Rare earth el e ments (REE) and tho rium in the youn gest Pleis to cene gla cial tills in Po land
Pawe³ KWECKO1, *
1 Pol ish Geo log i cal In sti tute – Na tional Re search In sti tute, Rakowiecka 4, 00-975 Warszawa, Po land
Kwecko, P., 2016. Rare earth el e ments (REE) and tho rium in the youn gest Pleis to cene gla cial tills in Po land. Geo log i cal Quar terly, 60 (2): 451–460, doi: 10.7306/gq.1295
The study en com passed out crops of gla cial tills (top soil, sub soil-1, sub soil-2) of the max i mum stadial of the Vistulian Gla - ci ation and of the Wartanian Stadial of the Odranian Gla ci ation, oc cur ring along the max i mum ex tent of the Vistulian ice sheet. The youn gest Pol ish gla cial tills show very sim i lar con cen tra tions of REE and Th. The con cen tra tions of these el e - ments vary across a wide range from 0.08 mg/kg (Tm and Lu) to 70.3 mg/kg (Ce), with slightly higher val ues for the older tills (Wartanian). Both these tills show clear frac tion ation of LREE and HREE, with a higher and more var ied LREE con cen - tra tion. The most prom i nent fea ture dis tin guish ing one till from the other is the dis tri bu tion of REE frac tions along their ver - ti cal sec tions. In the youn ger (Vistulian) tills the max i mum con cen tra tion of in di vid ual LREE is found at a depth of 1.0 m, and of HREE, Sc and Th, at 2.0 m; while in the older (Wartanian) tills the high est con cen tra tions of all el e ments in ves ti - gated are ob served at a depth of 1.0 m. Also, the min eral com po si tions of the tills are very alike. The dom i nant min er als are quartz (av er age 56%) and feld spars (ap prox i mately 9%), with a trend of de creas ing con cen tra tions with depth. There are no car bon ates in the top soil (0.3 m level), and the clay min er als are dom i nated by illite (ap prox i mately 16%) and kaolinite (av er age 5%). Sta tis ti cal anal y sis in di cates over a dozen fac tors de ter min ing the con cen tra tion of REE and Th in both tills.
Three of them have a cru cial (96% of to tal vari a tion) ef fect on the con cen tra tions of these el e ments. These fac tors are prob a bly of geogenic na ture, in ti mately as so ci ated with sim i lar source ar eas, and with sim i lar pro cesses of de po si tion, diagenesis and weath er ing of the tills.
Key words: REE, gla cial tills, Vistulian ice sheet, Wartanian Stadial.
INTRODUCTION
The rare earth el e ments (REE) com prise a group of 15 lanthanides – La, Ce, Pr, Nd, Pm – radionuclide, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu), scan dium (Sc) and yt trium (Y) (IUAPC..., 1970; Henderson, 1984; De Vos et al., 2006). The REE are usu ally di vided into two con ven tion ally termed groups:
light (LREE) in clud ing La through Eu (or oc ca sion ally Gd) and heavy (HREE) from Gd (or Tb) through Lu. Most sci en tists also dis crim i nate a third group that partly over laps the LREE and HREE: the me dium REE (MREE) group that com prises Sm through Ho. Al though Y is the light est REE, it is usu ally as - signed to the HREE due to its phys i cal and chem i cal sim i lar ity (Migaszewski and Ga³uszka, 2015).
REE con cen tra tion is usu ally pre sented not as an ab so lute value but a nor mal ized value, which al lows de ter min ing the rel - a tive en rich ment of en vi ron ments ana lysed for these el e ments.
Nor mal ized value is a ra tio of an a lyt i cally de ter mined con cen - tra tion of an el e ment to its con cen tra tion in ma te rial of a stan - dard (of me te or ite, ig ne ous rock, sed i men tary rock, soil). Nor -
mal iza tion is also help ful in ana lys ing both REE frac tion ation and anom a lies by de ter min ing their in ten sity us ing quan ti ta tive in di ca tors based on nor mal ized val ues. These val ues are usu - ally pre sented in the form of graphs that al low for easy de ter mi - na tion of the en rich ment/de ple tion of a group or of a sin gle el e - ment (Laveuf and Cornu, 2009). Hor i zon tal line of nor mal ized REE con cen tra tion de notes there is no en rich ment, and its ris - ing/fall ing trend along a given stretch in di cates there is an en - rich ment/de ple tion in the el e ment (or a group of REE).
The fre quency of REE oc cur rence in na ture is greater than of many rare met als, and their dis tri bu tion in rocks and soils is the sub ject of a grow ing num ber of non-eco nomic ge ol ogy stud ies.
REE are a use ful tool in geodynamic (e.g., Galbarczyk - -G¹siorowska, 2010), palaeo geo graphi cal (e.g., Singh and Rajamani, 2001) and strati graphic (e.g., D³ugosz, 2002) stud ies.
The pa per by Fedele et al. (2008) pres ents the con tents of REE dis tri bu tion in soils (and floodplain and stream sed i ments) across Eu rope. These au thors used data from the geo chem i cal at las of Eu rope (De Vos et al., 2006) de vel oped within the frame work of the FOREGS pro ject. In pre vi ous geo chem i cal stud ies of sed i - men tary de pos its in Po land, REE were not a com mon sub ject of in ter est (Duczmal-Czernikiewicz, 2012; Ma³ecka, 2012;
Bojakowska et al., 2013) and have not been so far used in the strati graphic cor re la tion of Qua ter nary de pos its. This study pro - vides an at tempt to an swer the ques tion of whether it is fea si ble to use vari a tions in REE con cen tra tions in sec tions of these tills for strati graphic stud ies in ar eas of late-gla cial re lief, and how the
* E-mail: pawel.kwecko@pgi.gov.pl
Received: February 4, 2016; accepted: May 6, 2016; first published online: May 19, 2016
var i ous REE (LREE, HREE) and Th con cen tra tions in these sec - tions can sup port map ping sur veys.
This pa per pres ents an anal y sis of the dis tri bu tion of REE (and Sc, Y and Th) con cen tra tions in gla cial tills of the youn gest glaciations (the max i mum stadial of the Vistulian Gla ci ation and the Wartanian Stadial of the Odranian Gla ci ation) in Po land.
The chem i cal and min eral com po si tion of gla cial tills de pends mostly on the great lithological vari abil ity of mother host rocks (the hard bed rock of the Bal tic Sea Ba sin and Scan di na via) eroded by the ice sheet. The tills of both glaciations are sim i lar in terms of source ar eas, pro cesses of de po si tion, diagenesis and weath er ing, but differ in the duration of weathering.
The most com mon di vi sion of REE into two sub groups is used in this pa per: LREE (light rare earths) rang ing from La to Eu, which in cludes el e ments of more al ka line prop er ties, and HREE (heavy rare earths) from Gd to Lu and Y, show ing less al ka line prop er ties (Charewicz, 1990).
Ac cord ing to the Pol ish stra tig ra phy as cur rently valid – In - struc tions of De tailed Geo log i cal Map of Po land in scale 1:50,000 (Instrukcja..., 2004), the older tills rep re sent the Warta - nian Gla ci ation, how ever, their strati graphic rank has re cently been re duced to the Wartanian Stadial of the Odranian Gla ci - ation (Ga³¹zka et al., 1999; Lindner and Marks, 2012) and such a strati graphic po si tion of the older tills is adopted in this pa per.
STUDY AREA AND METHODS
The study area is lo cated in north ern Po land and cov ers out crops of the youn gest Qua ter nary tills of the Odranian Gla ci - ation (Mid dle Pol ish Com plex) and the Vistulian Gla ci ation (North Pol ish Com plex). Eight test ar eas (mov ing from the east): VI, I, II, VIII, III, VII, IV and V (num ber ing in chro no log i cal or der; Fig. 1), were marked out along the max i mum ex tent of the Vistulian ice sheet (Marks, 2002).
The ar eas of sam pling sites were se lected based on se - lected Pol ish geo log i cal map sheets at a scale of 1:50,000. Af - ter ver i fi ca tion of the li thol ogy of sed i ments ex posed on the sur - face, the ar eas were marked out so that each of them cov ered out crops of tills of the Main Stadial of the Vistulian Gla ci ation (youn ger tills) and of the Wartanian Stadial of the Odranian Gla - ci ation (older tills) (Marks, 2005).
Rock sam ples for the anal y sis were taken from lodge ment till (de pos ited from ac tive ice un der the ice sheet) or melt-out till (rock ma te rial de pos ited from stag nant ice; Lisicki, 2003; Kenig, 2009). These are com pact plas tic (or hard plas tic) tills con tain ing a va ri ety of lithological ad mix ture of ig ne ous, meta mor phic and sed i men tary rocks. They com prise a broad spec trum of poorly sorted tills: sandy, sandy with gravel, silty, sandy-silty, silty with gravel (peb bles). The great di ver sity of tex tural and struc tural
Fig. 1. Lo ca tion of the study ar eas
fea tures of the tills made it im pos si ble to dis tin guish the char ac - ter is tic li thol ogy (lithotype) for a given area, level or gla ci ation.
Field work. In each test area, three hand-drilled bore holes (by a stan dard hand au ger set) were un der taken to a depth of 2 m in the youn ger tills (max i mum stadial of the Vistulian Gla ci - ation), and three in the older tills (Wartanian Stadial of the Odranian Gla ci ation). Ap prox i mately 500 g sam ples were col - lected from tills of each bore hole, at depth ranges of 0.0–0.3 m, 1.0–1.3 m, and 1.8–2.0 m. These three lev els are re ferred to here in af ter as top soil, sub soil-1, sub soil-2. Re fer ring to the cur - rent tax on omy of Pol ish soils (Systematyka..., 2011), these three ho ri zons gen er ally can be as so ci ated with lev els of soil:
top soil to the level of hu mus (A), sub soil-1 with the level of leach ing (E) and the sub soil-2 with level of en rich ment (B). A to - tal of 48 bore holes were drilled and a to tal of 144 till sam ples were taken.
Lab o ra tory work. Af ter crush ing and quar ter ing, the till sam ples were ground in ag ate ball mills to the <0.06 mm frac - tion. Sam ple min er al isa tion was car ried out in a mix ture of HNO3 + HClO4 + HF, and the con cen tra tions of REE (La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sc and Y) and Th were de ter mined by the ICP-MS method.
Most of the sam ples (108) were also ana lysed for de ter mi - na tion of min eral com po si tion us ing the XRD method af ter sep - a ra tion of the clay frac tion (<0.02 mm). Ori ented air-dry glyco - lated and heated (at 550°C) sam ples were ana lysed. Per cent - age con cen tra tions of the in di vid ual phases were semi -quan ti - ta tively eval u ated by an ex ter nal stan dard method (by com par - ing the in ten sity of an a lyt i cal peaks of min er als on X-ray graphs of standard samples and examined samples).
Sta tis ti cal anal y sis. The fol low ing sta tis ti cal pa ram e ters were used to as sess the na ture of the dis tri bu tion of el e ments stud ied: dis tri bu tion in ter val (D = min-max), dis tri bu tion cen tre [a
= (min + max)/2], min i mum to max i mum value ra tio (Ý = min/max), stan dard de vi a tion (s) and skew ness in dex dis tri bu - tion (q). The re sults of these in di ca tors com ply with the cri te ria of nor mal dis tri bu tion (Ý >0.1; m–w < s; 3< D/s <5; q <2) (Mazerski, 2009), thus the me dian and the arith me tic mean are con sid ered as the rep re sen ta tions of cen tral ten dency, and the stan dard de vi a tion as the dis per sion in dex (Ta ble 1).
RESULTS
Min eral com po si tion of the clay frac tion in the gla cial tills. The clay frac tion (<0.02 mm) of the tills of both glaciations is char ac ter ized by low qual i ta tive and quan ti ta tive vari abil ity.
Both the youn ger and the older tills are dom i nated by quartz, ac com pa nied by feld spars. The quartz con tent is es ti mated at 50–65% (av er age 56%) and the feld spar con tent at 8–10% (av - er age 9%) with a trend of de creas ing con tents of both min er als with depth. The ma jor ity of sam ples re veal the pres ence of cal - cite and do lo mite, but the char ac ter is tic fea ture is the lack of car bon ates in the sur face level (top soil). In both tills, illite is the most com mon min eral (~16%), fol lowed by kaolinite (5% on av - er age). In the deeper zones (sub soil-1, and sub soil-2) the con - tents of these min er als are higher com pared to the sur face level (top soil), how ever, it is slightly higher in the older tills (Wartanian). The amounts of ver mic u lite, mont mo ril lo nite and chlorites are sim i lar in the tills from both glaciations (an av er age of 2, 4 and 3%, re spec tively), with the high est con tent in the top - soil and slightly higher con tents in the youn ger tills (Vistulian).
Com mon min er als are am phi boles ac com pa nied, but only in the Vistulian tills and in trace amounts, by ser pen tine, mag ne - tite and talc. Mixed-lay ered min er als of chlorite/ver mic u lite type
are found in the whole sec tion of the youn ger tills (Vistulian), whereas in the older tills (Wartanian) they oc cur only at sub - soil-1.
Con cen tra tions of REE and Th. The con cen tra tions of these el e ments vary in a wide range from 0.08 mg/kg (Tm and Lu) to 70.3 mg/kg (Ce), while the av er age and me dian val ues in the Vistulian and Wartanian tills are sim i lar (both in the en tire sec tions and in top soil and sub soils), like the other sta tis ti cal pa - ram e ters of the LREE and HREE con cen tra tions. Gen er ally, slightly higher con cen tra tions of the el e ments ana lysed are found in the older tills (Wartanian Stadial of the Odranian Gla ci - ation; Ta ble 1).
As re gards the ver ti cal sec tions of both the youn ger and older tills, the low est con cen tra tions of the el e ments are char ac - ter is tic of the sur face level (top soil), whereas the max i mum con - cen tra tions show a dif fer ent dis tri bu tion and oc cur at var i ous depths de pend ing on the age. In the youn ger tills (Vistulian), sub soil-1 shows the high est con cen tra tions of most LREE (La, Ce, Pr, Nd and Sc and Th), while sub soil-2 has the HREE (in - clud ing Eu) con cen tra tions. How ever, in the older tills (Odranian) the max i mum con cen tra tions of all el e ments in ve s ti - gated oc cur in sub soil-1 (Ta ble 1).
Both the Vistulian and Wartanian tills clearly show dif fer - ences in the con cen tra tions of REE and Th, de pend ing on the geo graphic lo ca tion. In east ern Po land the con cen tra tions are much higher than in the west. The high est con cen tra tions of REE and Th were re corded in the Vistulian till in re gion I. In the older tills (Wartanian), en rich ment in Sc, Y and Ce is ob served in area I, while the high est con cen tra tions of other LREE (and HREE) and Th are found more to the east, in area VI. The low - est con cen tra tions of the el e ments ana lysed in the tills of both glaciations were found in the west ern area IV (Ta ble 2).
INTERPRETATION
The small est con cen tra tions of REE and Th in the top soils of both tills are prob a bly the re sult of weath er ing and pedogenic pro cesses (argilluviation, mi gra tion with or ganic mat ter and Fe-Mn ox ides). Low pH val ues fa vour this pro cess, and about 60% of the Pol ish soils is very acidic, acidic and slightly acidic (pH £6.7; Lis and Pasieczna, 1995). REE re moved by soil so lu - tions from the up per part of weath ered zone are in cor po rated (to vary ing de grees) into new min er als (Öhlan der et al., 1996;
Panahi et al., 2000; Taunton et al., 2000; Gnandi and Tobschall, 2003) that pre cip i tated at deeper lev els to en rich the lower zones of the sec tion with these el e ments (Braun et al., 1993;
Nesbitt and Markovics, 1997; Ma et al., 2002).
Con cen tra tion of LREE in weath ered ma te rial due to the eas ier re lease of HREE to mi grat ing so lu tions (Elderfield et al., 1990; Kabata-Pendias and Mukherjee, 2007; Galbarczyk - -G¹siorowska, 2010), re ported in weath er ing pro cesses, is also seen to oc cur in both the gla cial tills. This is in di cated by a de - creas ing ra tio of LREE/HREE frac tion ation with in creas ing depth. The low est REE con cen tra tion in the up per part of the sec tion con firms the gen eral phe nom e non of de creas ing REE con cen tra tions with the in creas ing de gree of rock weath er ing (Bonnot-Courtois, 1981; Boulangé and Colin, 1994; Öhlander et al., 1996; Taunton et al., 2000). In the de pos its ana lysed, this pat tern can be linked with the oc cur rence of the max i mum con - cen tra tion of LREE in the sub soil-1 of both tills.
The most im por tant fea ture to dis tin guish be tween the two tills is the pres ence of the max i mum con cen tra tion of HREE and Eu at dif fer ent depths. In the older tills (Wartanian) the peak con - cen tra tion oc curs in sub soil-1, while in the youn ger tills (Vistulian)
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it is in sub soil-2. The dif fer ences re late mainly to the av er age val - ues and, to a lesser ex tent, to the me dian val ues. These dif fer - ences are rel a tively small; how ever, it is dif fi cult to clearly iden tify the causes of the re corded higher HREE con cen tra tion at a greater depth in the youn ger de pos its. This may re sult from the di verse dis tri bu tion of mixed-lay ered min er als of chlorite/ver mic - u lite type ob served through the whole sec tion of the youn ger tills (Vistulian). Whereas, in the older tills (Wartanian) this only re fers to sub soil-1, bear ing in mind that smectite and chlorite are en - riched in HREE, while illite and ver mic u lite are en riched in LREE.
This can also be a re sult of a pro cess af fect ing the dis tri bu tion of pri mary sil ica min er als (e.g., gar nets, hornblende, orthopyro - xene), which are richer in HREE (Kanazawa and Kamitani, 2006), or the dis tri bu tion of de posit-form ing” REE min er als such as bastnäsite, monazite, loparite (en riched in LREE) or xeno time and ap a tite (en riched in HREE) (Zepf, 2013; Ryder and Nowak, 2015). A de crease in the pro por tion of pri mary car bon ates can also cause en rich ment in HREE (Reeder and Amer ica, 1983), and the tills of both glaciations con tain car bon ates in deeper zones (ex cept top soil) of the ver ti cal sec tion. The avail able study
re sults are in suf fi cient to re solve this ques tion, res o lu tion of which re quires fur ther re search.
REE in sed i men tary rocks are gen er ally nor mal ized to two stan dards: post-Archean Aus tra lia Shale – PAAS (Tay lor and McLennan, 1985; Fedele et al., 2008) and North Amer i can Shale Com pos ite – NASC (Gromet et al., 1984). Ad di tion ally, the anal y sis of nor mal ized con cen tra tion of REE and Th was per formed for the Vistulian and Wartanian tills with ref er ence to the av er aged com po si tion of sub soil and top soil in the area of Po land (FOREGS) (De Vos et al., 2006) and chondrite (Tay lor and McLennan, 2009).
Nor mal iza tion rel a tive to PASS (Fig. 2) and NASC (Fig. 3) pres ents a very sim i lar re sult. The con tent of REE and Th shows a sharp de ple tion (ex cept for Eu) in Vistulian and Wartanian tills at all lev els. Both of the normalizations ex pressly in di cate the low est abun dance of all el e ments ana lysed in the top soil level and a slightly greater range of di ver sity of con tents deeper (sub soil-1 and sub soil-2) in the older tills (Wartanian).
Nor mal iza tion to soils (sub soil: 0.5–2.0 m and top soil:
0.25 m) from Po land (FOREGS) in di cates an en rich ment of the T a b l e 2 REE and Th con cen tra tions in tills of the max i mum stadial of the Vistulian Gla ci ation and the Wartanian Stadial
of the Odranian Gla ci ation in the study ar eas
max. stadial (Vistulian) Wartanian stadial (Odranian)
V IV VII III VIII II I VI V IV VII III VIII II I VI
W ——————- ar eas ————————— E W ——————- ar eas ————————— E
mg/kg mg/kg
Sc 5.1 4.8 5.7 6.1 5.5 6.0 7.4 5.4 6.0 4.7 5.1 5.8 4.6 5.5 6.5 5.4
Y 10.0 9.5 12.9 12.4 12.9 13.0 15.3 14.6 13.2 9.2 11.5 11.7 11.5 12.9 15.7 14.9 La 16.8 15.2 19.5 16.6 20.8 19.4 23.8 22.6 21.1 14.0 18.5 17.3 17.5 20.2 23.0 23.5 Ce 35.5 32.5 40.9 36.2 42.5 43.8 53.0 47.9 44.6 30.0 37.6 36.5 35.3 46.5 49.8 49.2
Pr 4.1 3.7 4.7 4.2 5.1 4.7 5.8 5.4 5.1 3.4 4.4 4.2 4.2 4.9 5.6 5.8
Nd 15.8 14.6 17.9 16.0 19.6 18.1 21.8 20.9 19.6 13.0 17.1 15.9 15.9 19.0 21.6 22.3
Sm 3.0 2.7 0.7 3.0 0.8 3.5 4.2 3.9 3.7 2.5 0.7 3.1 0.7 3.7 4.2 4.3
Eu 0.6 0.6 3.4 0.7 3.7 0.7 0.9 0.9 0.8 0.6 3.2 0.7 3.0 0.8 0.9 0.9
Gd 2.6 2.3 2.9 2.7 3.2 3.0 3.6 3.5 3.3 2.1 2.8 2.6 2.6 3.0 3.6 3.7
Tb 0.4 0.3 0.4 0.4 0.5 0.4 0.5 0.5 0.5 0.3 0.4 0.4 0.4 0.4 0.5 0.5
Dy 2.0 2.0 2.5 2.2 2.6 2.5 3.0 2.7 2.4 1.9 2.2 2.3 2.2 2.6 3.0 3.0
Ho 0.4 0.4 0.5 0.4 0.5 0.5 0.6 0.5 0.5 0.4 0.4 0.4 0.4 0.5 0.6 0.6
Er 1.1 1.1 1.4 1.2 1.4 1.4 1.7 1.5 1.3 1.0 1.2 1.2 1.2 1.5 1.7 1.7
Tm 0.2 0.1 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.1 0.2 0.2 0.2 0.2 0.2 0.2
Yb 1.0 1.0 1.3 1.1 1.3 1.2 1.4 1.4 1.2 0.9 1.2 1.1 1.2 1.3 1.4 1.5
Lu 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.1 0.2 0.2 0.2 0.2 0.2 0.2
Th 5.6 4.8 5.7 5.4 5.9 6.2 6.7 7.1 7.0 4.8 5.6 5.8 5.0 6.5 6.6 7.2
Fig. 2. PASS-nor mal ized (Tay lor and McLennan, 1985) REE and Th con cen tra tions in tills of the Vistulian (max i mum stadial) and Odranian (Wartanian Stadial) glaciations
tills in REE, al beit to a lim ited ex tent. This is not sur pris ing, bear - ing in mind that most of brown earth soils (over 50%) and podsols (about 26%) of Po land have de vel oped on mo raine tills and loamy sands, and weath er ing and pedogenic pro cesses have im pov er ished these de pos its in re la tion to the par ent rock.
The en rich ment does not in volve the con cen tra tions of Y, Tm, Yb and Lu in both of the gla cial tills nor of Dy, Ho and Er in the top soil (0.3 m) of the older till (Wartanian). The char ac ter is tic fea ture of this nor mal iza tion is a very clear pos i tive Eu anom aly in di cat ing an en rich ment in both tills of this el e ment, and a greater di ver sity of HREE con cen tra tion in the older tills of the Wartanian Stadial of the Odranian Gla ci ation (Fig. 4).
The most uni ver sal and most com monly used chondrite nor mal iza tion (Nakamura, 1974; De Vos et al., 2006; Tay lor and McLennan, 2009) showed a sig nif i cant REE en rich ment of the tills of both glaciations. It in di cated LREE/HREE frac tion - ation, LREE en rich ment, pos i tive Eu ano m aly, con sid er able en - rich ment in Th, and de ple tion in Sc in both tills (Fig. 5).
Normalizations to sed i men tary rocks gen er ally show a de - ple tion in the tills of both glaciations of REE and Th. This may show that the de ple tion is caused by spe cific con di tions of weath er ing of “REE-bear ing” min er als which, dis solved and leached, are sub se quently pre cip i tated as sec ond ary min er als in deeper zones of the sec tion or trans ferred to other glacial deposits.
All the con cen tra tion normalizations for REE and Th in both of the tills in di cate: Eu en rich ment, REE and Th con cen tra tion di ver sity in the sec tions (higher in the older tills), and frac tion - ation of these elements.
The eu ro pium anom aly (Eu/Eu*) is the ra tio of de ter mined Eu con cen tra tion to its ex pected (nor mal ized) con cen tra tion (McLennan and Tay lor, 2012). It is the o ret i cally de ter mined by in ter po lat ing the con cen tra tions of two ad ja cent rare earth el e - ments (by their po si tion in the pe ri odic ta ble) and us ing chondrite-nor mal ized val ues.
The Eu/Eu* value in di cates an en rich ment in the tills of both glaciations of this el e ment in all depth ranges ana lysed in this study. In the youn ger tills (Vistulian) the value of this pos i tive anom aly in creases with depth (from 1.3 to 1.7 m), while in the older tills it has a con stant value (1.4) along the whole section.
The oc cur rence of a pos i tive Eu anom aly in the tills of both glaciations is in con tra dic tion with the neg a tive (and sig nif i cant) Eu/Eu* trend ob served in up per man tle rocks (McDonough and Sun, 1995) and in soils de vel oped on sed i men tary rocks (Chen and Yang, 2010). In creased con cen tra tion of Eu in sed i men tary rocks is most of ten in ter preted as in her ited from par ent ig ne ous rocks (Tay lor and McLennan, 1985; Awwiller, 1994; Nyakairu and Koeberl, 2001; McLennan and Tay lor, 2012), mainly acid rocks (Terekhov and Shcherbakova, 2006) which abound in Eu, and this is prob a bly the cause of this anom aly in both gla cial tills.
This ob ser va tion is sup ported by stud ies of gla cial tills in Swe den – one of the main source ar eas of rock ma te rial trans - ported by ice streams and lobes to Po land. The REE and Th con cen tra tions de ter mined in those tills is al most twice as high as those found in the Vistulian and Wartanian tills of Po land.
The Eu anom aly in the tills of Swe den marks min er ali sa tion zones in that area, with dom i nant min er als such as al la nite, Fig. 3. NASC-nor mal ized (Gromet et al., 1984) REE and Th con cen tra tions in tills of the Vistulian (max i mum
stadial) and Odranian (Wartanian Stadial) glaciations
Fig. 4. FOREGS-nor mal ized (De Vos et al., 2006) REE and Th con cen tra tions in tills of the Vistulian (max i mum stadial) and Odranian (Wartanian Stadial) glaciations
bastnäsite, monazite, ap a tite, zir con and flu o rite, which are rich in Eu (An der son et al., 2014).
An other ex pla na tion for the pos i tive eu ro pium anom aly in both tills may be the pres ence of plagioclases in their com po si - tion. Feld spars, as the only pri mary min er als, are char ac ter ized by the pres ence of a pos i tive Eu anom aly (Chase et al., 1963;
Towell et al., 1969; Henderson, 1984; Aubert et al., 2001;
Compton et al., 2003; Galán et al., 2007). The con tent of feld - spars in the tills ex am ined is sig nif i cant (~9%) and these min er - als are rel a tively highly prone to weath er ing pro cesses, which may cause mo bi li za tion and ac cu mu la tion of Eu in sec ond ary min er als (illites or smectites) that are rel a tively com mon con stit - u ents of the tills (~16% illite). Cer tainly, the pro cesses of weath - er ing, for ma tion of sec ond ary min er als, and trans por ta tion into deeper zones of the tills may have also sig nif i cantly af fected the for ma tion and dif fer en ti a tion of Eu anom aly val ues (Ta ble 3), al - though their con tri bu tion is dif fi cult to es ti mate.
The tills of both glaciations were ana lysed for REE frac tion - ation – the sep a ra tion into light el e ments (LREE: La-Ce-Pr-Nd - -Pm-Sm-Eu) and heavy el e ments (HREE: Gd-Tb-Dy-Ho- Er- Tm- Yb-Lu+Y) us ing chondrite-nor mal ized val ues (Tay lor and McLennan, 2009) and La/Lu, La/Yb ra tios.
The ra tios have sim i lar val ues for the tills of both glaciations and point to marked frac tion ation of the el e ments. In both the youn ger and the older tills, the en rich ment in LREE is over three times greater as com pared to HREE (av er age 3.3), and the LREE/HREE ra tio slightly de creases with depth. Anal y sis of the La/Lu and La/Yb ra tios in di cates an over ten-fold de ple tion of the tills in Lu and Yb (HREE) as com pared with La (LREE), with a slight vari a tion of these ra tios in the ver ti cal sec tion of both tills. In the older tills (Wartanian) the La/Yb ra tio de creases with depth
(from 11.2 to 10.6), while in the youn ger tills (Vistulian) the ra tio has a value of 10.9 in the top soil and sub soil-1 (Ta ble 3).
The de creas ing LREE/HREE frac tion ation with depth and higher val ues of frac tion ation ra tios of the older tills (Wartanian) sug gest that the en rich ment in LREE is due mainly to weath er ing pro cesses re sult ing in eas ier dis so lu tion and mi gra tion of HREE in the sec tion, caus ing a “pas sive” con cen tra tion of LREE, as shown by many ear lier stud ies (Nesbitt, 1979; Duddy, 1980; Topp et al., 1984; Braun et al., 1990; Xing and Dudas, 1993; Boulangé and Colin, 1994; Ma et al., 2002; Compton et al., 2003).
Re la tion ships be tween the el e ments ana lysed were de ter - mined by the Pearson’s cor re la tion co ef fi cient (r). For most of the el e ments the r val ues were >0.9 (sta tis ti cal sig nif i cance p
<0.05), in di cat ing a very strong sim i lar ity of the dis tri bu tions of REE and Th el e ments in the till sec tions of both glacia tions.
This pat tern may in di cate a sim i lar (mainly qual i ta tive) com po si - tion of source ma te rial and sim i lar pro cesses of trans port, de po - si tion and diagenesis of gla cial ma te rial dur ing both glaciations.
The Wartanian tills of the Odranian Gla ci ation show a slightly greater pro por tion of higher val ues of the cor re la tion co ef fi cient, in di cates a stron ger re la tion ship of REE as a group in the older tills, which may be related to a higher degree of sediment diagenesis.
In or der to iden tify the likely sources of REE in the tills, a fac tor anal y sis was per formed on raw data us ing the Varimax method.
The anal y sis shows that there are three fac tors that have a crit i cal ef fect on the REE dis tri bu tions in the tills of both glaciations de fin - ing >96% of the to tal vari a tion (Ta ble 4).
The con tri bu tion of the ef fect of the first fac tor to the dis tri bu - tion of REE is >80%, and this fac tor in flu ences the con cen tra - tions of not only HREE and Gd but also Nd, Pr, La in the tills of Fig. 5. Chondrite-nor mal ized (Tay lor and Mac Lennan, 2009) con cen tra tions of REE and Th
in tills of the Vistulian (max i mum stadial) and Odranian (Wartanian Stadial) glaciations
T a b l e 3 Val ues of La/Yb, La/Lu, Ce and Eu anom a lies and LREE/HREE
(chondrite-nor mal ized) frac tion ation ra tios in tills of the max i mum stadial (Vistulian) and the Wartanian Stadial (Odranian)
Level La/Yb La/Lu Ce/Ce* Eu/Eu* LREE/HREE
max. st.
Vistulian
n = 72 0.3–2.0 10.7 10.7 1.0 1.5 3.3
n = 24
0.3 10.9 10.5 1.0 1.3 3.5
1.0 10.9 11.0 1.0 1.6 3.4
2.0 10.4 10.7 1.0 1.7 3.2
Wartanian st.
Odranian
n = 72 0.3–2.0 10.8 10.9 1.0 1.4 3.3
n = 24
0.3 11.2 10.7 1.1 1.4 3.5
1.0 10.8 10.8 1.0 1.4 3.3
2.0 10.6 10.8 1.0 1.4 3.3
both glaciations, and the Ce con cen tra tion in the older tills (Wartanian Stadial of the Odranian Gla ci ation). The sec ond fac tor ac counts for only 9% of the REE con cen tra tion vari a tion.
It in volves the Sm and Eu con cen tra tions in both tills. The con - tri bu tion of the ef fect of the third fac tor to the dis tri bu tion of REE is only 3% in the tills of both glaciations. The con cen tra tions of Th and Ce are related to the third factor.
The above fac tors af fect the same (or very sim i lar) el e men - tal as so ci a tions in the tills of both glaciations, which again points to sim i lar con di tions and pro cesses af fect ing the for ma - tion of gla cial tills of the youn gest glaciations. These fac tors are of geogenic na ture and are closely re lated to the pro cesses of the ac qui si tion of rock ma te rial (by gla cial ero sion and in cor po - ra tion), its trans port, de po si tion and diagenesis. Dur ing these pro cesses and long-term weath er ing, both pri mary and sec ond - ary clay min er als be come the most im por tant source of REE (Polañski, 1988; Kabata-Pendias and Mukherejee, 2007). Dis - tinc tion Eu in the sec ond fac tor and Ce and Th in the third fac tor shows a greater con tri bu tion of heavy min er als to the REE ac - cu mu la tion. Dis tri bu tion of Sm and Eu in the tills ana lysed may be as so ci ated with the pres ence of monazite and bastnäsite, while Th may be linked with weath er ing-re sis tant min er als. Tho - rium bound in this form in a sed i men tary and diagenetic en vi - ron ment is not mo bi lized, and the dif fer ences in the con cen tra - tions may re flect the con tri bu tion of de tri tal ma te rial to the rock mass (Krishnaswami, 1976; Cochran et al., 1986).
DISCUSSION
It should be borne in mind that the chem i cal and min eral com po si tion of gla cial tills de pends mostly on the par ent host
rocks. The main source ma te rial for tills is the hard bed rock of the Bal tic Sea Ba sin and Scan di na via, eroded by the ice sheet. The out crops of the bed rock show great lithological vari abil ity and oc cur at very dif fer ent lo ca tions and to dif fer ent ex tents. Par ent rocks in clude out crops of sed i men tary rocks (Or do vi - cian and Si lu rian lime stone, marl, sand stones and shales; Cam brian shale, De vo nian do lo mite; Pa leo - zoic sand stones and shales) dom i nant in the Bal tic Sea Ba sin, Pre cam brian (mainly) ig ne ous rocks (grani to ids, diorite, syenite), meta mor phic rocks (gneiss es) and an allochthonous cover of Qua ter nary de pos its (Jasiewicz, 2006). The sim i lar con cen tra - tions of REE and Th (al though slightly higher in the older, Wartanian tills) point to very sim i lar con di tions and for ma tion pro cesses, as well as a sim i lar source ma te rial for Qua ter nary gla cial tills of the youn gest glaciations in Po land.
Lower con cen tra tions of REE and Th in the youn - gest (Vistulian and Wartanian) tills of Po land com - pared to those from a part of the source area, i.e. the tills from the area of Swe den, can be at trib uted to in - tense weath er ing pro cesses of source rock ma te rial both dur ing south ward trans port and af ter de po si tion.
The de ci sive fac tors in the mo bi li za tion of these el e - ments were chem i cal weath er ing pro cesses re leas ing REE (mainly from the sur faces of crys tal struc tures) from min er als, caus ing de ple tion of the tills in the orig i - nally ac cu mu lated com po nents.
The most im por tant fea ture dis tin guish ing be - tween the two tills is the dif fer ent dis tri bu tion of REE frac tions in the ver ti cal sec tions. The max i mum con - cen tra tions of LREE in the youn ger (Vistulian) tills are found in sub soil-1, and of HREE and Sc and Th in sub soil-2, while the high est con cen tra tions of all these el e ments in the older (Wartanian) tills were de ter mined in sub soil-1. This di ver sity could be used to de ter mine the age of the tills in ar eas of uncertain stratigraphic position.
The sig nif i cantly higher REE con cen tra tion in the tills of both glaciations in the east ern ar eas com pared to the west ern re - gions sug gests dif fer ent po si tions of source ar eas for in di vid ual ice lobes. Sim i lar con clu sions are in ferred from the anal y sis of min eral com po si tion of the clay frac tion, which does not change sig nif i cantly due to the age of the tills and the depth of their oc - cur rence, but changes due to their geo graphic po si tion. In ad di - tion to illite and kaolinite, the tills from the east ern re gions con - tain feld spars, car bon ates, ver mic u lite, chlorite and am phi - boles, while in the west ern ar eas, illite and kaolinite pre dom i - nate in the clay frac tion. There fore, it can be thought that the di - ver sity of the com po si tion of the till ana lysed is less af fected by the strati graphic fac tor – their age (gla ci ation), but largely by the palaeogeographic fac tor – the ex tent and source area of a given ice lobe. The lat i tu di nal vari abil ity of both the REE con cen tra tion and the min eral com po si tion may in di cate dif fer ent com po si - tions of the ma te rial trans ported by the var i ous ice streams, and asyn chron ous prop a ga tion of gla cial lobes across Po land (Marks, 2010).
In terms of REE and Th con cen tra tions, the Vistulian and Wartanian tills are de pleted com pared to the stan dards of sed i - men tary rocks (nor mal iza tion to NASC, PAAS), and en riched when com pared to chondrite as well as to soils in north ern Po - land (FOREGS). En rich ment in the tills of the el e ments ana - lysed rel a tive to the soils is caused by weath er ing and pedogenetic pro cesses that im pov er ish the sur face layer (top - soil) in these el e ments. On the other hand, the en rich ment rel a - tive to chondrite is prob a bly as so ci ated with el e vated REE con - cen tra tions in the source (Scan di na vian) ma te rial. This is con - T a b l e 4
Fac tor eigenvalues, cu mu la tive value, and fac tor co or di nates of REE and Th con cen tra tions in tills of the max i mum stadial (Vistulian)
and the Wartanian Stadial (Odranian)
max. stadial – Vistulian Wartanian Stadial – Odranian
FACTOR FACTOR
1 2 3 1 2 3
eigenvalue 14.10 1.69 0.56 eigenvalue 14.44 1.51 0.45
% of to tal 82.95 9.91 3.27 % of to tal 84.95 8.90 2.64 cu mu la tive
% of to tal 82.95 92.86 96.14 cu mu la tive
% of to tal 84.95 93.85 96.49
Lu 0.916 –0.040 0.316 Er 0.925 0.052 0.277
Ho 0.913 0.017 0.290 Ho 0.921 0.048 0.269
Er 0.912 0.016 0.310 Tm 0.918 –0.031 0.312
Tm 0.910 –0.057 0.333 Dy 0.917 0.048 0.286
Yb 0.908 –0.060 0.345 Lu 0.910 –0.001 0.315
Dy 0.906 0.011 0.290 Yb 0.907 –0.021 0.337
Y 0.905 0.025 0.251 Gd 0.905 0.039 0.328
Gd 0.902 0.010 0.316 Y 0.894 0.002 0.230
Tb 0.878 0.010 0.305 Tb 0.877 0.055 0.334
Nd 0.829 0.000 0.424 Nd 0.870 0.038 0.417
Pr 0.801 0.011 0.457 Pr 0.850 0.045 0.439
La 0.752 –0.007 0.545 La 0.817 0.022 0.459
Ce 0.685 0.084 0.577 Ce 0.707 0.116 0.595
Sc 0.497 0.104 0.387 Sm 0.591 0.722 0.303
Th 0.482 0.139 0.822 Sc 0.557 0.026 0.350
Eu 0.439 –0.882 0.111 Th 0.535 0.166 0.776
Sm 0.350 0.890 0.226 Eu 0.200 –0.978 0.014
Ab so lute val ues above 0.3 are marked in bold
sis tent with the pos i tive Eu anom aly ob served in the tills stud - ied, which is unique in sur face en vi ron ments and is in her ited from the par ent (mainly ig ne ous) rocks of the source area. Tills in Swe den (one of the main source ar eas) con tain al most twice as much REE and Th as gla cial tills in Po land, and the Eu anom aly in Swe den marks min er ali sa tion zones. The fol low ing min er als are in di cated as the source of Eu in these zones: al la - nite, bastnäsite, monazite, ap a tite, zir con and flu o rite (An der - son et al., 2014).
CONCLUSION
Sim i lar REE and Th con cen tra tions, as well as in suf fi cient data, do not al low us ing REE con cen tra tion vari abil ity as a good chronostratigraphic in di ca tor un equiv o cally dif fer en ti at ing the youn gest gla cial tills: Vistulian (max i mum stadial) and Odranian
(Wartanian Stadial). The ob served east-west vari abil ity in the con tents of el e ments ana lysed in the till of the same gla ci ation in - di cates the het er o ge ne ity of the ice sheet which can be as so ci - ated with var i ous un der ly ing lithologies tra versed by dif fer ent ice streams. A more prom is ing re search di rec tion may be to use changes in REE con cen tra tion and min eral com po si tion as tools of to con strain the move ment of for mer ice streams (ice lobes).
Ac knowl edge ments. The au thor thanks Dr. A. Pasieczna for sub stan tive as sis tance in text prep a ra tion. Prof. L. Marks and Dr. K. Pochocka-Szwarc are ac knowl edged for „Qua ter - nary con sul ta tions”. I ex press pro found grat i tude to all the re - view ers of this work – Prof. Z Migaszewski, Prof. S. Wo³kowicz and anon y mous re viewer for their in sight ful com ments, im por - tant sug ges tions and help in the pro cess of writ ing, and to the ed i tor, Prof. T.M. Peryt, for his ed i to rial as sis tance.
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