De tri tal tour ma line as an in di ca tor of source rock li thol ogy: an ex am ple from the Ropianka and Menilite for ma tions (Skole Nappe, Pol ish Flysch Carpathians)
Dorota SALATA1, *
1 In sti tute of Geo log i cal Sci ences, Jagiellonian Uni ver sity, Oleandry 2a, 30-063 Kraków, Po land
Salata D. (2014) De tri tal tour ma line as an in di ca tor of source rock li thol ogy: an ex am ple from the Ropianka and Menilite for - ma tions (Skole Nappe, Pol ish Flysch Carpathians). Geo log i cal Quar terly, 58 (1): 19–30, doi: 10.7306/gq.1133
Tour ma line pop u la tions stud ied from the Campanian–Maastrichtian part of the Ropianka (Up per Cre ta ceous–Paleocene) and Menilite (Oligocene) for ma tions of the Pol ish Carpathians, rep re sent a mix ture of first-cy cle and polycyclic grains. The tour ma lines of the de pos its stud ied dis play very strong re sem blance in terms of op ti cal fea tures and chem i cal com po si tion.
They be long mostly to the schorl-dravite se ries with a mi nor con tri bu tion of tour ma lines of foititic or Mg-foititic com po si tion.
Euhedral tour ma lines orig i nated from metasedimentary rocks, while the rounded grains crys tal lised in Li-poor gra nitic rocks or in pegmatites, Al-poor and Al-rich metasedimentary rocks. Most of the tour ma lines stud ied crys tal lised dur ing a sin gle ig - ne ous or meta mor phic event. How ever, tour ma lines form ing in evolv ing chem i cal con di tions as well as polymetamorphic grains (hav ing a meta mor phic de tri tal core and meta mor phic overgrowths) are also pres ent. The chem i cal com po si tion of the meta mor phic tour ma lines stud ied in di cates their for ma tion in me dium-grade meta mor phic con di tions. This is sup ported by the crystallisation tem per a ture of the gar net-bi o tite in clu sion pres ent in one of rounded meta mor phic tour ma lines from the Ropianka For ma tion. The euhedral grains de rive from meta sedi ments, di rectly from a mas sif lo cated close to the Skole Ba - sin. The scar city of euhedral grains in the tour ma line pop u la tions stud ied sug gests that their source rocks were poor in these min er als. The di rect sources of rounded tour ma lines (most prob a bly polycyclic grains), may have been Pa leo zoic and Me so - zoic sed i men tary rocks of the Skole Ba sin fore land or crys tal line rocks of re mote source ar eas. The ini tial ig ne ous and meta - mor phic host rocks of the tour ma lines may have been crys tal line do mains of the Bo he mian Mas sif and/or the crys tal line base ment of Brunovistulicum.
Key words: de tri tal tour ma line, source rocks, Ropianka Fm., Menilite Fm., Skole Nappe, Outer Carpathians.
INTRODUCTION
Tour ma line is a min eral of ten found as a con stit u ent of gran ites and as so ci ated pegmatites and re gion ally meta mor - phosed sed i men tary rocks. How ever, it may be also a prod uct of diagenetic pro cesses (e.g., Henry and Guidotti, 1985; Henry and Dutrow, 1996; Dutrow and Henry, 2011 and ref er ences therein; Hinsberg et al., 2011a, b). Tour ma line is sen si tive to physicochemical con di tions in the host en vi ron ment, re flect ing these in its chem i cal com po si tion. Due to its high re sis tance to weath er ing, me chan i cal abra sion and burial diagenesis, it pre - serves in the sed i men tary en vi ron ment, be ing able to sur vive mul ti ple cy cles of sed i men ta tion (Mor ton and Hallsworth, 1999, 2007). The tour ma line crystallisation en vi ron ment may be elu ci - dated us ing data ob tained by means of the com monly avail able elec tron microprobe. Ig ne ous tour ma line can be dis crim i nated from metasedimentary tour ma line by means of mo lec u lar pro - por tions of Mg, Fe, Ca, and Al (Henry and Guidotti, 1985; Henry and Dutrow, 1996) and also of flu o ride ions and lith ium con tent
(Henry and Dutrow, 1996). There fore, tour ma line is a valu able min eral in source rock li thol ogy de ter mi na tion, es pe cially for heavy min eral as sem blages of an cient or re worked sed i ments, usu ally de pleted in highly di ag nos tic min er als, that are un sta ble dur ing burial diagenesis (e.g., Mor ton and Hallsworth, 1999, 2007).
This study of tour ma line pop u la tions pres ents an a lyt i cal data con cern ing this min eral in the Campanian–Maastrichtian part of the Ropianka For ma tion (Up per Cre ta ceous–Paleo - cene) and the Kliva and Boryslav sand stones of the Menilite For ma tion (Oligocene). Re cent data con cern ing tour ma lines from the Menilite For ma tion (Salata, 2013a) are sup ple mented with ad di tional de tails and com bined with new data on tour ma - lines from the Ropianka For ma tion. The cur rent work is a com - pi la tion of an a lyt i cal data and com par i son of tour ma line oc cur - ring in heavy min eral as sem blages of the parts of the Ropianka and Menilite for ma tions stud ied. The data ob tained en able de - ter mi na tion of the source rock li thol ogy of the tour ma line pop u - la tions stud ied and shed more light on their source ar eas pos si - ble lo ca tion and li thol ogy.
GEOLOGICAL SETTING AND SAMPLING
The Skole Nappe is sit u ated at the north east ern mar gin of the Outer Carpathians in Po land (Fig. 1A). It was a trough ini -
* E-mail: dorota.salata@uj.edu.pl
Received: August 9, 2013; accepted: September 27, 2013; first published online: November 21, 2013
20 Dorota Salata
Fig. 1. Geo log i cal maps with lo ca tion of the pro files sam pled for heavy min eral anal y ses: A – sam pled lo cal i ties of the Boryslav and Kliva sand stones of the Menilite For ma tion (black cir cles); B – sam pled lo cal i ties of the Ropianka For ma tion sand stones (red cir cles) (Salata and Uchman, 2013; Salata, 2013c)
Part A based on Kotlarczyk and Leœniak (1990); part B based on Wdowiarz (1949) with mod i fied de scrip tions of the lithostratigraphic units
tially about 150 km wide (G¹ga³a et al., 2012) that was bor dered by the Eu ro pean Plat form in the north and by the Subsilesian Ridge in the south (e.g., Ksi¹¿kiewicz, 1962). The sed i ment fill of the ba sin was folded and thrusted north wards dur ing the Mio - cene, and so the south ern mar gin of the ba sin fore land lies now be neath the Carpathian nappes, un avail able for di rect in ves ti - ga tion. The palaeotransport di rec tions show that the part of Skole Ba sin stud ied here was sup plied mainly from the north- west dur ing sed i men ta tion of the Ropianka and Menilite for ma - tions (e.g., Ksi¹¿kiewicz, 1962; Kotlarczyk, 1966, 1976;
Œl¹ czka and Unrug, 1966; Bromowicz, 1974; Kotlarczyk and Leœniak, 1990). Sed i ments in these for ma tions are be lieved to have been de rived from the North ern Mar ginal Cor dil lera that was sit u ated some where at the lon gi tude of the pres ent-day lo - ca tion of Tarnów (e.g., Ksi¹¿kiewicz, 1962; Unrug, 1979).
There fore, the ar eas of the Skole Nappe stud ied, south-east of Rzeszów and £añcut (Fig. 1), rep re sent re gions lo cated close to the south ern mar gin of the Skole Ba sin fore land.
The Up per Cre ta ceous–Paleocene de pos its of the Skole Nappe are dis tin guished as the Ropianka For ma tion (called also the Inoceramian Beds in the older lit er a ture; Kotlarczyk, 1978 and ref er ences therein). They are over lain by the up per Paleocene–Eocene mudstone-dom i nated Var ie gated Shale For ma tion and the Eocene Hi ero glyphic For ma tion (Rajchel, 1990; Fig. 2). The de pos its stud ied, sam pled in the area SE of
£añcut, be long to the Wiar and Leszczyny mem bers of the Ropianka For ma tion (Kotlarczyk, 1978), which were de pos ited by den sity-flow cur rents. The sand stone-dom i nated sec tions rep re sent prox i mal parts of the depositional sys tem (the chan - nel fa cies of a sub ma rine fan in the Manasterz, Husów – Pat ria, Husów – Biedroniówka, Niewa¿ka sec tions) and more dis tal parts of the sys tem (depositional lobes, interlobes or fan fringes in the Husów – Gaj, Husów – B¹kowiec, Husów – Bagnisty Stream, Rzeki – G¹szcz Stream, Tarnawka – leœniczówka A, B, Tarnawka 1–5, Tarnawka Quarry sec tions; Fig. 1B; for de tails of sam pled sec tions see Salata and Uchman, 2013). The sand - stones of the Ropianka For ma tion, in the area stud ied, are quartz-dom i nated but they con tain also feld spars, lithic frag - ments and subordinately mica, glauconite and coalified plant de bris. Among the lithic frag ments, lime stones and si li ceous rocks pre vail. Ad di tion ally, ig ne ous rocks, such as fine-grained granitoids, dacites, mica-schists and gneiss es, are also pres ent (e.g., Bromowicz, 1974, 1986 and ref er ences therein). The sand stones rep re sent mainly fine- to me dium-grained and well- to mod er ately-sorted sublitharenite and sub or di nate subarkose types (Bromowicz, 1974).
The Oligocene and Lower Mio cene infill of the Skole Ba sin be longs to the Menilite and Krosno for ma tions – the high est de - pos its of the sed i men tary suc ces sion of the Skole Nappe (Kotlarczyk, 1966; Kotlarczyk and Leœniak, 1990). The char ac - ter is tic rocks of the Menilite For ma tion are dark, black or brown shales, though thick sand stone units are also pres ent (Fig. 2).
Sand stones dom i nate in the Kliva and the Boryslav Sand stone mem bers, which were de pos ited as grav ity-driven flows, mainly in the Rzeszów and £añcut chan nel zones, but the Kliva sand - stone types may be also found out side them (Kotlarczyk and Leœniak, 1990). The sand stones for heavy min eral and the tour - ma lines anal y ses were sam pled in the de pos its of the north ern parts of the chan nel zones (Fig. 1A; for de tails of sam pled sec - tions see Salata and Uchman, 2012). The Kliva and the Bory - slav sand stone types are lithologically sim i lar. They are quartz- dom i nated, mostly fine- to me dium-grained and well- to mod er - ately-sorted. Quartz is ac com pa nied by feld spars and mus co - vite, and in some places by glauconite. Among clasts, coal pieces, cherts and siltstones are com mon. The sand stones are poorly ce mented, mostly mas sive, rarely lam i nated (e.g., ¯giet, 1963; Kotlarczyk, 1966, 1976; Œl¹czka and Unrug, 1966).
ANALYTICAL METHODS
The sand stones sam ples are weakly or very weakly con sol i - dated rocks in both for ma tions. There fore, the pre pa ra tory pro - ce dure to heavy-min eral sep a ra tion in cluded only gen tle dis in - te gra tion and rins ing with wa ter to clean off the clay frac tion, fol - lowed by siev ing to ob tain the 63–250 µm frac tion. The heavy min er als were sep a rated us ing the grav i ta tional method in so - dium polytungstate with a den sity of 2.9 g/cm3. The sep a rated heavy-min eral frac tion was mounted in Can ada bal sam, and de scribed and counted us ing a polar is ing op ti cal mi cro scope. In each sam ple, 200 to 300 grains of trans par ent, non-micaceous min er als were counted, ac cord ing to the rib bon method (Gale - house, 1971). Min eral fre quen cies were cal cu lated as num ber per cent ages (Salata and Uchman, 2012, 2013).
Ob ser va tions in the microfield and iden ti fi ca tion of min eral in clu sions in tour ma line grains were per formed us ing a Hitachi S-4700 Field Emis sion Scan ning Elec tron Mi cro scope in the Lab o ra tory of Field Emis sion Scan ning Elec tron Mi cros copy and Microanalysis, at the In sti tute of Geo log i cal Sci ences, Jagiellonian Uni ver sity, Kraków. The chem i cal com po si tion of tour ma lines, and gar net and bi o tite in clu sions for ther mo met ric
Fig. 2. Strati graphic scheme of the Skole Nappe (based on Gasiñski and Uchman, 2009 and ref er ences therein) with in di ca tion of the time-span in ter vals of the Ropia - nka and Menilite for ma tions stud ied (grey rect an gles) Fm. – for ma tion, Mb. – mem ber, Ss – sand stone, TRShMb – Trójca Red Shale Mem ber, VSh – Var ie gated Shale, ChSMb – Chmielnik Striped Sand stone Mem ber
data, was de ter mined in car bon-coated, pol ished thin sec tions, us ing a Cameca SX-100 elec tron microprobe (EMP), op er ated in wave length dis per sion (WDS) mode, at the Joint-In sti tute An - a lyt i cal Com plex for Min er als and Syn thetic Sub stances of War saw Uni ver sity. The WDS an a lyt i cal con di tions were as fol - lows: 15 kV ac cel er at ing volt age, 20 nA beam cur rent and a fo - cused beam. The fol low ing, syn thetic and nat u ral, min eral stan - dards were used for cal i bra tion: Si (wollastonite and di op side), Al and K (orthoclase), Cr (Cr2O3), Ti (rutile), Mg (di op side), Fe (Fe2O3), Mn (rhodo nite), Ca (di op side and wollastonite), Na (al - bite), F (phlogopite). Tour ma lines were ana lysed us ing sin - gle-spots (one or two spots per grain) as well as along tra - verses. Tour ma line grains for sin gle-spot microprobe anal y ses were cho sen ran domly for elec tron anal y ses. Tour ma lines for tra verse-anal y ses were hand picked un der a stereomicroscope and ar ranged in rows. To check chem i cal inhomogeneity, pre - lim i nary tra verse anal y ses were per formed for tour ma lines dis - play ing vis i ble changes in col our and those look ing ho mog e - nous. In ter nal col our inhomogeneity, vis i ble in trans mit ted light, was also re flected as darker or lighter zones in back-scat tered elec tron im ages (BSE). Tra verse anal y ses re vealed that change in chem i cal com po si tion was dis played only by tour ma - lines that were non-ho mog e nous in terms of col our. There fore, for homogenously-look ing tour ma lines only sin gle or two-spot anal y ses were made. In to tal, microprobe anal y ses were made for 153 tour ma line grains in the Ropianka For ma tion and 123 grains in the Menilite For ma tion.
The amounts of B, H and Li were not mea sured in the tour - ma lines. The con tents of these el e ments were cal cu lated us ing stoichiometric con straints, as sum ing B = 3 apfu (at oms per for - mula unit), OH + F = 4 apfu, Li = 15 – (T + Z + Y) and that all iron is Fe2+. The struc tural for mula cal cu la tions were nor mal ised to 31 an ions. Al though the cal cu la tion method ig nores oxy-tour - ma line spe cies and means that the ex act con tents of non-mea - sured el e ments and ac cord ingly the cal cu lated cat ion amounts are not pre cise (in par tic u lar Li2O and H2O amounts are likely over es ti mated), the re sults are suf fi ciently truth ful for sed i men - tary prov e nance in ter pre ta tions (e.g., Henry and Guidotti, 1985;
Henry et al., 2011).
The gar net-bi o tite geothermometer of Holdaway (2000, 2004) was used to es ti mate the tem per a ture of the gar net-bi o - tite in clu sion and its host tour ma line crystallisation.
RESULTS
TOURMALINE CONTENT AND VARIETIES
Tour ma line be longs among the main con stit u ents of heavy min eral as sem blages in the Ropianka and Menilite for ma tions, com pris ing amounts of 19–31% and 20–35% re spec tively. To the re main ing com po nents, co ex ist ing with tour ma line in the heavy min eral as sem blages stud ied, be long zir con, rutile, gar - net, staurolite, Al2O5 poly morphs (platy kyan ite and less fre - quently an da lu site; the lat ter de tected only in the Menilite For ma - tion), ap a tite, sin gle grains of am phi bole (found only in the Ropianka For ma tion), epidote and Cr-spinel. By com par i son, the Ropianka For ma tion dis plays rel a tively higher amounts of zir con, gar net and ap a tite, while the Menilite For ma tion con tains more kyan ite and staurolite, whereas ap a tite is al most ab sent. The zir - con–tour ma line–rutile in dex value (ZTR; Hubert, 1962) in both for ma tions var ies across a broad range com pris ing 27–95% and 29–55% in the Ropianka and Menilite for ma tions re spec tively.
Higher val ues of the ZTR in dex in the Ropianka For ma tion, in re - la tion to the Menilite For ma tion, re sult mainly from el e vated zir - con fre quen cies (Salata and Uchman, 2012, 2013).
In the tour ma line pop u la tions stud ied, the same and com - pa ra ble amounts of tour ma line va ri et ies are pres ent both in the Ropianka and Menilite for ma tions. Con sid er ing the round ness de gree, three types of grains were dis tin guished in both for ma - tions (Salata and Uchman, 2013):
– euhedral crys tals or frag ments of them (Fig. 3A, B);
– subrounded grains (Fig. 3C, D);
– highly rounded grains (Fig. 3E).
Among these, grains with smoothed sur faces (Fig. 3A–E), not dis play ing post-depositional diagenetic dis so lu tion fea tures, are most fre quent, but highly cor roded ones (Fig. 3F) may be also found. In terms of col our, brown and ol ive-brown, green, blue and pink va ri et ies oc cur in both for ma tions stud ied (Salata and Uchman, 2012, 2013). Rounded and subrounded brown tour ma line grains are dom i nant com pris ing 30–60% and 10–30% of tour ma line pop u la tions re spec tively. Amounts of rounded and subrounded green tour ma line reach 10%, while pink and blue tour ma line is pres ent rarely in in di vid ual sam ples, in amounts lower than 1%. Among the an gu lar and euhedral tour ma line group, brown va ri et ies are most typ i cal com pris ing up to 20%, while green tour ma line is less fre quent, oc cur ring in amounts from 1 to 5%. An gu lar tour ma line frag ments and euhedral pink and blue tour ma line is very rare, less fre quent than 1%, and pres ent only in a few sam ples (Salata and
22 Dorota Salata
Fig. 3. Tour ma line types in terms of their round ness de gree SEM im ages: A, B – frag ment of a euhedral crys tal; C – frag ment of a prism with mod er ately rounded edges; D – tour ma line prism with highly rounded edges but still dis tin guish able shape; E – highly rounded grain; F – piece of tour ma line with ad vanced cor ro sion microtextures
Uchman, 2013). The tour ma lines ex am ined are mostly ho mo - ge neous in col our when seen in the trans mit ted light in Can ada bal sam. The inhomo geneous tour ma lines dis play var i ous col - our zonation pat terns rang ing from very reg u lar os cil la tory to ir - reg u lar and “patchy” (Fig. 4).
TOURMALINE COMPOSITION
The microprobe anal y ses have re vealed that the chem i cal com po si tion of the tour ma lines ana lysed from the Ropianka and Menilite for ma tions is very sim i lar. The dom i nant cat ion oc - cu py ing the X-site in the greater part of the tour ma line stud ied, both chem i cally ho mo ge neous and zonal, is Na, the amounts of which vary mostly in the range of 0.4–0.9 apfu (Fig. 5 and Ap - pen di ces 1–3*). The Ca con tent is usu ally lower than 0.2 apfu but over a dozen tour ma lines of the Ropianka For ma tion dis - play slightly el e vated val ues, com pared to the Menilite For ma - tion, amounts of this el e ment reach ing up to 0.5 apfu (Fig. 5).
The po tas sium con tent is sub or di nate, not ex ceed ing 0.02 apfu.
The tour ma lines dis play X-site va cancy (Xvac) val ues gen er ally lower than 0.5, which en ables one to clas sify them to the al kali pri mary group. Only few grains, with Xvac slightly above 0.5, be - long to the X-va cant group (Fig. 5; Henry et al., 2011).
The dom i nant di va lent cat ions in the Y-site po si tion of the tour ma line struc ture are Fe and Mg, the amounts of which, and ac cord ingly the Mg/(Mg + Fe) ra tio val ues, vary in a very broad range from nearly 0.0 to over 0.8 (Fig. 5 and Ap pen di ces 1–3).
There fore, most of the tour ma line rep re sents the schorl-dravite se ries. The in fre quent Fe- and Mg-rich tour ma line, with el e - vated Al con tents, dis plays foititic and Mg-foititic com po si tion re spec tively (Fig. 5 and Ap pen di ces 1–3). Such a com po si tion was es tab lished in the pop u la tion of ho mo ge neous tour ma line and in zones of some zonal tour ma lines (Fig. 6 and Ap pen di ces 1–3). The scarce euhedral tour ma line or grains with slightly rounded edges dis play dravitic com po si tion or com po si tions chang ing from schorl in the cen tral part to dravite in the rim (grains M_t3_rz1, R_t10_rz1, R_t12_rz1; Fig. 6 and Ap pen di - ces 2, 3). The flu o ride ion, Ti as well as the cal cu lated Li amounts in all tour ma lines are very low and do not ex ceed 0.3 apfu, while the re main ing Mn and Cr con tents mostly do not ex ceed 0.04 apfu (Ap pen di ces 1–3). The tet ra he dral po si tion is mostly fully oc cu pied by Si, while Al, if pres ent, is usu ally much lower than 0.2 apfu (Ap pen di ces 1–3).
The tour ma line that is ho mo ge neous in col our does not dis - play chem i cal zon ing ei ther, while in tour ma line that shows dis - tinct changes of col our, fluc tu a tions in Fe and Mg con tent and, less fre quently, in Ca, Na (Fig. 6 and Ap pen di ces 2, 3) or Al amounts (Ap pen di ces 2, 3), were ob served. Such a change in the con tent of el e ments be tween col our zones of ten does not in flu ence af fil i a tion to a min eral spe cies, even if the vi sual col - our change be tween zones was pro nounced (Figs. 4, 6 and Ap - pen di ces 2, 3). How ever, in sev eral grains, the com po si tion of tour ma line changes through their cross-sec tions. In such cases, mainly schorl « dravite and less fre quently schorl « foitite or com bi na tions of schorl « foitite « dravite tran si tions were ob served (Fig. 6 and Ap pen di ces 2, 3). Two grains, la - belled R_t5_rz5 and R_t7_rz2 from the Ropianka For ma tion, seem to dis play com plex struc ture with an older de tri tal core and sub se quent rim (Fig. 4). The for mer grain dis plays dravitic com po si tion in the core and schorlitic in the rim, while in the lat -
ter grain the compositional change is re versed (Fig. 6 and Ap - pen dix 2).
The tour ma line stud ied con tains nu mer ous solid in clu sions.
To the most typ i cal be long quartz, TiO2 poly morphs, zir con, bi o - tite and monazite (Fig. 7A–D). Less fre quently in clu sions of Fe-ox ides, ap a tite, py rite, cal cite, feld spar, ti tan ite and gar net oc cur. An in clu sion of co ex ist ing almandine gar net and bi o tite (Ap pen dix 4) was found in a cer tain tour ma line of dravitic com - po si tion (R_t13_rz3) in the Ropianka For ma tion (Fig. 7E). The crystallisation tem per a ture of the gar net-bi o tite in clu sion, es ti - mated with the use of the gar net-bi o tite geothermometer of Holdaway (2000, 2004), was 511 ± 20°C (Ap pen dix 4).
DISCUSSION OF TOURMALINE PROVENANCE
GENERAL REMARKS
Chem i cal anal y ses re vealed that gra nitic and meta mor phic tour ma lines oc cur in the tour ma line pop u la tions ana lysed (Fig.
8A), but the lat ter pre vail in both for ma tions. Gra nitic tour ma - lines com prise 41% and meta mor phic tour ma lines 59% of to tal tour ma line grains ex am ined in the Ropianka For ma tion, where - as they com prise 38 and 62% in the Menilite For ma tion, re spec - tively. The data show that the tour ma lines orig i nate from litholo - gically very sim i lar source rock types. The ig ne ous tour ma lines rep re sent Li-poor gran ites or as so ci ated peg ma tite bod ies, while the group of meta mor phic tour ma lines orig i nate from Al-poor and Al-rich metasedimentary rocks (Fig. 8A), as in di - cated by con tents of Al, Fe and Mg. Ad di tion ally, the low con - tents of Al in the T-sites and Xvac val ues rang ing from 0.2–0.5 apfu, of tour ma lines from both for ma tions stud ied, plot - ting in the field of Al-rich metapelites, in di cate their cry - stallisation be low tem per a tures of about 700°C (Henry and Dutrow, 1996). This is sup ported by the crystallisation tem per a - ture cal cu lated as 511 ± 20°C of the gar net-bi o tite in clu sion pres ent in a meta mor phic tour ma line grain from the Ropianka For ma tion (R_t13_rz3; Figs. 4, 7E and Ap pen dix 4). Most of the chem i cally zoned meta mor phic and ig ne ous tour ma lines ap - pear to have formed dur ing sta ble crystallisation con di tions, as points de not ing their com po si tion plot close to each other in the en vi ron men tal di a gram (Fig. 8A). Only some points re flect ing the chem is try of tour ma lines and dis play ing dis tinct chem i cal change (mainly in the Al and less fre quently in the Mg or Fe con - tents) plot in dif fer ent fields of the prov e nance di a gram (Fig.
8A). This may in di cate that the crystallisation en vi ron ment evolved dur ing for ma tion of the tour ma lines, fin ger print ing the tour ma line com po si tion. Such a change in the tour ma line pop u - la tion of the Ropia nka For ma tion was ob served mainly for some meta mor phic tour ma lines, the dis crim i na tion points of which move be tween fields de not ing Al-undersaturated and Al-sat u - rated con di tions (Fig. 8A). The sit u a tion is more com plex for some tour ma lines of the Menilite For ma tion, the chem is try of which sug gests that their crystallisation con di tions were chang - ing be tween ig ne ous and Al-undersaturated and Al-sat u rated meta mor phic en vi ron ments (grains M_t19_rz3, M_t9_rz3; Fig.
8A). The scarce euhedral grains ana lysed in both for ma tions orig i nate from metapelites (Fig. 8A). The lack or very low con - tent of tet ra he dral Al and the Xvac val ues rang ing from 0.2–0.3 apfu (Ap pen di ces 2 and 3) sug gest me dium-grade
* Supplementary data associated with this article can be found, in the online version, at doi: 10.7306/gq.1133
meta mor phic con di tions dur ing their crystallisation (Henry and Dutrow, 1996). The two grains from the Ropianka For ma tion that have de tri tal cores (R_t5_rz5, R_t7_rz2) dis play a sim i lar prov e nance. Points de not ing the chem is try of the de tri tal cores of these grains plot in the field of Fe3+-rich quartz-tour ma line rocks, calc-sil i cates and metapelites, while points de not ing over growth com po si tion are lo cated in fields in di cat ing prov e - nance of the tour ma lines from metapelites (Fig. 8A).
The co ex is tence of var i ously etched and highly rounded, subrounded and fresh euhedral grains sug gests mixed first-cy -
cle and polycyclic prov e nance of the tour ma lines stud ied, thus their or i gin should be con sid ered sep a rately.
EUHEDRAL TOURMALINE
The scarce euhedral tour ma lines most prob a bly rep re sent first-cy cle de liv ery and come from a source mas sif lo cated close to the Skole Ba sin. Ac cord ing to older lit er a ture (e.g., Ksi¹¿kiewicz, 1962; Unrug, 1979), dur ing sed i men ta tion of the
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Fig. 4. Rep re sen ta tive tour ma line grains of the Ropianka (grain la bels start with R) and Menilite (grain la bels start with M) for ma tions show ing typ i cal col our and zonation pat terns Lines de note lo ca tion of tra verses dur ing microprobe anal y ses and dots with num bers, stand for an a - lyt i cal spots; they cor re spond with the di a grams shown in Fig ure 6; thin sec tion, plane-polar ised light
Ropianka and Menilite for ma tions in the area stud ied, such a mas sif, the North ern Mar ginal Cor dil lera, was lo cated in the north west ern mar gin of the ba sin, which is in di cated by palaeo - transport di rec tions (e.g., Ksi¹¿kiewicz, 1962; Kotlarczyk, 1966, 1976; Œl¹czka and Unrug, 1966; Bromowicz, 1974; Kotlarczyk and Leœniak, 1990). The dis cov ery of peb bles and clasts of gneiss and mica-schist in the Ropianka For ma tion, sup port the ex is tence of po ten tial source rocks for tour ma lines in this sou - rce mas sif. How ever, the scar city of euhedral tour ma lines in the de pos its stud ied sug gests that the meta mor phic source rocks build ing the cor dil lera were not rich in these min er als. Judg ing by the tour ma line com po si tion, the same rocks may have been
a source for euhedral tour ma lines of the Menilite For ma tion ei - ther. How ever, de pos its of the Kliva and Boryslav sand stone mem bers may rep re sent, at least in part, pa limp sest sed i ments sensu McManus (1975) (Salata and Uchman, 2013).
ROUNDED TOURMALINE
The ques tion of prov e nance of the rounded tour ma line pop u - la tion is more com plex. Tour ma line is highly re sis tant to both chem i cal weath er ing and trans port pro cesses, thus may sur vive long trans por ta tion over a few cy cles of sed i men ta tion. There -
Fig. 5. Clas si fi ca tion di a grams (ac cord ing to Henry et al., 2011) and com po si tion of tour ma lines from
the Ropianka and Menilite for ma tions
fore, the rounded tour ma line pop u la tion may have been eroded from clastic rocks of the Skole Ba sin fore land or from meta - psammites pres ent in the North ern Mar ginal Cor dil lera, in which rounded tour ma line would rep re sent in her ited pri mary de - tri tal grains. How ever, in both these cases tour ma line rep re sents polycyclic grains. Fur ther more, the round ing may have been pro - duced in coastal en vi ron ments of the Skole Ba sin or dur ing flu - vial trans por ta tion from re mote source ar eas. None the less, the pres ence of Car bon if er ous coal clasts, and clasts of Me so zoic sed i men tary rocks in de pos its both of the Ropia nka and Menilite
for ma tions (Wdowiarz, 1949; Kotlarczyk and Œliwowa, 1963;
Nowak, 1963; Œl¹czka and Unrug, 1966; Bro mowicz, 1974, 1986; Kotlarczyk, 1976; Rajchel and Mysz kowska, 1998 and ref - er ence therein) sup port the idea of ero sion of the sed i men tary cover of the Skole Ba sin fore land dur ing sed i men ta tion of these for ma tions. Tak ing into con sid er ation the prob a ble ini tial lo ca tion of the Skole Ba sin (e.g., Golonka et al., 2006) and the sub se - quent ro ta tion of the Carpa thian orogen, the area stud ied may have been sup plied from the sed i men tary cover of the Ma³o - polska Block and the east ern part of the Up per Silesian Block.
26 Dorota Salata
Fig. 6. Main el e ment con tents and compositional pro files along tra verses in tour ma line grains shown in Fig ure 4
Col our va ri et ies of tour ma lines oc cur ring in the Up per Car bon if - er ous and Mid dle Ju ras sic clastic de pos its of the Up per Silesian and Ma³opolska blocks (e.g., Turnau-Morawska and £ydka, 1954; £ydka, 1955, 1958; Krysowska, 1959; Krysowska et al., 1960; ¯achuñ, 1996) and the chem i cal sim i lar ity of the tour ma - lines stud ied to those oc cur ring in the clastic infill of the pre- Callovian Ju ras sic palaeo karst in the Kraków–Wieluñ Up land (Fig. 8B; Salata, 2013b), pro vide fur ther ev i dence re in forc ing this idea. If the rounded tour ma lines stud ied were de rived from sed i - men tary or meta sedimentary (as in her ited grains) rocks, the ques tion is where the protoliths, in which the tour ma lines ini tially crys tal lised, were lo cated. The high re sis tance of tour ma lines al - lows a dis tant source area(s) for the rounded grains, but the same fea ture makes es tab lish ing the lo ca tion of it (or them) dif fi - cult and un cer tain. The pos si ble sources are re mote mas sifs of the Bo he mian Mas sif and up lifted parts of the base ment of Bruno vistulicum (in clud ing the part of that cur rently un der the Carpa thians), which sup plied Up per Car bon if er ous (e.g., Pasz - kowski et al., 1995) and Me so zoic (e.g., Salata, 2013a and ref er - ences therein) clastic de pos its of the Up per Silesian Block; the ma te rial could have been dis persed also on the Ma³opolska Block. A land mass lo cated south of the Kra ków–Wieluñ Up land was also sug gested as a source for de tri tal gar net oc cur ring in the Mid dle Ju ras sic clastic de pos its of the Kraków area (Méres et al., 2012). The sed i men tary rocks of the Up per Silesian and Ma³o polska blocks sub se quently com prised sources of a clastic ma te rial de pos ited fi nally in the Skole Ba sin. How ever, tour ma - line was not re ported as a con stit u ent of crys tal line rocks build ing the base ment of the Up per Silesian Block (e.g., Heflik and Konior, 1970, 1972, 1974; Górska and Heflik, 1975), but it can not be ex cluded that tour ma line oc curs in that part of it that was overthrusted by the Carpathians. By con trast, tour ma line is a com mon con stit u ent of rock bod ies in the Bo he mian Mas sif, cur - rently ex posed and avail able for com par a tive stud ies. The rounded tour ma lines stud ied dis play compositional re sem bla nce to tour ma lines oc cur ring in var i ous meta mor phic and ig ne ous bod ies of the Moldanubian and Saxothuringian zones of the Bo - he mian Mas sif, in clud ing the Sudetic part of it (Fig. 8B; e.g., Pieczka, 1996; Burianek and Novák, 2004, 2007; Novák et al., 2004, 2013; Breiter et al., 2005; S³aby and Koz³owski, 2005;
Žáèek and Sulovský, 2005; Novák, 2007; Èopja ková et al., 2009). The tour ma lines stud ied are also alike in com po si tion to de tri tal tour ma lines shown to be de rived mainly from the Bo he - mian Mas sif, oc cur ring in de pos its of the North Sudetic Syn - clinorium and Fore-Sudetic Homocline (Fig. 8B; Biernacka, 2012; Kowal- Linka and Stawikowski, 2013). There fore, both the Bo he mian Mas sif and a land mass(es) sup ply ing the Carpathian bas ins fore land with clastic ma te rial are equally pos si ble as sources, where the rounded tour ma lines stud ied ini tially crys tal - lised. The prov e nance of the two polymetamorphic grains from the Ropianka For ma tion (R_t5_rz5, R_t7_rz2) is more com plex.
The metapelitic overgrowths of the tour ma lines could have been formed in meta mor phic com plexes of the cor dil lera lo cated in mar ginal parts of the Skole Ba sin, as the tour ma lines are weakly rounded. The de tri tal cores (lo cat ing in the field of quartz-tour ma - line rocks, calc-sil i cates or metapelites; Fig. 8A) of these two tour ma lines may have the same type of protolith as some tour - ma lines from the Czatkowice palaeokarst infill (Sala ta, 2013a) or from re de pos ited tourmalinites from the West ern Carpathians (¦«èek et al., 2008 and ref er ences therein; Fig. 8B).
CONCLUSIONS
1. The de tri tal tour ma lines, both euhedral and rounded, from the Ropianka and Menilite for ma tions dis play very strong re sem blance in terms of op ti cal fea tures and chem i cal com po - si tion. The tour ma lines be long mostly to the schorl-dravite se - ries with a mi nor con tri bu tion of tour ma lines dis play ing foititic or Mg-foititic com po si tion.
2. The chem i cal com po si tion of the tour ma lines stud ied in di - cates their crystallisation in Li-poor gra nitic rocks or pegmatites and Al-poor and Al-rich metasedimentary rocks. Grains com ing from metasedimentary rocks pre vail in tour ma line pop u la tions of both the Ropianka and Menilite for ma tions. Ad di tion ally, the low con tent of tet ra he dral Al and X-va cancy val ues of tour ma - lines de rived from Al-rich metapelites shows me dium-grade meta mor phic con di tions of their for ma tion. This is sup ported by the crystallisation tem per a ture of the gar net-bi o tite in clu sion, Fig. 7. Typ i cal min eral in clu sion types pres ent in tour ma lines from the for ma tions stud ied
Bt – bi o tite, Grt – gar net, Mnz – monazite, TiO2 – TiO2 polymorph, Zrn – zir con
28 Dorota Salata
Fig. 8A – dis tri bu tion of points re flect ing com po si tions of the tour ma lines stud ied on prov e nance di a grams of Henry and Guidotti (1985); col oured fields in di a grams of zonal tour ma lines stud ied en cir cle all points mea - sured in a cer tain tour ma line grain in di cated; B – compositional fields of tour ma lines from var i ous rocks of the Bo he mian Mas sif and de tri tal tour ma lines re ported as orig i nat ing from crys tal line do mains of the mas sif.
The num bered fields cor re spond to the fol low ing rock types: 1 – Li-rich granitoids, pegmatites and aplites; 2 – Li-poor granitoids, pegmatites and aplites; 3 – hy dro ther mally al tered, gra nitic rocks; 4 – Al-rich metapelites and metapsammites; 5 – Al-poor metapelites and metapsammites; 6 – Fe3+-rich quartz-tour ma line rocks, calcsilicates and metapelites; 7 – Ca-poor ultramafites; 8 – metacarbonates and metapyroxenites. Compo - sitional fields in part B ac cord ing to an a lyt i cal data from: Pieczka, 1996; Burianek and Novák, 2004, 2007;
Novák et al., 2004, 2013; Breiter et al., 2005; S³aby and Koz³owski, 2005; Baèík and Sulovský, 2005; Novák, 2007; Baèík et al., 2008; Èopjaková et al., 2009; Biernacka, 2012; Kowal-Linka and Stawikowski, 2013; Salata, 2013b). Ex pla na tion of sym bols as in Fig ure 5
pres ent in a dravitic tour ma line grain from the Ropianka For ma - tion. Fur ther more, the tour ma line com po si tions in di cates that most of them crys tal lised dur ing a sin gle sta ble ig ne ous or meta mor phic event. How ever, tour ma lines formed in evolv ing chem i cal con di tions as well as poly-meta mor phic grains are also pres ent.
3. Judg ing from the round ing, the tour ma line pop u la tions stud ied rep re sent a mix ture of first-cy cle and polycyclic grains.
Euhedral tour ma lines rep re sent ing the first-cy cle de liv ery are metasedimentary in or i gin and are de rived from a source lo - cated near to the Skole Ba sin (e.g., the North ern Mar ginal Cor - dil lera). The scar city of euhedral grains in the tour ma line pop u - la tions stud ied sug gests that the source rocks were poor in these min er als. The par ent ig ne ous and meta mor phic rocks of the rounded tour ma lines may have been crys tal line do mains of
the Bo he mian Mas sif and/or the crys tal line base ment of Bruno - vistulicum. The sources ini tially sup plied Up per Pa leo zoic and partly Me so zoic clastic sed i ments de pos ited on the Up per Silesia and Ma³opolska blocks, which be came the ul ti mate sources for the clastic ma te rial form ing sand stones of the Ropianka and Menilite for ma tions.
Ac knowl edg ments. I am grate ful to the re view ers: M. No - vák (Masaryk Uni ver sity) and J. Rajchel (AGH Uni ver sity of Sci - ence and Tech nol ogy) for their con struc tive re marks and com - ments, which helped to im prove the manu script. The au thor is also in debted to L. Je¿ak and P. Dzier¿anowski (War saw Uni - ver sity) for their as sis tance in EMPA anal y ses. The study was fi nanced by the Jagiellonian Uni ver sity and partly sup ported by the NCN grant 2013/09/B/ST10/00591.
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30 Dorota Salata
