Rare earth el e ments dis tri bu tion in fine-grained de pos its from the up per most Tri as sic and Lower Ju ras sic of the Pol ish Ba sin: prov e nance and weath er ing in the source area
Pawe³ BRAÑSKI1 and Stanis³aw Zbigniew MIKULSKI1, *
1 Pol ish Geo log i cal In sti tute – Na tional Re search In sti tute, Rakowiecka 4, 00-975 Warszawa, Po land
Brañski, P., Mikulski, S.Z., 2016. Rare earth el e ments dis tri bu tion in fine-grained de pos its from the up per most Tri as sic and Lower Ju ras sic of the Pol ish Ba sin: prov e nance and weath er ing in the source area. Geo log i cal Quar terly, 60 (2): 441–450, doi: 10.7306/gq.1288
Nine teen sam ples of up per most Tri as sic and Lower Ju ras sic claystones and mudstones, which were formed in the epicontinental Pol ish Ba sin, were ana lysed by in duc tively cou pled plasma mass spec trom e try (ICP-MS) for rare earth el e - ments (REE) and other se lected trace el e ments (Sc, Y, Th, Zr and U). The re sults in di cate that the source of most of the claystones and mudstones stud ied were sed i men tary rocks of the up per con ti nen tal crust of old cratonic ar eas, where the protolith had a mainly fel sic char ac ter. How ever, in the lat est Tri as sic a char ac ter is tic layer formed, im ply ing sig nif i cant in put from mafic vol ca nic protolith. It was also found that mod er ately in tense chem i cal weath er ing usu ally fa voured in creased con - cen tra tion of the rare earths. Ex tremely strong hy dro ly sis, re lated to ep i sodes of very hot and hu mid cli mate (green house events), caused con spic u ous im pov er ish ment in REE in re sid ual clays. Weath er ing and re cy cling pro cesses mod i fied the com po si tion of REE to some ex tent, but gen er ally did not oblit er ate the orig i nal char ac ter is tics of the protolith. In some sam - ples, en rich ment in rare earth el e ments was ob served, caused by ad mix tures of ac ces sory min er als (be ing a main car rier of REE) and/or in creased sort ing dur ing re cy cling.
Key words: rare earth el e ments, prov e nance, palaeo-weath er ing, up per most Tri as sic and Lower Ju ras sic, Pol ish Ba sin.
INTRODUCTION
Rare earth el e ments and other se lected trace el e ments that oc cur in siliciclastic rocks, can pro vide im por tant in for ma tion on sed i ment prov e nance. The chem i cal com po si tion of sed i men - tary rocks usu ally re flects the com po si tion of the sed i ments and of tec tonic con di tions dur ing their for ma tion, and the na ture of protolith (a pri mary source), ei ther ig ne ous or meta mor phic rocks (Tay lor and McLennan, 1985; Bhatia and Crook, 1986;
Cullers et al., 1988; McLennan, 1989; McLennan et al., 1993;
Cullers, 2000). At the same time, it is nec es sary to con sider that the orig i nal com po si tion of sed i ments stud ied could be sig nif i - cantly mod i fied, es pe cially in chem i cal weath er ing pro cesses, re cy cling and hy drau lic sort ing in the en vi ron ment of de po si tion, and some times also by diagenetic and hy dro ther mal pro cesses (e.g., Nesbitt, 1979; Cullers, 1988; Condie et al., 1995; Cox et al., 1995; Nesbitt and Markovics, 1997; Bauluz et al., 2000;
Singh and Rajamani, 2001).
Pre lim i nary re search into the REE geo chem is try de scribed here was car ried out at the Pol ish Geo log i cal In sti tute-Na tional Re search In sti tute (Mikulski et al., 2014, 2015). Nine teen sam - ples of claystones and mudstones were taken from the se lected ar chive bore holes, which pen e trated siliciclastic rocks of the up -
per most Tri as sic and Lower Ju ras sic (Mikulski et al., 2014).
These rocks were formed in the Pol ish epicontinental ba sin, and most of them come from the Mid-Pol ish Trough (Fig. 1).
Over the past few years, var i ous as pects of the min er al og i cal and geo chem i cal com po si tion of these de pos its, along with palaeoenvironmental and palaeoclimatic in ter pre ta tions, have been stud ied (e.g., Brañski, 2010, 2012, 2014; Pieñkowski et al., 2014; Brañski and Pieñkowski, 2014). REE and en vi ron - men tal changes across the Tri as sic–Ju ras sic bound ary have been stud ied also in the Tethyan do main (Pálfy and Zajzon, 2012; Lintnerová et al., 2013). How ever, ef fects of weath er ing on the dis tri bu tion of REE in sed i ment suc ces sions has not been fully ex plained, and still raises con tro ver sies (e.g., Wronkiewicz and Condie, 1987; Middelburg et al., 1988;
Banfield and Eggleton, 1989; Price et al., 1991; Nyakairu and Koeberl, 2001; Duzgoren-Aydin and Aydin, 2009).
The pur pose of this work is ini tial char ac ter iza tion of the rare earths in fine-grained sed i men tary rocks formed in the lat est Tri as sic and Early Ju ras sic in the Pol ish sed i men tary ba sin. The study also at tempts to de ter mine their or i gins and, in par tic u lar, the in flu ence of the li thol ogy of the source ar eas and weath er ing pro cesses on the REE com po si tions.
GEOLOGICAL SETTING
Dur ing the lat est Tri as sic and Early Ju ras sic, sed i men ta tion of siliciclastic, con ti nen tal, mar ginal-ma rine and spo rad i cally ma rine de pos its oc curred in a large Pol ish epicontinental sed i -
* Corresponding author, e-mail: stanislaw.mikulski@pgi.gov.pl Received: February 23, 2016; accepted: April 2, 2016; first published online: April 8, 2016
men tary ba sin (Pieñkowski, 2004; Pieñkowski and Schudack, 2008). The max i mum sub si dence, re sult ing in max i mum thick - ness of these de pos its, oc curred in the ax ial zone of this ba sin, called the Mid-Pol ish Trough (MPT). At the end of the Tri as sic, sed i men ta tion took place in ter res trial con di tions. The Rhaetian was mostly a tec toni cally quiet time, but at the Tri as sic-Ju ras sic bound ary re ju ve na tion of the MPT took place. In Early Hettangian times, ther mal sub si dence, which had been grad u - ally de clin ing since the Early Tri as sic (Dadlez et al., 1995), con - spic u ously ac cel er ated. More over, pro nounced transtension - -re lated lo cal sub si dence was su per im posed on the ther mal sub si dence in the MPT, par tic u larly in the Holy Cross Moun - tains seg ment of the MPT (Hakenberg and Œwidrowska, 1997;
Brañski, 2006, 2011). The youn ger stages of the Lower Ju ras - sic were formed mainly un der con di tions of grad u ally de cel er at - ing sub si dence, and sed i men ta tion was mostly con trolled by sea level changes (Pieñkowski, 2004; Pieñkowski and Schu - dack, 2008). The stra tig ra phy of the Tri as sic/Ju ras sic tran si tion and of the Lower Ju ras sic is shown in Ta ble 1. Be cause these for ma tions have rel a tively poor biostratigraphic doc u men ta tion, the strati graphic sub di vi sion is based on the se quence strati - graphic cor re la tion and chemostratigraphy (Pieñkowski, 2004;
Hesselbo and Pieñkowski, 2011; Pieñkowski et al., 2012).
Fine-grained sed i men ta tion, which dom i nated in the low er - most and up per Zagaje For ma tion (Up per Rhaetian and Lower Hettangian), took place also dur ing de po si tion of the Lower - -Mid dle Rhaetian Wielichowo Beds (Wag ner, 2008; Pieñ kowski et al., 2012, 2014), of the Przysucha Ore-bear ing For ma tion (Up per Hettangian, oc cur ring only in the Holy Cross Moun tains re gion), of the Gielniów For ma tion (Lower Pliens bachian), and
of the Ciechocinek For ma tion (Lower Toarcian). The fine - -grained rocks (interbedded with heterolithic de pos its and sub - or di nate fine-grained sand stones) are cal cium-free. The re - main ing Lower Ju ras sic for ma tions in the Pol ish Ba sin are dom - i nated by sand stones and sandy heterolithic de pos its. The Rhaetian–low er most Hettangian sed i ments were de pos ited in con ti nen tal, al lu vial-lac us trine en vi ron ments. The re main ing Fig. 1. Gen eral palaeo ge ogra phy and lo ca tion of the bore hole sec tions stud ied
(mod i fied from Pieñkowski, 2004; Brañski, 2012, 2014) HCM – Holy Cross Moun tains
T a b l e 1 Stra tig ra phy of the up per most Tri as sic and Lower Ju ras sic
in the epicontinental Pol ish Ba sin (af ter Pieñkowski, 2004;
Wag ner, 2008; Pieñkowski et al., 2012)
Sys tem Stage For ma tion
Ju ras sic
Toarcian Borucice For ma tion Ciechocinek For ma tion
Pliensbachian
Drzewica (Komorowo, Blanowice) For ma tion
Gielniów (£obez) For ma tion Sinemurian Ostrowiec For ma tion
Hettangian
Przysucha Ore-bear ing For ma tion (Sk³oby For ma tion)
Sk³oby For ma tion Zagaje For ma tion
Tri as sic Rhaetian
Wielichowo Beds
Norian Zb¹szynek Beds
Lower Ju ras sic strata rep re sent brack ish-ma rine/mar ginal-ma - rine de pos its with deltaic/flu vial in ter vals (Pieñkowski, 2004;
Brañski, 2011). The up per most Tri as sic and Lower Ju ras sic de - pos its were bur ied to depths of ap prox i mately 1000–3000 m (Brañski, 2011, 2012, 2014). This took place un til the Late Cre - ta ceous, when the MPT area was up lifted and sub jected to re - cur rent weath er ing and in ten sive ero sion, which oc curred mainly in the Paleogene.
It should be noted that the up per most Tri as sic–Lower Ju - ras sic de pos its were formed in a very dy namic pe riod of Earth’s his tory. In re cent years, abun dant ev i dence of large-scale, rapid global en vi ron men tal change has been col lected. The most se - vere changes, re lated to large mag matic prov inces and marked car bon cy cle per tur ba tions, took place at the Tri as sic–Ju ras sic (Cen tral At lan tic Mag matic Prov ince – CAMP) and Pliensba - chian–Toarcian (Karoo-Ferrar mag matic prov ince) tran si tion in - ter vals (e.g., McElwain et al., 1999; Hesselbo et al., 2000, 2002;
Pálfy et al., 2001; Co hen and Coe, 2007; Co hen et al., 2007).
Ris ing at mo spheric car bon di ox ide con cen tra tions caused a green house cli mate and re sult ing abun dant rain fall, ris ing tem - per a tures and in ten si fi ca tion of weath er ing and ero sion in the source ar eas. Oc cur rence of cli ma tic shifts in the Pol ish Ba sin has also been sup ported by pat terns of min er al og i cal and geo - chem i cal data (cf. Brañski, 2009a, b, 2010, 2011, 2012, 2014;
Hesselbo and Pieñkowski, 2011, Pieñkowski et al., 2012, 2014;
Brañski and Pieñkowski, 2014).
MATERIALS AND METHODS OF REE RESEARCH
Rare earth el e ments were ex am ined in nine teen sam ples of mudstone and claystone, col lected from the cores of var i ous ar - chive bore holes drilled in the Pol ish Ba sin and rep re sent ing dif - fer ent strati graphic units of the up per most Tri as sic and the Lower Ju ras sic. The stud ies cov ered sec tions of the Niek³añ PIG 1, Kaszewy 1, Mechowo IG 1 and Brody-Lubienia BL-1 bore holes. In di vid ual sam ples from the Gródek OP-2 and Gorzów Wielkopolski IG 1 bore holes were also ex am ined (Fig.
1 and Ta ble 2).
The REE, Sc, Y, and Th anal y ses were per formed in the Chem i cal Lab o ra tory of the Pol ish Geo log i cal In sti tute – Na tional Re search In sti tute, us ing mass spec trom e try with ICP-MS tech - nic. Af ter acid di ges tion, the sam ples were di luted 20 times with a so lu tion of 1% HNO3. To tal so lu tion of el e ments con tained in the sam ples was achieved by use of hy dro flu oric acid and chlor ic acid (VII – ox i da tion of flu o rine and chlo rine in acid). Dried and pow dered sam ples were ini tially treated with ni tric acid (V) in or - der to dis trib ute or ganic mat ter and dis solved in a mix ture of perchloric and hy dro flu oric acid (VII). In or der to im prove the pro - ce dure for dis so lu tion, di ges tion was re peated three times. In the last stage, af ter evap o ra tion to dry ness (on a hot plate, to a tem - per a ture of 150 ± 10°C) the res i due was dis solved in di lute ni tric acid (V). The so lu tion ob tained was sub mit ted to anal y sis by ICP-MS. De tec tion lim its were 0.5 ppm for LREE and 0.05 ppm for HREE. The re sults are col lected in Ap pen dix 1*. Some other
T a b l e 2 List of claystone and mudstone sam ples from the Up per Tri as sic and Lower Ju ras sic stud ied by ICP-MS
No. Sam ple Bore hole Beds or For ma tion Stra tig ra phy
1. Nk/187.5
Niek³añ PIG 1
Zb¹szynek Beds Tri as sic, Norian
2. Nk/178.4 Wielichowo Beds Tri as sic, Rhaetian
3. Nk/167.8 Wielichowo Beds Tri as sic, Rhaetian
4. Nk/162.3 Zagaje For ma tion Tri as sic, Rhaetian
5. Nk/157.7 Zagaje For ma tion Ju ras sic, Hettangian
6. Nk/32.0 Zagaje For ma tion Ju ras sic, Hettangian
7. Gr/204.1 Gródek OP-2 Przysucha Ore-bear ing For ma tion Ju ras sic, Hettangian 8. K/1973.8
Kaszewy 1
Zb¹szynek Beds Tri as sic, Norian
9. K/1480.3 Ostrowiec For ma tion Ju ras sic, Sinemurian
10. K/1465.2 Ostrowiec For ma tion Ju ras sic, Sinemurian
11. K/1464.3 Gielniów For ma tion Ju ras sic, Pliensbachian
12. K/1463.7 Gielniów For ma tion Ju ras sic, Pliensbachian
13. K/1462.3 Gielniów For ma tion Ju ras sic, Pliensbachian
14. M/1130.0
Mechowo IG 1 Zagaje For ma tion Tri as sic, Rhaetian
15. M/700.5 Gielniów For ma tion Ju ras sic, Pliensbachian
16. BL/185.5
Brody-Lubienia BL-1
Drzewica For ma tion Ju ras sic, Pliensbachian
17. BL/162.0 Ciechocinek For ma tion Ju ras sic, Toarcian
18. BL/159.0 Ciechocinek For ma tion Ju ras sic, Toarcian
19. GW/815.0 Gorzów Wlkp. IG 1 Ciechocinek For ma tion Ju ras sic, Toarcian
Nk, Gr, BL – Holy Cross Mts. seg ment of MPT, K – Kuyavian seg ment of MPT, M – Pom er a nian seg ment of MPT, GW – Fore-Sudetic Monocline (north ern part)
* Supplementary data associated with this article can be found, in the online version, at doi: 10.7306/gq.1288
el e ments ana lysed by por ta ble spec trom e ter (i.e. Zr and U) were in cluded in the data in ter pre ta tion.
The over all in ter pre ta tion was re in forced by re sults of prior pub lished anal y ses: whole-rock min eral com po si tion, clay min - eral com po si tion (in <0.002 mm frac tion) and the ma jor el e ment con tents (Brañski, 2010, 2012, 2014; Pieñkowski et al., 2014).
Var i ous min er al og i cal and geo chem i cal weath er ing in di ces have also been cal cu lated (Brañski, 2014; Pieñkowski et al., 2014). Se lected re sults of these pre vi ous stud ies are col lected in Ap pen dix 2.
RARE EARTH ELEMENT RESULTS
The most im por tant re sults of the re search are shown in tab u lar form (Ta ble 3, Ap pen dixes 1 and 3) and in the charts (Figs. 2–6). Char ac ter is tics of the rare earths are shown (Fig. 3) in graphs stan dard ized in re la tion to chondrite (Tay lor and McLennan, 1985). In ad di tion, the con tents of el e ments in the sam ples ana lysed are shown also in re la tion to stan dard mud - rocks (Fig. 4), in this case to post-Ar chaic Aus tra lian shale – PAAS (Tay lor and McLennan, 1985), con sid ered to be a typ i cal de posit of cratonic prov e nance, de rived from pas sive con ti nen - tal mar gins (McLennan, 1989).
REEs IN MUDSTONES AND CLAYSTONES OF THE LOWER JURASSIC
In sam ples of fine-grained rocks rep re sent ing the Lower Ju - ras sic, the con tents of the el e ments ana lysed are not very var - ied and are gen er ally sim i lar to their con tents in stan dard shale.
The to tal con tent of lanthanide el e ments ranges usu ally from 136 to 334 ppm, the av er age of their con tents in the mudstone sam ples stud ied (241.3 ppm) is slightly higher than in the case of PAAS (184.8 ppm). Only in one sam ple, K/1463.7 (from the low est Pliensbachian in the Kaszewy bore hole sec tion) the con - tent of lanthanide el e ments is sig nif i cantly higher – 509.6 ppm (Ap pen dix 1 and Ta ble 3). The ra tio of light to heavy REEs in these sam ples is also some what higher than in the ref er ence shale and var ies within the lim its of 8.9–15.9 (av er age 12.3).
The eu ro pium anom aly is sim i lar to that in stan dard shale. The ra tio of Eu/Eu* var ies in a fairly nar row range 0.53–0.68 (0.63 on av er age), which is slightly higher or slightly lower than in PAAS (Ta ble 3 and Ap pen dix 3). The scan dium con tent var ies from 8 to 24 ppm, yt trium from 14 up to 40 ppm, and tho rium from 11 to 52 ppm. The high est con tent of these el e ments was also found in sam ple K/1463.7 sam ple, which is also sig nif i - cantly en riched in lanthanide el e ments.
Graphic char ac ter is tics of the rare earths in these Lower Ju - ras sic claystone and mudstone sam ples are sim i lar to those of PAAS (Fig. 3). There is an en rich ment of light rare earth el e ments (LREEs), and dis tinct frac tion ation within them, al most flat curves as re gards heavy rare earth el e - ments (HREEs), and a mod er ate-sized eu ro pium anom - aly. To tal REE frac tion ation (LaN/YbN – 12.09 on av er age), frac tion ation within LREEs (LaN/GdN – me dium 7.58) and also within HREEs (GdN/YbN – 1.64 on av er age) are slightly larger than in PAAS (Ta ble 3). The gen eral sim i lar - ity of all the sam ples taken from the Lower Ju ras sic to the stan dard shale is clearly vis i ble on the chart show ing the REE con tent in re la tion to PAAS, where their char ac ter is tic pat terns are al most flat (Fig. 4).
Only sam ple Nk/1463.7 shows sig nif i cant (more than dou bled) en rich ment in rare earth el e ments. Nev er the less, the shape of the REE con tent plot in re la tion to the chon drite (Fig. 3) in this sam ple is very sim i lar to the graphic char ac - ter is tics of the av er age con tri bu tion of all the el e ments in PAAS. This means that en rich ments of the in di vid ual el e - ments are in gen eral dis trib uted evenly in this sam ple, al - though their frac tion ation (es pe cially within the LREE) is greater (LaN/YbN = 13.41; LaN/GdN – 11.73) (Ap pen dix 3).
REE IN MUDSTONES AND CLAYSTONES OF THE UPPERMOST TRIASSIC
In four spec i mens ex am ined rep re sent ing the Up per Tri as sic, the con tents of the el e ments ana lysed are more vari able than in the Ju ras sic sam ples (Ap pen dix 1 and Ta - ble 3). Only in two sam ples (Nk/187.5 and M/1130.0) are the con tents of REEs close to their con tent in stan dard shale (PAAS). The to tal share of lanthanide el e ments is very broad, rang ing from just 34 up to 2450 ppm (Ta ble 3).
The high est REE con tent was ob served in sam ple Nk/178.4 of the Lower–Mid dle Rhaetian and the low est one in sam ple Nk/162.3, rep re sent ing the Up per Rhaetian (Ap pen dix 1). Both sam ples come from the Niek³añ PIG 1 bore hole core and they are sep a rated in the pro file just by 16 metres. In the first case, the to tal con tent of rare earths is more than an or der of mag ni tude higher, and in the sec - ond sev eral times lower than in the ref er ence shale. Also, T a b l e 3
Min i mum, max i mum and av er age con tents of the rare earth el e ments (REEs) and se lected trace el e ments
in the sam ples stud ied
Tri as sic Ju ras sic PAAS1
Sc 10.2–24.1 (16.7) 7.9–23.7 (15.0) 16
Y 10.8–81.1 (35.2) 14.5–39.5 (22.0) 27
La 4.8–441.6 (114.0) 28.8–114.7 (49.4) 38.2 Ce 8.8–1131.9 (270.0) 58.5–234.4 (105.9) 79.6
Pr 0.9–128.8 (30.4) 6.7–25.3 (11.3) 8.8
Nd 3.5–499.6 (118.4) 25.3–86.9 (41.1) 33.9
Sm 1.11–97.45 (23.23) 4.64–13.83 (7.29) 5.55
Eu 0.35–19.09 (4.57) 0.76–2.32 (1.35) 1.08
Gd 2.16–70.77 (17.65) 4.02–8.76 (5.36) 4.66
Tb 0.35–8.28 (2.21) 0.53–1.32 (0.78) 0.77
Dy 2.12–33.44 (10.25) 2.97–7.80 (4.50) 4.68
Ho 0.44–4.29 (1.61) 0.56–1.59 (0.90) 0.99
Er 1.33–8.75 (4.06) 1.62–5.17 (2.74) 2.85
Tm 0.21–0.92 (0.53) 0.24–0.83 (0.41) 0.41
Yb 1.59–4.68 (3.37) 1.61–5.78 (2.75) 2.82
Lu 0.24–0.68 (0.47) 0.25–0.91 (0.43) 0.43
Th 12.13–23.40 (17.26) 10.99–51.89 (20.21) 14.60 SLREE 19.5–2318.4 (560.6) 124.7–477.4 (223.4) 167.2
SHREE 8.4–131.7 (40.1) 11.3–32.2 (17.9) 17.6
STREE 34.1–2450.1 (600.7) 136.0–509.6 (241.3) 184.8
L/H* 1.3–17.6 (9.8) 8.9–15.9 (12.3) 9.5
LaN/YbN 0.88–63.77 (18.54) 8.76–17.25 (12.09) 9.16 LaN/GdN 1.85–6.41 (5.06) 5.21–11.73 (7.58) 6.84
GdN/YbN 0.48–12.26 (1.08) 1.12–2.00 (1.64) 1.34
Eu/Eu* 0.48–0.70 (0.64) 0.53–0.68 (0.63) 0.65
Th/Sc 0.77–2.29 (1.13) 0.73–2.82 (1.37) 0.91
La/Sc 0.20–37.42 (8.99) 2.27–5.08 (3.35) 2.39
La/Th 0.21–35.70 (8.85) 1.80–3.39 (1.75) 2.62
1 – af ter Tay lor and McLennan (1985); * – LREE/HREE
the ra tio of light to heavy REEs is very di verse and var ies within a very wide limit of 1.3–17.6 (Ta ble 3). This means that two sam ples taken from the up per most Tri as sic are strongly en - riched in light rare earth el e ments, while two oth ers are very poor in these el e ments and rel a tively en riched in the heavy el e -
ments. The sam ples stud ied show both slightly smaller and slightly larger eu ro pium anom a lies than in stan dard shale (Ap pen dix 1 and Ta ble 3).
Scan dium and tho rium con tents are rel a tively sta - ble and range be tween 10–24 ppm and 12–23 ppm, re spec tively. The high est share of scan dium was found in sam ple Nk/162.3, which is at the same time very poor in REEs. The yt trium con cen tra tion is more var ied (from 11 to 81 ppm), and its high est con tent was ob served in sam ple Nk/178.4 sam ple, which was par tic u larly rich in REEs.
Graphic char ac ter is tics of the rare earths in the up per most Tri as sic mudstone sam ples are quite dif - fer ent in re la tion to that of ref er ence shale (Figs. 3 and 4). Only in the case of two sam ples with REE con tents close to PAAS (Nk/187.5 and M/1130.0), their graphic char ac ter is tics are sim i lar to the av er - age char ac ter is tics of the stan dard shale (sig nif i cant en rich ment and quite dis tinct frac tion ation within LREE and al most flat HREE curves). In their case, the con tent of REEs stan dard ized to PAAS, shows as al most a hor i zon tal line with a value of 1 (Fig. 4).
Of note is the rel a tively sig nif i cant neg a tive eu ro - pium anom aly of sam ple M/1130.0 (Eu/Eu* = 0.48), as well as its con sid er able en rich ment in tho rium and im pov er ish ment in scan dium in re la tion to the ref er ence shale (Ap pen dixes 1 and 3).
In the case of the sam ple rich est in the lantha - nides (Nk/178.4; rep re sent ing the Lower–Mid dle Rhaetian in the Niek³añ bore hole sec tion), the graph of their stan dard con tents nor mal ized to chondrite clearly de vi ates from the char ac ter is tics of the av er age val ues for PAAS (Fig. 3). Of note here are not only very high con tents of REEs, but also their very strong frac tion ation (LaN/YbN – up to 63.77) (Ap pen dix 3). There is also ex tremely strong HREE frac tion ation (GdN/YbN – up to 12.26), which is re - corded as a very steep curve, while the curve of light el e ments is sim i lar to the av er age char ac ter is tics of the ref er ence shale (LaN/GdN – 5.20). De tailed anal y sis of each REE con tent in this sam ple (Ap pen dix 1) and their pat tern in re la tion to PAAS Fig. 2. Rare earth el e ments in sam ples of the fine-grained rocks stud ied
A – to tal REE, B – ra tio of the light to heavy el e ments
Fig. 3. Char ac ter is tics of the rare earths in the sam ples stud ied nor mal ized to chondrite (Tay lor and McLennan, 1985) A – Up per Tri as sic, B – Lower Ju ras sic
(Fig. 4) re veals that the en rich ment in REEs ap plies in par tic u lar to light and me dium el e ments, while the heavy el e ments are el - e vated to a much lesser de gree. Com pared to the ref er ence shale, the sam ple is en riched three times in yt trium, while slightly de pleted in scan dium and tho rium (Ap pen dix 1).
The REE char ac ter is tics (nor mal ized to chondrite) of sam ple K/1973.8 (Up per Norian in the Kaszewy 1 pro file; Fig. 3), also dif - fers from the REE char ac ter is tics of PAAS. This sam ple also con tains much higher lanthanides than does the ref er ence shale
and is char ac ter ized by much stron ger frac tion ation (LaN/YbN – 20.93). It is worth of no tice that the frac - tion ation of light REEs (LaN/GdN – 6.41) here is al - most the same as in PAAS, while the HREE curve shows a clear slope (GdN/YbN – 3.26) (Ap pen dix 3 and Fig. 3). A slight pos i tive anom aly of the MREEs (me dium rare earth el e ments; sa mar ium, eu ro pium, and gad o lin ium) is also ob served – it is vis i ble es pe - cially in the chart show ing re la tion of REE to PAAS con tent (Fig. 4). This sam ple is clearly en riched in yt - trium and slightly de pleted in tho rium, and the con - tent of scan dium is al most the same as in PAAS (Ap pen dix 1).
A to tally dif fer ent, com pletely un usual REE char - ac ter is tic has been ob served in sam ple Nk/162.3 that con tains the least amount of rare earths. The graphic char ac ter is tics of the nor mal ized val ues to chondrite (Fig. 3) shows rel a tive de ple tion of light el - e ments in re la tion to heavy (LaN/YbN just 0.88), as well as in crease of suc ces sive val ues within the HREEs (GdN/YbN – 0.48) (Ap pen dix 3), caus ing a re verse slope of the curve, i.e. en rich ment in heavy el e ments in re la tion to the me dium ones. The con - tent of the light est lantha nides (lan tha num-neo dym - ium) is 8–10 times less than the stan dard con tent, while heavy el e ments con cen tra tion is sim i lar to their share in PAAS, and, in the case of yt ter bium, even higher (Ap pen dix 1 and Fig. 4). The layer from which this sam ple was taken, is sig nif i cantly en riched in scan dium and tho rium, while slightly de pleted in yt - trium (Ap pen dix 1).
In the case of the next sam ple rep re sent ing the Rhaetian (Nk/167.8), the value curve stan dard ized to chondrite (Fig. 3) is sim i lar to the av er age REE pat terns in PAAS, al though frac tion ation of el e ments is smaller (LaN/YbN – 6.85) (Ap pen dix 3). In gen eral, al though the sam ple con tains sig - nif i cantly less rare earths than the ref er ence shale, de ple tion in in di vid ual rare earth el e ments (more or less twice) is noted here fairly evenly, which clearly il lus trates the al most hor i zon tal line when nor mal ized to PAAS (Fig. 4). The sam ple is sig nif i cantly en riched in scan dium and tho rium, while clearly im pov er ished in yt trium (Ap pen dix 1).
Fig. 4. Char ac ter is tics of the rare earths in the sam ples stud ied nor mal ized to post-Archean Aus tra lian shale – PAAS (Tay lor and McLennan, 1985)
A – Up per Tri as sic, B – Lower Ju ras sic
Fig. 5. Eu ro pium anom aly (A) and the ra tio of Th/Sc (B) in the sam ples of fine-grained rocks stud ied
REE PROVENANCE AND THE INFLUENCE OF PALAEOWEATHERING
In al most all claystone and mudstone sam ples of the Lower Ju ras sic, but only in two of the sam ples rep re sent ing fine - -grained rocks of the up per most Tri as sic, rare earth con cen tra - tions are not very var ied and are close to the REE con tent in stan dard shale (Ap pen dix 1, Figs. 2–4 and 6). Their com mon char ac ter is tics, namely: mod er ately high to tal REEs (sim i lar to the av er age in PAAS), mod er ate en rich ment of LREEs in re la - tion to HREEs, a flat HREE dis tri bu tion and a clear neg a tive eu - ro pium anom aly in di cate that orig i nal source of these sed i - ments was mainly re cy cled and weath ered fel sic rocks (cf. Tay -
lor and McLennan, 1985; McLennan et al., 1993; Cullers, 2000). In the case of the PAAS av er age, the to tal con tent of rare earths and their char ac ter is tics gen er ally sug gest a granodiorite protolith (Tay lor and McLennan, 1985; Nesbitt and Markovics, 1997). Also chondrite-nor mal ized re la tions of La/Yb and Gd/Yb (Ta ble 3 and Ap pen dix 3) have val ues sim i lar to the typ i cal post-archean mudrocks of cratonic prov e nance. This means that the dom i nant source of sed i men tary ma te rial de - pos ited dur ing Early Ju ras sic times in the con ti nen tal, and then in the brack ish-ma rine Pol ish Ba sin, was old up per con ti nen tal crust. This con clu sion is also sup ported by the most im por tant geo chem i cal fac tors (Th/Sc = 0.73–2.82; La/Sc = 2.27–5.08).
The REE con cen tra tions found in the mudrocks stud ied are gen er ally el e vated in com par i son to PAAS, which sug gests more in tense weath er ing and/or re cy cling than in the case of source ar eas for the ref er ence shale. Ura nium and tho rium re la - tion ships (U/Th = 0.23–0.39) and zir co nium and scan dium (Zr/Sc = 20.2–59.9) also sug gests quite strong chem i cal weath - er ing of source ar eas and sed i men ta tion in an oxi dis ing en vi - ron ment, with lo cal im pact of sed i ment re cy cling and hy drau lic sort ing (Fig. 6). The wide spread con trol of gen er ally strong hy - dro ly sis in ar eas sur round ing the Pol ish sed i men tary ba sin had al ready been rec og nized on the ba sis of clay min eral com po si - tion and ma jor el e ment con tents (e.g., Brañski, 2012, 2014;
Pieñkowski et al., 2014; Brañski and Pieñkowski, 2014). A slight va ri ety in the REE con cen tra tion in the fine-grained rocks stud - ied may also have been caused by changes in the in ten sity of weath er ing, dif fer ences in ero sion of palaeosol lev els (or in zones of weath er ing cov ers) and lo cally by the in flu ence of hy - drau lic sort ing dur ing trans port and de po si tion (cf. Condie et al., 1995; Nesbitt and Markovics, 1997; Bauluz et al., 2000).
Among the sam ples rep re sent ing the fine-grained rocks of the Lower Ju ras sic, only sam ple K/1463.7 of claystone, taken from a level lo cated just above the bound ary be tween the Sinemurian and Pliensbachian in the Kaszewy 1 bore hole, shows sig nif i cantly el e vated (by al most three times) share of rare earth el e ments. Sig nif i cant and gen er ally uni form en rich - ment in LREEs, a flat pat tern within the HREEs, a eu ro pium anom aly and the re la tion ships be tween tho rium, lan tha num and scan dium (Ap pen dixes 1 and 3), in di cate the fel sic na ture of the claystone protolith also in this case. Nev er the less, dis tinctly higher REE con cen tra tions and some dif fer ences in their char - ac ter is tics (e.g., strong frac tion ation within LREE) were most likely caused by very in ten sive re cy cling of de pos its, as dem on - strated by the ex tremely high pro por tion of Zr, sev eral times higher than in the stan dard shale (Zr/Sc is as high as 200), as well as by sig nif i cantly in creased Th/Sc ra tio (e.g., McLennan et al., 1993; Hassan et al., 1999; Lintnerova et al., 2013). These pro cesses have taken place in con di tions of mod er ate chem i cal weath er ing (CIA about 79; the ra tio of kaolinite/illite – 0.35; U/Th
= 0.35), be fore a pre sumed green house event at the be gin ning of Pliensbachian (Brañski and Pieñkowski, 2014). This layer most likely point to the ep i sodic en hance ment of ero sion and redeposition.
Un like the fine-grained rocks of the Lower Ju ras sic, only one-third of the sam ples rep re sent ing the claystones and mudstones of the up per most Tri as sic show con cen tra tions of rare earths and REE char ac ter is tics close to the av er age of PAAS. Some lay ers (K/1973.8 sam ple and, in par tic u lar, the sam ple Nk/178.4) con tain a much higher lanthanide con tent than the ref er ence shale. Sam ple Nk/178.4 (rep re sent ing the bot tom mudstone layer in the Wielichowo Beds of the Lower–Mid dle Rhaetian in the Niek³añ PIG 1 bore hole) is ex tremely en riched in lanthanides and their graphic char ac ter is tics strongly dif fer from Fig. 6. Bi nary com par i son charts show ing the prov e nance of
the sed i ments stud ied: A – LaN/YbN against to tal REE (the ar eas cor re spond ing to the source rocks are based on Yan et al., 2012); B – Th/Sc ra tio against Sc con tent (mod i fied from Fedo et al., 1997)
char ac ter is tics of the av er age val ues of PAAS (Ap pen dix 1, Figs.
3 and 4). Also in this case, most pa ram e ters in di cate a fel sic char ac ter of the protolith (for ex am ple, Eu/Eu* = 0.70; Th/Sc = 1.05). In ad di tion, this layer is a kaolinite mudstone (Ap pen dix 2) and it most likely re cords the first Rhaetian green house ep i sode and in tense chem i cal weath er ing in the source ar eas (Brañski, 2014; Pieñkowski et al., 2014). How ever, such a strong en rich - ment and frac tion ation of the REEs is hard to ex plain only by a fel sic na ture of the protolith and by chem i cal weath er ing pro - cesses (Fig. 6A). The main rea son for such a high con cen tra tion of rare earths and their un usual char ac ter is tics is most likely a sig nif i cant ad mix ture of ac ces sory min er als. Very high REE con - tents (es pe cially of light REEs), a re mark ably steep con tent dis - tri bu tion of the HREEs (GdN/YbN – 12.26), a slight but dis tinct rel - a tive en rich ment in the MREEs (Figs. 3 and 4) and the in creased share of P2O5 sug gest that source of this con cen tra tion may be an ad mix ture of monazite (McLennan et al., 1993). How ever, such a con clu sion seems to be chal lenged by the rel a tively low tho rium con tents and high con cen tra tion of yt trium (Ap pen dix 1), which may sug gest the pres ence of other REE min er als. In the case of this layer we are prob a bly deal ing with the im pact of in - creased ad mix tures of ac ces sory min er als (ap a tite, monazite, xeno time?), as the main car ri ers of REE. Even trace amounts of these min er als in the sam ple can cause a dras tic in crease in REE con tents (Gromet and Sil ver, 1983; Cullers et al., 1987;
McLennan et al., 1993; Condie et al., 1995; Bauluz et al., 2000).
Pre sum ably, the con cen tra tion of ac ces sory min er als was largely in her ited from the weath ered sed i men tary cover in the source area. The Zr con tents are only a lit tle higher than in the case of PAAS (Zr/Sc = 22.0) and this sug gests an in sig nif i cant role of re cy cling or hy drau lic sort ing. A rel a tively high ra tio of ura - nium to tho rium (U/Th = 0.90), in doc u mented con di tions of in - tense chem i cal weath er ing (Brañski, 2014; Pieñkowski et al., 2014; Ap pen dix 2), may be just the re sult of ac ces sory min eral ad mix tures (which were also a car rier of ura nium) or re flect less oxic con di tions dur ing sed i men ta tion (Jones and Man ning, 1994). Sim i lar (though less ex treme) REE char ac ter is tics oc cur also in sam ple K/1973.8, from the high est Norian in the Kaszewy 1 bore hole sec tion. Also in this case, we ob serve a very sig nif i - cant (more than tri ple) en rich ment in rare earth el e ments and their in creased frac tion ation, an in crease in the slope of the HREE curve, a small MREE pos i tive anom aly and mean ing ful en rich ment in yt trium. Such data also in di cate the im por tance of the fel sic protolith and en rich ment in ac ces sory min er als, al - though in smaller quan ti ties than in the case of sam ple Nk/178.4.
In turn, the REE char ac ter is tics of some other lay ers rep re - sent ing the Rhaetian (Nk/167.8; and es pe cially Nk/162.3) re - veal the in flu ence of very in tense chem i cal weath er ing, which led to a very sig nif i cant de cline in REE con tents. Mod er ate Zr con tents (Zr/Sc = 11.8–23.7) sug gests an un im por tant role of re cy cling and sort ing. More over, the re sults of the REE study in these Rhaetian lay ers in di cate a dif fer ent na ture of the protolith in the source ar eas, which had al ready been sug gested by pre - vi ous geo chem i cal and min er al og i cal re search (Brañski, 2014).
In the case of sam ple Nk/167.8, the REE con cen tra tion is much smaller, but their graphic char ac ter is tics (Figs. 3 and 4) are sim - i lar to the av er age char ac ter is tics of stan dard shale, and the most im por tant pa ram e ters (Eu/Eu* = 763; Th/Sc = 0.88) still sug gest a fel sic protolith. On the other hand, other fac tors (La/Sc = 0.69; La/Th = 0.79) sug gest a rather mixed char ac ter of pri mary rocks with some par tic i pa tion of mafic com po nents.
Nev er the less, the REE char ac ter is tics of the over lay ing layer of al most pure kaolinitic claystone (sam ple Nk/162.3; Ap pen dix 2) al ready in di cates a mafic com po nent in the source area (Fig.
6A). Kaolinite may dom i nate in con di tions of ex treme chem i cal weath er ing re gard less of the pri mary rock com po si tion (e.g.,
Chamley, 1989). Graph i cal char ac ter is tics (Figs. 3 and 4) and co ef fi cients, show their frac tion ation (Ap pen dix 3) and point to the fol low ing fea tures:
1 – very small con cen tra tion of REE in gen eral (more than five times lower than in PAAS);
2 – de ple tion of light el e ments rel a tive to heavy el e ments;
3 – de ple tion of me dium el e ments in re la tion to heavy ones (the re verse slope of the HREE curve).
This means that es pe cially strong REE de ple tion oc curs within the light el e ments, a slighter one within the MREEs, while there is lit tle or no de ple tion in heavy el e ments. These char ac - ter is tics, as well as an in creased con tent of scan dium and some other pa ram e ters (La/Sc = 0.20; La/Th = 0.21), sug gest a more mafic protolith for this claystone, for ex am ple, the pres ence of vol ca nic de tri tus (Cullers et al., 1987, 1988; Cullers, 1988, 1994, 2000; McLennan et al., 1993). Un like most of the sec tions stud ied sec tions, de liv ery of sed i men tary ma te rial to the vi cin ity of the Niek³añ PIG 1 bore hole was most prob a bly from the south (Pieñkowski, 2004), and source ar eas were most likely lo cated on the Fore-Carpathian area. Note wor thy, in the ear lier stud ies, ex treme chem i cal weath er ing dur ing for ma tion of this kaolinite claystone and its as so ci a tion with the green house event at the end of the Tri as sic pe riod had been pos tu lated (Brañski, 2014;
Pieñkowski et al., 2014 and ref er ences therein). This view is sup ported by the very low ura nium to tho rium ra tio (U/Th = 0.11). Most prob a bly, the char ac ter is tics of dif fer ent REE prov e - nance were un der scored by ex tremely strong weath er ing as so - ci ated with ep i sodes of hu mid trop i cal cli mate. Ac cord ing to some au thors (e.g., Roddaz et al., 2006), de ple tion of de pos its in light rare earth el e ments (that is, the rel a tive en rich ment in HREEs in re la tion to LREEs) may be just due to the fact that their source ar eas com prised very in ten sively weath ered, older sed i men tary rocks. The neg a tive eu ro pium anom aly (Eu/Eu* = 0.68) points to very in tense hy dro ly sis that led to a com plete trans for ma tion of plagioclase. To sum ma rize, re cent REE char - ac ter is tics in re sid ual clay rep re sented by sam ple Nk/162.3 is most likely as so ci ated with both vol ca nic protolith and very in - tense chem i cal weath er ing at the end of the Tri as sic.
De spite the fact that the in flu ence of weath er ing on the dis tri - bu tion of REE in sed i ment can be con tro ver sial, most au thors con sider that mod er ately in tense chem i cal weath er ing leads to the en rich ment of sed i ments in the rare earth el e ments (in LREEs in par tic u lar), while ex tremely strong weath er ing can cause pro nounced REE de ple tion as a re sult of their leach ing (e.g., Nesbitt, 1979; Nesbitt et al., 1990; Morey and Setterholm, 1997; Nesbitt and Markovics, 1997; Braun et al., 1998; Roddaz et al., 2006). The re sults pre sented herein seem to sup port this sug ges tion.
CONCLUSIONS
Re sults of anal y ses of rare earths and some other trace el e - ments (es pe cially in Lower Ju ras sic strata), are mostly close to the av er age data from the ref er ence mudrocks – post-Ar chaic Aus tra lian shale. They in di cate that the dom i nant source of the claystones and mudstones stud ied com prised sed i men tary rocks of the up per con ti nen tal crust of old cratonic ar eas, where the protolith had a mainly fel sic char ac ter of granodiorite type.
Some what higher than PAAS con cen tra tions of lanthanides (es pe cially LREE) re flect a higher de gree of ma tu rity of the rocks stud ied. On the other hand, the Up per Tri as sic strata in - clude also lay ers with el e vated con tents of scan dium, and sig - nif i cantly de pleted in lanthanides (es pe cially LREEs), with graphic char ac ter is tics sug gest a sig nif i cant share of mafic vol -
ca nic protolith (es pe cially the residual Rhae tian layer represented by sample Nk/162.3).
In gen eral, it can be con cluded that al though the pro cesses of weath er ing and re cy cling mod i fied the REE com po si tion to some ex tent, it did not re move the in flu ence of tec tonic do main as well of the main protolith type. In most cases, the lanthanides and some trace el e ments may be used to spec ify the prov e - nance even of ma ture sed i men tary rocks, de spite the ef fect of weath er ing and re cy cling. On the other hand, REE char ac ter is - tics are not a good di ag nos tic tool to de ter mine changes in the weath er ing re gime and in palaeoclimatic con di tions – for such in ter pre ta tions, clay min eral com po si tions and re la tions between selected major elements provide a better tool.
Sig nif i cant REE en rich ment was found only in very few lay - ers, most likely en riched in ac ces sory min er als, which were car ri - ers of a va ri ety of REEs. En hanced sort ing in re cy cling could also have con trib uted to REE en rich ment. Mod er ately in tense chem i - cal weath er ing usu ally fa vours (along with re cy cling) an in crease in con cen tra tion of rare earths. How ever, dur ing ex tremely
strong hy dro ly sis (linked to trop i cal cli mate ep i sodes) even the re sis tant com po nents may be leached. Such con di tions took place, for ex am ple, at the end of the Tri as sic, as a re sult of cat a - strophic green house events. Con se quently, a clear de crease in REE in some lay ers of re sid ual clays was ob served.
Ac knowl edge ments. The REE re search was funded by the Pol ish Geo log i cal In sti tute – Na tional Re search In sti tute through in ter nal grant no. 61.6705.1301.00.0. for SM. Geo chem i cal and min er al og i cal stud ies of clay min er als pro vided in this pa per were made as a part of a pro ject fi nanced from re sources of the Pol ish Na tional Sci ence Cen tre, granted on the ba sis of de ci sion no.
DEC-2012/06/M/ST10/00478 (P.B.). Dr I. Wysocka and MSc.
D. Karmasz (PGI-NRI) are ac knowl edged for per form ing ICP-MS anal y ses. Prof. O. Lintnerová and Prof. G. Pieñkowski are thanked for very valu able com ments that im proved our pa - per. We would like to thank Prof. T. Peryt, GQ Ed i tor-in-Chief and Prof. A. Wysocka, for their use ful re marks and cor rec tions.
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