrong - -Altrin, 2013). Fields of three main tec tonic set tings, is land or con ti nen tal arc (ac tive vol ca nism), con ti nen tal rift (ex ten sion) and col li sion (com pres sion), are shown. These two multi-di - men sional di a grams can be con sid ered a tool for suc cess ful dis crim i na tion of the geotectonic set ting of older sed i men tary
bas ins (Armstrong-Altrin, 2015). On these high-sil ica and low-sil ica multi-di men sional di a grams (Fig. 6), the sed i ments stud ied are plot ted mostly in the col li sion field with se ri ous over - lap into the con ti nen tal rift field.
In ad di tion to the above, the mean val ues of REE pa ram e - ters of the Tomanová and Dudziniec for ma tions were com - pared to REE pa ram e ters in sed i ments of the oce anic is land arc, con ti nen tal is land arc, An dean-type con ti nen tal mar gin and pas sive mar gins (Ta ble 2). Most val ues of the REE pa ram e ters of the stud ied sed i ments are sim i lar to those of sed i ments from the pas sive mar gins. Spe cif i cally, the La, Ce, SREE and SLREE/SHREE val ues from the Tomanová For ma tion sam ples and the La/Yb, LaN/YbN and Eu/Eu* val ues from the Dudziniec For ma tion sam ples in di cate pas sive mar gin sed i ments.
DISCUSSION
The geo chem i cal com po si tion of clastic sed i men tary rocks is es pe cially a func tion of tec tonic set ting, prov e nance, weath - er ing, trans por ta tion and diagenesis. Trace el e ments (Th, Zr, Co, Ti and Sc) are the least mo bile el e ments dur ing weath er ing, trans por ta tion, de po si tion and diagenesis and are con sid ered the most use ful for de ter mi na tion of the na ture of tec tonic set - tings of sed i men tary rocks (Bhatia and Crook, 1986). Var i ous au thors (e.g., Zaid et al., 2015; Maslov et al., 2016; Hernández - -Hinojosa et al., 2018) used the ma jor and trace el e ment as - sem blage from clastic sed i ments to de ter mine their tec tonic set tings. Nev er the less, some sec ond ary pro cesses, such as diagenesis and weath er ing, could af fect the geo chem i cal com - po si tion. Our pre vi ous study re vealed that the in ten sity of dia - genetic over print in sed i ments from the Tomanová and Du - Fig. 3. Tec tonic dis crim i na tion di a gram (Roser and Korsch,
1986) of sed i ment sam ples from the Tomanová and Dudziniec for ma tions
Some sam ples were not plot ted in the di a gram, be cause
their val ues were out of the dis crim i na tion range Fig. 4. SiO2/Al2O3–K2O/Na2O di a gram (Roser and Korsch, 1986) dis crim i nat ing the tec tonic set ting of sed i ments sam pled from the Tomanová and Dudziniec for ma tions Dashed bound ary be tween arc and evolved arc set ting fields em - pha sizes the tran si tional na ture of these set tings; two sam ples (CU13R and CU13R1) from the Tomanová For ma tion with more anom a lous com po si tion (high Fe2O3 con tent) are marked by open cir cles, while the other Tomanová sam ples are marked by solid cir - cles
dziniec for ma tions was no ta bly low, but weath er ing was in tense as doc u mented by the high Th/U, CIW and CIA val ues (Lintnerová et al., 2013). The REE dis tri bu tions also in di cate en rich ment dur ing only the weath er ing pro cess. En rich ment of sta ble (Si, Al, Ti) and de ple tion of la bile (K, Na, Ca, Mg) ma jor el e ments are typ i cal fea tures of weath ered sil i cate rocks. Be - cause the ma jor and trace el e ment com po si tion of the Toma - nová For ma tion sam ples showed chem i cal ho mo ge ne ity, we sup pose that the weath er ing pro cess was dom i nantly iso che - mical, and el e men tal re dis tri bu tion was lim ited. Con se quently, the tec tonic set ting of the sed i men tary ba sin could be in ferred from the chem i cal com po si tion of the sam ples stud ied.
Crai gie (2018) pointed that mix ing of var i ous sources can sig nif i cantly change the prov e nance re sults, mak ing the ap pli - ca tion of tec tonic set ting di a grams mis lead ing. For tu nately, the over all set ting of the stud ied for ma tions re stricts any pos si - bil ity of source mix ing. We sup pose that re cy cling was also not so im por tant to af fect sig nif i cantly the chem i cal com po si tion of the in ves ti gated sed i ments. Con se quently, the prov e nance plots could be ap plied for the sam ples from the Tomanová and Dudziniec for ma tions. As in di cated in Fig ures 3–5, our sam - ples can be clas si fied as de rived from the pas sive to (for merly) ac tive con ti nen tal mar gin. Fig ure 6 sug gests that they came from the (Variscan) con ti nen tal col li sion and the (Palaeo -
alpine) rift set ting. Sim i larly, the REE char ac ter is tics in di cate that the sam ples bear mostly at trib utes of pas sive con ti nen tal mar gin sed i ments (Ta ble 2). More over, ac cord ing to Lintne - rová et al. (2013), the rel a tive in crease in Hf and higher Zr/Sc ra tios in these sam ples sug gest only fel sic or mixed fel sic ma - te rial from a pas sive con ti nen tal source but not from any vol ca - nic rocks. To sum ma rize, these data in di cate that the sed i - ments were de rived from the pas sive con ti nen tal mar gin. Al - though the sed i ments were most likely de pos ited on the pas - sive con ti nen tal mar gin, some sam ples bear at trib utes of ac - Fig. 5. Th–Co–Zr/10 and Th–Sc–Zr/10 plots (Bhatia and
Crook, 1986) of sed i ments sam pled from the Tomanová and Dudziniec for ma tions, il lus trat ing dis crim i na tion of tec tonic set ting
Dashed lines rep re sent dom i nant fields of var i ous tec tonic set tings; two sam ples (CU13R and CU13R1) from the Toma - nová For ma tion with more anom a lous com po si tion (high Fe2O3 con tent) are marked by open cir cles, while the other Tomanová sam ples are marked by solid cir cles
Fig. 6. Multi-di men sional discriminant func tion di a gram of high-sil ica sed i ments of the Tomanová and Dudziniec for ma - tions (up) and multi-di men sional discriminant func tion di a gram of low-sil ica sed i ments of the Tomanová and Dudziniec for ma - tions (down) (Verma and Armstrong-Altrin, 2013)
The m1 sub script in DF1 and DF2 rep re sents the high-sil ica di a gram based on loge-ra tios of ma jor el e ments and the m2 sub script in DF1 and DF2 rep re sents the low-sil ica di a gram based on loge-ra tios of ma jor el e ments. The discriminant func tion DF1 and DF2 equa tions come from Verma and Armstrong-Altrin (2013). The prob a bil ity bound aries for 70 and 90% prob a bil i ties are also shown as dot ted and dashed curves, re spec tively. Two sam ples (CU13R and CU13R1) from the Tomanová For ma tion with more anom a lous com - po si tion (high Fe2O3 con tent) are marked by open cir cles, while the other Tomanová sam ples are marked by solid cir cles
tive con ti nen tal mar gin prov e nance (Figs. 3–5), which very likely re flects old in her ited in for ma tion about their or i gin. Nev - er the less, this in ter pre ta tion of the tec tonic set ting in the source ar eas is open to fur ther dis cus sion, be cause it is based on lim ited data, and an in te grated petrographic-geo chem i cal ap proach could be more ac cu rate.
A con tin ual sup ply of clastic ma te rial from the con ti nen tal Palaeo-Eu ro pean fore land onto the Tethyan shelf dur ing the Tri as sic and Early Ju ras sic was in ter rupted dur ing the ex - tremely dry Mid dle Tri as sic time in ter val only. As con cerns the or i gin of this ma te rial, Michalík (1993, 1994) cal cu lated the size of the pos si ble source ar eas vs the size of bod ies of Lower Tri - as sic clastics, and he con cluded that the Al pine -Carpathian part of the north ern Tethyan shelf must have been sit u ated SW of the Bo he mian Mas sif. Mišík and Jablonský (2000) pointed that the Lower Tri as sic sand stones should have been sourced from the area be tween the Moldanubic Unit of the Bo he mian Mas sif and the Armorician Mas sif. Uher (1999) and Baèík and Uher (2007) ar gued that clasts or tour ma line-rich rocks could have been de rived from the west ern part of the Bo he mian Mas - sif, but they ex cluded their trans port from its east ern part.
Aubrecht et al. (2017) stated that the trans port of the Lower Carnian fine clastics onto the shelf would be pos si ble only through the de pres sion (gate) be tween the Bo he mian and Armorician mas sifs, and a huge delta of the Lunz Beds must have formed im me di ately south of it. The Carnian-Norian Carpathian Keuper var ie gated shales in the Tatricum con tain fre quent psam mit ic clastic rocks, in con trast to the more dis tal ar eas, typ i fied by do lo mite in ter ca la tions. Clastic ad mix ture is pres ent in the up per most Tri as sic and Lower Ju ras sic rocks (Baboš Quartz ite) in the Tatricum and the mar ginal Fatricum (McCann, 2008). In con trast, the Up per Ju ras sic and Lower Cre ta ceous siliciclastic in put came to the Fatric Ba sin mostly from the south (Michalík, 2007). The or i gin and trans port routes
of weath ered ma te rial onto the Al pine -Carpathian shelf have not been suf fi ciently ex plained, es pe cially, at the end of this time, when these ways should have been al ready cut by the open ing of the Penninic Rift (McCann, 2008).
CONCLUSIONS
The tec tonic set ting of the Tomanová and Dudziniec for ma - tions was il lus trated by chem i cal com po si tion of 13 sed i ment sam ples, us ing a se ries of var i ous di ag nos tic dis crim i na tion di a - grams. As in di cated by high-sil ica and low-sil ica multi-di men - sional di a grams, the ana lysed sed i ments bear signs of the con - ti nen tal col li sion/rift set ting. Di a grams of K2O/Na2O ver sus SiO2, SiO2/Al2O3 ver sus K2O/Na2O, Th-Co-Zr/10 and Th-Sc - -Zr/10 de ter mined their or i gin from the tec toni cally ac tive and pas sive con ti nen tal mar gin set ting. The ma jor ity of the REE pa - ram e ters sug gested the pas sive mar gin tec tonic set ting. The most prob a ble source of clastic ad mix ture in the Scythian to Domerian sed i ments in the Tatric Unit was the Vindelician High - lands, as a rem nant of the Variscan collisional orogen. The in - put of this ma te rial in flu enced also the mar ginal parts of the Fatricum (e.g., Vysoká or Havran units).
Ac knowl edge ments. The study was sup ported by the Sci - en tific Grant Agency of the Min is try of Ed u ca tion, sci ence, re - search and sport of the Slo vak Re pub lic and the Slo vak Acad - emy of Sci ences un der the grant VEGA 2/0090/19, and by the Slo vak Re search and De vel op ment Agency un der the con tract No. APVV-14-0118. We thank Prof. Tadeusz Marek Peryt and two anon y mous ref er ees for their valu able com ments and help.
Prof. A. Pfiffner and Mr. R. Li from the In sti tute of Ge ol ogy, Bern, are ac knowl edged for in spir ing con sul ta tions.
REFERENCES
Armstrong-Altrin, J.S., 2015. Eval u a tion of two mul ti di men sional dis crim i na tion di a grams from beach and deep-sea sed i ments from the Gulf of Mex ico and their ap pli ca tion to Pre cam brian clastic sed i men tary rocks. In ter na tional Ge ol ogy Re view, 57: 1446–1461.
Aubrecht, R., Sýkora, M., Uher, P., Li, X.-H., Yang, Y.-H., Putiš, M., Plašienka, D., 2017. Prov e nance of the Lunz For ma tion (Carnian) in the West ern Carpathians, Slovakia: heavy min eral study and in situ
T a b l e 2 Mean val ues of REE pa ram e ters of sed i ments from the Tomanová and Dudziniec for ma tions,
com pared to those of sed i ments from var i ous tec tonic set tings (af ter Bhatia, 1985)
REE pa ram e ters
Tomanová For ma tion (n = 9)
Dudziniec For ma tion (n = 4)
Sed i ments of oce anic is land arc
Sed i ments of con ti nen tal
is land arc
Sed i ments of An dean-type
con ti nen tal mar gin
Sed i ments of pas sive mar gins
La 49 21 8 ±1.7 27 ±4.5 37 39
Ce 106 41 19 ±3.7 59 ±8.2 78 85
SREE 244 113 58 ±10 146 ±20 186 210
La/Yb 12.9 17.0 4.2 ±1.3 11.0 ±3.6 12.5 15.9
LaN/YbN 8.7 11.5 2.8 ±0.9 7.5 ±2.5 8.5 10.8
SLREE/SHREE 8.7 5.0 3.8 ±0.9 7.7 ±1.7 9.1 8.5
Eu/Eu* 0.79 0.45 1.04 ±0.11 0.79 ±0.13 0.60 0.56
For the sake of sim plic ity and easy com par i son with Bhatia (1985), La, Ce and SREE mean val ues are pro vided in ppm
LA–ICP–MS U–Pb de tri tal zir con dat ing. Palaeo ge ogra phy, Palaeo - climatology, Palaeo ec ol ogy, 471: 233–253.
Baèík, P., Uher, P., 2007. Tour ma line group min er als from re de - pos ited tourmalinites in Lower Tri as sic quartzites of Tatric Unit, West - ern Carpathians: com po si tion and petro gen etic sig nif i cance (in Slo vak with Eng lish sum mary). Mineralia Slovaca, 39: 185–196.
Berra, F., Jadoul, F., Anelli, A., 2010. En vi ron men tal con trol on the end of the Dolomia Principale/Hauptdolomit depositional sys tem in the cen tral Alps: cou pling sea-level and cli mate changes. Palaeo ge - ogra phy, Palaeoclimatology, Palaeo ec ol ogy, 290: 138–150.
Bezák, V., Fleischer, P., Hanzel, V., Chovancová, B., Koreò, M., Kyselová, Z., Madarás, J., Maglay, J., Ostrožlík, M., Pavlarèík, S., Reichwalder, P., Bohuš, I., Èurlík, J., Ferenc, Š., Ferenèík, J., Michalík, D., Soják, M., Kuchariè, ¼., Michalík, J., Olšavský, M., Gross, P., Sýkora, M., Borecka, A., Danel, W., Derkacz, M., GaŸdzicka, E., Iwanow, A., Piotrowska, K., Zabielski, R., 2011. Tatry Mts. Geo log i cal ed u ca tional maps of Slovakia (map and guide book) (in Slo vak). State Geo log i cal In sti tute of Dionýz Štúr, Bratislava.
Bhatia, M.R., 1985. Rare earth el e ment geo chem is try of Aus tra lian Pa leo zoic graywackes and mudrocks: prov e nance and tec tonic con trol.
Sed i men tary Ge ol ogy, 45: 97–113.
Bhatia, M.R., Crook, K.A.W., 1986. Trace el e ment char ac ter is tics of graywackes and tec tonic set ting dis crim i na tion of sed i men tary bas - ins. Con tri bu tions to Min er al ogy and Pe trol ogy, 92: 181–193.
Boynton, W.V., 1984. Geo chem is try of the rare earth el e ments:
me te or ite stud ies. In: Rare Earth El e ment Geo chem is try (ed. P. Hen - der son): 63–114. Elsevier, New York.
Crai gie, N., 2018. Prin ci ples of El e men tal Chemostratigraphy. A Prac ti cal User Guide. Springer In ter na tional Pub lish ing, Cham.
Feist-Burkhardt, S., Götz, A.E., Szulc, J., Borkhataria, R., Geluk, M., Haas, J., Hornung, J., Jor dan, P., Kempf, G., Michalík, J., Nawrocki, J., Reinhardt, L., Ricken, W., Röhling, H.-G., Rüffer, T., Török, Á., Zühlke, R., 2008. Tri as sic. In: The Ge ol ogy of Cen tral Eu - rope, 2: Me so zoic and Ce no zoic (ed. T. McCann): 749–822. Geo log i cal So ci ety of Lon don, Lon don.
Hernández-Hinojosa, V., Montiel-García, P.C., Armstrong - -Altrin, J.S., Nagarajan, R., Kasper-Zubillaga, J.J., 2018. Tex tural and geo chem i cal char ac ter is tics of beach sands along the west ern Gulf of Mex ico, Mex ico. Carpathian Jour nal of Earth and En vi ron men tal Sci - ences, 13: 161–174.
Hornibrook, E.R.C., Longstaffe, F.J., 1996. Berthierine from the lower Cre ta ceous Clearwater For ma tion, Al berta, Can ada. Clays and Clay Min er als, 44: 1–21.
Jach, R., Rychliñski, T., Uchman, A., 2014. Sed i men tary Rocks of the Tatra Mts. Tatrzañski Park Narodowy, Wydawnictwa Zakopane.
Kisch, H.J., 1983. Min er al ogy and pe trol ogy of burial diagenesis (burial meta mor phism) and in cip i ent meta mor phism in clastic rocks.
De vel op ments in Sedimentology, 25B: 289–493.
Kotañski, Z., 1959. Stra tig ra phy, sedimentology and palaeo ge - ogra phy of the high-tatric Tri as sic in the Tatra Mts. Acta Geologica Polonica, 9: 113–145.
Lintnerová, O., Michalík, J., Uhlík, P., Soták, J., Weissová, Z., 2013. Lat est Tri as sic cli mate humidification and kaolinite for ma tion (West ern Carpathians, Tatric Unit of the Tatra Mts.). Geo log i cal Quar - terly, 57 (4): 701–728.
Maslov, A.V., Yalysheva, A.I., Podkovyrov, V.N., Glavatskikh, S.P., Graunov, O.V., Sergeeva, N.D., 2016. Lithochemical com po si - tion of sand stones of the Vendian Asha Group, South Urals. Li thol ogy and Min eral Re sources, 51: 347–374.
McCann, T., 2008. The Ge ol ogy of Cen tral Eu rope, 2: Me so zoic and Ce no zoic. Geo log i cal So ci ety of Lon don, Lon don.
Michalík, J., 1993. Me so zoic ten sional bas ins in the Al pine - -Carpathian shelf. Acta Geologica Hungarica, 36: 395–403.
Michalík, J., 1994. Notes on the paleogeography and paleo tectonics of the West ern Carpathian area dur ing the Me so zoic. Mitteilungen der Österreichishen Geologischen Gesellschaft, 86: 101–110.
Michalík, J. ed., 2003. Tri as sic/Ju ras sic Bound ary Events. Geo - log i cal In sti tute of the Slo vak Acad emy of Sci ences, Bratislava.
Michalík, J., 2007. Sed i men tary rock re cord and microfacies in di - ca tors of the lat est Tri as sic to mid-Cre ta ceous ten sional de vel op ment of the Zliechov Ba sin (Cen tral West ern Carpathians). Geologica Carpa - thica, 58: 443–453.
Michalík, J., Planderová, E., Sýkora, M., 1976. To the strati - graphic and paleogeographic po si tion of the Tomanová For ma tion in the up per most Tri as sic of the West Carpathians. Geologický Zborník Geologica Carpathica, 27: 299–318.
Michalík, J., Kátlovský, V., Hluštík, A., 1988. Plant re mains in the Tomanová For ma tion (up per most Tri as sic, West Carpathians): their or - i gin, com po si tion and diagenetic al ter ation. Geologický Zborník Geolo - gica Carpathica, 39: 523–537.
Michalík, J., Lintnerová, O., GaŸdzicki, A., Soták, J., 2007. Re - cord of en vi ron men tal changes in the Tri as sic-Ju ras sic bound ary in ter - val in the Zliechov Ba sin, West ern Carpathians. Palaeo ge ogra phy, Palaeoclimatology, Palaeo ec ol ogy, 244: 71–88.
Michalík, J., Biroò, A., Lintnerová, O., Götz, A.E., Ruckwied, K., 2010. Cli ma tic change at the T/J bound ary in the NW Tethyan Realm (Tatra Mts, Slovakia). Acta Geologica Polonica, 60: 535–548.
Mišík, M., Jablonský, J., 2000. Lower Tri as sic quartzites of the West ern Carpathians: trans port di rec tions, source of clastics. Geolo - gica Carpathica, 51: 251–264.
NiedŸwiedzki, G., 2011. A Late Tri as sic di no saur-dom i nated ichno fauna from the Tomanová For ma tion of the Tatra Mts, cen tral Eu - rope. Acta Palaeontologica Polonica, 58: 291–300.
Pollastro, R.M., 1993. Con sid er ations and ap pli ca tions of the illite/smectite geothermometer in hy dro car bon-bear ing rocks of Mio - cene to Mis sis sip pian age. Clays and Clay Min er als, 41: 119–133.
Raciborski, M., 1890. Rha etic flora in the Tatra Mts (in Pol ish).
Rozprawy Wydzia³u Matematyczno-Przyrodniczego, Akademia Umie - jêtnoœci Kraków, 21: 243–260.
Radwañski, A., 1968. Pet ro graph i cal and sedimentological study of the High-Tatric Rha etic in the Tatra Mts. (in Pol ish with Eng lish sum - mary). Studia Geologica Polonica, 25: 1–146.
Roser, B.P., Korsch, R.J., 1986. De ter mi na tion of tec tonic set ting of sand stone-mudstone suites us ing SiO2 con tent and K2O/Na2O ra tio.
The Jour nal of Ge ol ogy, 94: 635–650.
Uher, P., 1999. Clasts of tour ma line-rich rocks in Lower Tri as sic quartzites, the Tatric Unit, Cen tral West ern Carpathians: tour ma line com po si tion and prob lem of source ar eas. Geologica Carpathica, 50:
140–141.
Uhlig, V., 1897. Geologie der Tatragebirges I. Einleitung und der stratigraphisches Theil. Anzeiger der Akademische Wissenschaften, Mathematisch-Naturwissenschafliche Klasse, 64: 643–684.
Verma, S.P., Armstrong-Altrin, J.S., 2013. New multi-di men - sional di a grams for tec tonic dis crim i na tion of siliciclastic sed i ments and their ap pli ca tion to Pre cam brian bas ins. Chem i cal Ge ol ogy, 355:
117–133.
Zaid, S.M., Elbadry, O., Ramadan, F., Mohamed, M., 2015. Pe - trog ra phy and geo chem is try of Pharaonic sand stone mon u ments in Tall San Al Hagr, Al Sharqiya Governorate, Egypt: im pli ca tions for prov - e nance and tec tonic set ting. Turk ish Jour nal of Earth Sci ences, 24:
344–364.
