Maciej Pawlikowski, Beata Kępińska, Magdalena Sikorska, Lucyna Natkaniec-Nowak, Magdalena Dumańska-Słowik & Marian Kosuth

PRE LIMI NARY MIN ERA LOGI CAL AND PET RO GRAPHI CAL

STUD IES OF VEINS WITHIN THE COUN TRY ROCKS OF THE

NEO GENE VOL CAN ITES OF THE PI EN INY KLIP PEN BELT

AS IN DI CA TORS OF PO TEN TIAL GEO THER MAL PROC ESSES

Ma ciej PAWLIKOWSKI1, Beata KÊPIÑSKA4, Mag dalena SIKORSKA3,

Lucyna NATKANIEC- NOWAK1, Mag dalena DUMAÑSKA-S£OWIK1 & Mar ian KO SUTH2 1

De part ment of Min er al ogy, Petrog ra phy and Geo chem is try, Fac ulty of Ge ol ogy, Geo phys ics and En vi ron men tal Pro tec tion, AGH- University of Sci ence and Tech nol ogy, Al. Mickiewicza 30, 30- 059 Kra ków, Poland,

e-mails: pawlik@uci.agh.edu.pl, nat kan@uci.agh.edu.pl, du man ska@agh.edu.pl

2

Faculty of Min ing, Ecol ogy, Proc ess Con trol and Geo tech nol ogy, In sti tute of Geo sci ences, The Tech ni cal Uni ver sity of Ko ëice, 15 Komen skú Park, 042 00 Koëice,Slovakia, e-mail:Mar ian.Ko suth@tuke.sk

3

Polish Geo logi cal In sti tute, 4 Ra kow iecka Str., 00- 975 War saw, Poland, e-mail:mjaw@pgi.gov.pl

4

Polish Acad emy of Sci ences, Min eral and En ergy Econ omy Re search In sti tute, ul. Wy bickiego 7, 31- 261 Kra ków, Poland, e-mail: lab geo_bk@in te ria.pl

Pawlikowski, M., Kêpi ñska, B., Sik or ska, M., Natkaniec- Nowak, L., Du mañska-S³owik, M. & Ko suth, M.. 2009. Pre limi nary min era logi cal and pet ro graphi cal stud ies of veins within the coun try rocks of the Neo gene vol can ites of the Pi en iny Klip pen Belt as in di ca tors of po ten tial geo ther mal pro cesses. An nales So cie ta tis Ge olo go rum Po lo niae, 79: 177–185.

Ab stract: Field and as min era logi cal and pet ro graphi cal ex ami na tions of sedi men tary rocks pres ent in the area sur round ing the Pi en iny Klip pen Belt were per formed. The aim of these in ves ti ga tions was to iden tify the symp toms of hy dro ther mal pro cesses within the stud ied rocks. Moreo ver, the ar eas pro spec tive for the oc cur -rences of geo ther mal wa ters, al ter na tive source of ther mal en ergy in stead of tra di tional power pro duc tion us ing fos sil fu els, were in di cated. Ana lyti cal in ves ti ga tions were fo cused mainly on min era logi cal com po si tion of rocks as well as on the fre quency of oc cur rences of vari ous veins (mainly built of car bon ate min er als) in ter sect ing the rocks from the neigh bour hood of Neo gene an desitic rocks from the Pi en iny Klip pen Belt. The high est quan tity and thick ness of the veins was ob served in the rocks from the area of Piekie³ko stream near Kroœci enko. The clas tic rocks (sand stones) from this area con tain many frac tures which are cru cial for po ten tial geo ther mal wa ter cir cu la tion.

Key words: dia gene sis, hy dro ther mal ac tiv ity, geo ther mal en ergy, Pi en iny Klip pen Belt. Manu script re ceived 29 September 2008, ac cepted 1 July 2009

IN TRO DUC TION

coun tries is re spon si ble for grow ing de mand for var i ous mi- neral re sources. Grow ing global de mand for en ergy causes in creas ing need of al ter na tive en ergy sources. Large scale use of geo ther mal en ergy (di rect use and lo cal heat ing sys -tems, elec tric ity gen er a tions, geo ther mal heat pumps etc.) is glob ally im por tant as a per spec tive re new able en ergy source. In Po land, geo ther mal heat sta tions at Mszczonów, Pyrzyce, S³omniki, Uniejów and Stargard Szczeciñski have been com pleted yet. How ever, the in ter est in geo ther mal en -ergy is still grow ing (e.g. Soko³owski, 1995; Kêpiñska et

al., 2000; Kêpiñska, 2001, 2006; Kêpiñska & £owczowska,

2002; Chowaniec, 1989; Chowaniec et al., 1999; Pawli-kowski & Mazurek, 2000).

The Pi en iny Klip pen Belt is a north ern bar rier for the Pod hale geo ther mal sys tem (Kêpi ñska, 2001, 2006). The zero elec tro mag netic in duc tion anom aly is as cribed to it, what sug gests the oc cur rence of geo ther mal wa ters at great depths (Jan kowski et al., 1982). In the tec tonic con tact zone be tween the Pod hale Ba sin and the Pi en iny Klip pen Belt, a sur face ther mal posi tive anom aly was re corded at 0.5–1°C above the av er age back ground val ues (Po mi anowski, 1988). It is proba bly caused by the in creased heat (wa ter?) trans port from the lower crust and up per man tle to wards the Earth sur face in the peri-Pieniny strike- slip fault.

The Pi en iny Klip pen Belt is geo logi cally com pletely dif fer ent from the Pod hale Ba sin sys tem, which is an im por tant res er voir of ther mal wa ters (Kêpi ñska, 2006). In this re

-gion, nu mer ous out crops of mag matic rocks can be found (Ma³kowski, 1948, 1958; Wo jciechowski, 1955; Birk en ma -jer, 1958, 1962, 1965, 1979; Pawlikowski & Wiewiórka, 1979; Para cho niak & Pawlikowski, 1980). Tec tonic engagement of both clas tic and car bon ate rocks was also ob served. Car bon ate rocks showing high per me abil ity and nu -mer ous frac tures are pre ferred sedi ments for karst pro cesses. These con di tions are fa vour able for geo ther mal wa -ter oc cur rence. The above men tioned prem ises call an ar gue for the ex is tence of geo ther mal wa ters in some parts of the Pi en iny Klip pen Belt. The towns as Szczawnica and Kroœci enko, situ ated in the Pi en iny Mts., are still wait ing for eco logi cal heat ing sys tems us ing geo ther mal en ergy. The ques -tion if these re new able en ergy sources can be ac quired just from the Pi en iny Klip pen Belt re sources is still open.

The bib li og ra phy on ge ol ogy as well as on min er al ogy and pe trog ra phy of rocks pres ent in the ex am ined area is very rich (Ma³kowski, 1948, 1958; Birkenmajer, 1958, 1962, 1965, 1979, 1986; Birkenmajer & Pécskay, 2000; Golonka et al., 2005, and oth ers). How ever, in this re gion the geo ther mal in ves ti ga tions have not yet been car ried out in de tail. Con se quently, ad e quate stud ies of geo ther mal en ergy po ten tial in the Pieniny Klippen Belt should be ini ti -ated as soon as pos si ble. The in ter est in pos si ble geo ther mal wa ters oc cur rence there is still in creas ing. Po ten tial in ves

-tors are en cour aged by the fact that in the ad ja cent Podhale re gion (Bañska, Zakopane), ther mal wa ters have been ex -ploited for heat ing and rec re ation pur poses for a dozen of years (Soko³owski, 1984, 1995; Kêpiñska & £owczowska, 2002). In Bukowina Tatrzañska, Bia³ka Tatrzañska and Zakopane, dif fer ent geo ther mal in vest ments are still in prog -ress. On the other hand, in Slovakia, geo ther mal wa ters are used for balneotherapy and rec re ation in much broader scope than in Po land (Fendek et al., 1995; Fendek & Franko, 2000). Ther mal spas, wa ter rec re ation cen ters in Poprad, Vranov and Beëenova and many oth ers of fer all-year-round wide choice of var i ous ser vices and at trac tions.

The in ves ti ga tions of geo ther mal sys tems are very ad -vanced in Europe (e.g. Four nier & Trues dell, 1973, 1974; Krist manns dot tir & Tomas son, 1978; Browne, 1978, 1993; Ar nors son, 1983; Kêpi ñska, 2001, 2006). Con se quently, the rec og ni tion of hy dro ther mal ac tiv ity symp toms within the coun try rocks of Pi en iny Klip pen Belt was the main aim of this pa per. These hy dro ther mal pro cesses have re sulted from the cir cu la tion of min er al ized so lu tions within the coun try rocks dur ing and af ter an des ites crys tal li za tion (Sze liga et al., 2005). The pre sented re sults in clude macroand mi cro scopic stud ies macroand catho do lu mi nes cence (CL) ob ser va tions of 26 rocks sam ples host ing nu mer ous min er al -ized veins.

178

METH ODS

Field works in cluded the sam pling of se lected rock se -ries cut by many veins filled with min er als (Figs 1, 2). The pres ence of con tact zones of vari ous geo logi cal units (e.g. be tween the Pi en iny Klip pen Belt rocks and Ma gura Pala-eo gene se ries, Pod hale Palaeo gene flysch), the zones of fault ing as well as the prox im ity of an des ite out crops were ad di tional cri te ria for sam pling (Fig. 2). The sam ples of rocks con tain ing min er ali za tion veins were mostly col lected along the streams. The fre quency of veins oc cur rence (amount per m2) within the rocks was de ter mined in the scale of 1–5 (were 1 is the small est and 5 is the high est). Their thick ness was meas ured dur ing field works too (Ta ble 1).

The macro- and mi cro scopic in ves ti ga tions of the rocks were car ried out at the labo ra to ries of De part ment of Min er -al ogy, Petrog ra phy and Geo chem is try, Fac ulty of Ge ol ogy, Geo phys ics and En vi ron mental Pro tec tion, AGH- UST (Uni ver sity of Sci ence and Tech nol ogy) in Kraków, and in the Pol ish Geo logi cal In sti tute in War saw (catho do lu mi nes -cence analy sis).

Stan dard op ti cal analy ses were car ried out on pol ished thin sec tions with the use of a po lar iz ing mi cro scope (Olym -pus BX 51 with DP 12 cam era).

Catho do lu mi nes cence analy ses (CL) were car ried out on pol ished thin sec tions us ing the Cam bridge Im age Tech -nol ogy CCL 8200 MK3 de vice (cold cath ode) linked to a

Nikon Op ti phot 2 po lar is ing mi cro scope. CL pho tos were taken us ing a Mi cro flex UFX–DX cam era.

The mi cro scopic and catho do lu mi nes cence analy ses were ap plied to de scribe min era logi cal and pet ro graphi cal char ac ter of the stud ied rocks as well as the vein min er ali za -tion.

RE SULTS

The re sults of mac ro scopic char ac teri za tion of the rocks (sand stones and lime stones) are shown in Table 1. Vari ous forms of veins in ter sect ing these rocks are pre sented on fig ures 3A and 3B. The most nu mer ous and thick est vein min er ali za tion (on the base of about 50 meas ur -ments) ap pears within rocks sam pled from the vi cin ity of the Piekie³ko stream situ ated west of Kroœci enko (sam ple nos 5, 6, 7) and from the re gion be tween Szczawnica and the Ho mole ra vine re serve (sam ples nos 25, 26) (Figs 5, 6). Me dium fre quency of veins in the stud ied rocks is most of ten ob served (Fig. 5). It is noted at fol low ing out crops 1–5 and 8–22, while the maxi mum fre quency was ob served at points of sam pling nos 6, 7 and 23–27. The thick est veins were ob served at the same places were they are most fre -quent (Fig. 6).

The mi cro scopic ob ser va tions have shown that the ma jor ity of veins in ter sect ing the rocks are com posed mainly of car bon ate min er als (cal cite) and sub or di nately of

Fig. 2. Geo log i cal sketch-map of Szczawnica-Kroœcienko area. 1 – Palaeogene flysch (Magura Nappe); 2 – Pieniny Klippen Belt (Grajcarek Unit, Klippen nappes, Klippen cover: Ju ras sic–Cre ta ceous); 3 – am phi bolean de site in tru sions (1st phase), ex posed at the sur -face; 4 – subsurface an de site in tru sions as traced by magnetometric sur vey; 5 – north ern bound ary strike-slip fault (Early Mio cene) of the Pieniny Klippen Belt; 6 – transversal and oblique strike-slip faults (Mid dle Mio cene) (af ter Birkenmajer & Pécskay, 2000)

180

Ta ble 1

Char ac ter is tics of veins from coun try rocks of the Pieniny Klippen Belt

Sample

No Localization

Characterization of rocks containing the secondary mineralization Max. thickness of veins (cm) Frequency of veins occurrence (scale 1-5) 1 Ochotnica - the Gorcowy stream Brown-gray fine-grained sandstone 0.4 1 2 Ochotnica - the Jurgowski stream Brown-gray fine-grained sandstone with the

admixture of silt matrix 0.5 2

3 Ochotnica exit Brown-gray fine-grained sandstone 0.8 1

4 E bank of the Dunajec river Brown-gray fine-grained sandstone with the

admixture of carbonate cement 0.05 2

5 The Piekie³ko stream Brown- gray micrite limestone 3.5 5

6 N bank of the Kroœnieñski stream Brown-gray fine-grained sandstone 3.0 4

7 Kluszkowce Yellowish fine-grained sandstone 3.5 2

8 The drift on the way to Sromowce Gray-brownish fine-grained sandstone 1.5 1

9 Niedzica, the castle neighbourhood Gray micrite limestone 2.0 2

10 Èerveny Klaštor Gray-brown sandstone with the admixture of

carbonate cement 2.0 3

11 The stream, E from Èerveny Klaštor Gray-brown medium-grained sandstone 1.5 1 12 The stream, E from Èerveny Klaštor Brown-gray fine-grained sandstone 1.5 2 13 W bank of the stream in £apsze Brown-gray sandstone with the admixture of silt

matrix 1.0 1

14 W bank of the stream in £apsze Brown-gray fine-grained sandstone 0.9 2 15 W bank of the stream in £apsze Brown-gray fine-grained sandstone 2.2 2 16 W bank of the stream in Spišska Stará Ves Brown-gray coarse-grained sandstone 0.9 2 17 W bank of the stream in Spišska Stará Ves Brown-gray fine-grained sandstone 2.7 2 18 W bank of the stream in Spišska Stará Ves Brown-gray coarse-grained sandstone 1.6 2 19 W bank of the stream in Spišska Stará Ves Brown-gray fine-grained sandstone 1.0 1 20 The Wielka Leœna stream, W bank Brown-gray fine-grained sandstone with the

admixture of carbonate minerals 0.8 1

21 The Wielka Leœna stream, W bank Brown-gray fine-grained sandstone with the

admixture of silt matrix 0.6 1

22 The stream between Spišska Stará Ves and Èerveny

Klaštor Brown-gray fine-grained sandstone 2.2 3

23 The stream between Spišska Stará Ves and Èerveny

Klaštor Brown-gray fine-grained sandstone 4.2 4

24 N bank of the Dunajec River, over Sromowce

Wy¿ne Gray micrite-sparite limestone 4.5 4

25 The Grajcarek stream near Szczawnica Brown-gray coarse-grained sandstone 1.5 4 26 The Grajcarek stream near Szczawnica Brown-gray fine-grained sandstone 1.5 4

Fig. 3. A, B – macrophotographs of sand stones with car bon ate veins (sam ple no 15 and 6), C – con cen tra tion of py rite crys tals in cen tral part of a cal cite vein (sam ple no 6; partly crossed polarizers), D – three gen er a tions of cal cite in veins: fine crys tal line (the old est gen -er a tion), me dium crys tal line (youn g-er gen -er a tion), coarse crys tal line (the youn gest gen -er a tion), sam ple no 10, partly crossed polariz-ers; E – idiomorphic quartz crys tal (Q) at the con tact with coarse crys tal line cal cite (C), sam ple no 16, partly crossed polarizers; F – idiomorphic quartz crys tal con cen trated along the con tact of vein with sand stone (sam ple no 20, crossed polarizers); G – ac cu mu la tion of or ganic mat ter be tween cal cite crys tals of two gen er a tions oc cur ring in veins (sam ple no 23, partly crossed polarizers); H – de formed struc ture of cal -cite crys tals (pres ent in vein) in a fis sure sub ject to tec tonic move ments (sam ple no 16, partly crossed polarizers)

quartz. Fe sul phides and or ganic sub stance oc cur in traces. The sizes of cal cite crys tals range from very small (5 µm) xe no mor phic – to large (1.5 cm) idio mor phic in di vidu als showing per fect rhom bo he dral cleav age. Fe sul phides (mainly py rite, sub or di nately mar ca site) are ob served in veins cut ting rocks oc cur ring near Kroœcienko (Fig. 1, sam -ple nos 5, 6). They form mi cro crys tal line con cre tions or idio mor phic crys tals oc cur ring both in the cen tre of veins and in the con tact zone of the veins with the rock (Fig. 3C).

Sev eral cal cite gen era tions were ob served in car bon ate veins in ter sect ing sedi men tary rocks (sand stones, lime stones) both in Po land and Slo va kia (Fig. 3D). Their oc cur -rence in di cates that the crys tal li za tion of this min eral took place dur ing re peated broad en ing and con tract ing of the fis -sures within the rocks in ques tion.

Quartz oc curs only in veins from the Palaeo gene sand stones of the Slo vak part of the Pi en iny Klip pen Belt (out -crops nos 23–27). It is lo cated in the cen tre of car bon ate veins (younger gen era tion) or at the con tact zone of the vein and the host rock (older gen era tion). The quartz forms idio mor phic crys tals up to 4 mm in size (Fig 3E, F) and some -times is sur rounded by ore min er als (iron suphides).

The mi cro scopic ob ser va tions show that the min er al iz ing so lu tions, which pene trated frac tured rocks, also con -tained hy dro car bons. Their ac cu mu la tion be tween grains of dif fer ent cal cite gen era tions were ob served in veins pres ent at Slo vak out crops of these rocks (Fig. 3G).

The solid in clu sions of platy min er als show ing low in -ter fer ence colours (kaolinite?) oc cur in the close vi cin ity of quartz crys tals, in cen tral part of veins (i.e. the youn gest gen er a tion of veins).

The cy cli cal na ture of postmag matic and tec tonic ac tiv ity of the Pieniny Klippen Belt is man i fested by the pres -ence of sev eral cal cite gen er a tions within the veins as well as by di ver si fied ren o va tion of frac tures. It is ob served both in cen tral parts of veins (sym met ri cal fis sures along the vein axis) and at the con tact with the host rock. Petrographic cha- racter (mostly ori en tated struc ture of rocks) seems to in di -cate the place mode of re new ing pro cess of the fis sures. In com pact sand stones with car bon ate ce ment, cal cite crys tals fill ing veins are firmly con nected with the host rocks and the fis sures ap pear only within the veins it self. On the other side, in sand stones with less com pact ce ment ing ma te rial com posed of e.g. clay min er als, the fis sures can be found at the con tact between the vein and host rock.

The ef fects of tec tonic pro cesses within the sand stones studied can be man i fested by the de for ma tion and dis lo ca tion of com po nents of veins. Nu mer ous elon gated and de -formed cal cite crys tals are ob served (Fig. 3H). Af ter the ren o va tion and ex ten sion of veins, as a re sult of me chan i cal ac tiv ity, a new gen er a tion of crystals was formed.

The cathodoluminescence ob ser va tions con firm that

the vein min er al iza tion in the stud ied rocks pro ceeded in sev eral stages. Car bon ate veins show light and dark or ange CL col our, at trib uted to sev eral cal cite gen er a tions. Com plex struc ture of these veins, in ter sect ing the forms of dif -fer ent gen e sis, as well as mul ti ple open ing and heal ing of fis sures can be eas ily found dur ing CL anal y sis (Fig 4. A, B). Some thin veins run ning in side larger ones, which are in vis i ble un der mi cro scopic ob ser va tions, are well ob served on CL pho tos. Some car bon ate veins ex hibit zonal struc ture. It is ob served that the crys tal li za tion pro cess started on fissure walls and proceeded toward the centre (Fig. 4C, D). Cal cite oc curs also in inter gra nu lar spaces of sand -stones and some times forms pseudo morphs af ter quartz (?). Three gen er a tions of cal cite, show ing var i ous CL colours, can be dis tin guished within one con cen tra tion of the car -bon ate ce ment, but the de ter mi na tion of their se quence of generations is difficult.

An ker ite was iden ti fied in one car bon ate vein (sam ple no 13). It does not show lu mi nes cence in CL due to the sig -nif i cant amount of iron in its struc ture (Fig. 4E, F).

Kaolinite is an other min eral which ap pears in car bon ate veins in dis persed form within cal cite crys tals. Some times it fills voids within the veins and oc curs along the stylolite seams. On the CL pho tos, kaolinite shows dark blue lu mi -nes cence col our (Fig. 4G, H).

Quartz was found in two crys tal line forms: i.e. idio-morphic crys tals (found near the veins’ walls) and ir reg u lar in di vid u als (fill ing the frac tures within cal cite veins). It does not show CL col our what in di cates its low-tem per a ture or i gin.

CON CLU SIONS

Literature data con cern ing min er al og i cal and pet ro graph i cal in ves ti ga tions of res er voir rocks host ing geo ther -mal aqui fer from the Podhale re gion in di cate that the vein min er al iza tion con sists mainly of cal cite, do lo mite and sub-ordinately of sid er ite, quartz, clay min er als, while Fe-sul-phides and hy dro car bons ap pear only in traces (Chowaniec

et al., 1999; Kêpiñska, 2001, 2006; Cebulak et al., 2004).

Sim i lar min eral phases were rec og nized by the pres ent au -thors within veins in ter sect ing coun try rocks of the Neo gene andesites from the Pieniny Klippen Belt. Mi cro scopic observations have shown that cal cite was the main com po -nent of these veins. In the rocks from the Pol ish part of the Pieniny Mts. Fesulphides were found, whereas in the sand -stones from Slovakia quartz, kaolinite and organic sub-stance (hy drocar bons?) were identified.

Fig. 4. A – sev eral gen er a tions of cal cite in veins formed in fine grained sand stone (sam ple no 8, crossed polarizers); B – CL im age of cal cium car bon ate veins (vide Fig. 4a); C – frag ment of a vein built of coarse-crys tal line cal cite (sam ple no 16, crossed polarizers); D – CL im age of a cal cite vein (vide Fig. 4c) with kaolinite (?) con cen tra tion (vi o let CL col our); E – frag ment of a vein built of coarse-crys tal line cal cite (sam ple no 13, crossed polarizers); F – CL im age of a vein (vide Fig. 4E). Ac cu mu la tion of an ker ite (black CL col our) in the cen tre of a cal cite vein (or ange CL col our); G – con cen tra tion of kaolinite in a cal cite vein (sam ple no 16, crossed polarizers); H – CL im age of a vein (vide Fig. 4G). Con cen tra tion of kaolinite (vi o let CL col our)

The fre quency of oc cur rences and thick ness of the veins in the stud ied rock sam ples is pre sented in fig ures 5 and 6. The crys tal li za tion of min er als within these car bon ate veins took place in stages. This is the re sult of sev eral repeated tec tonic ep i sodes af fect ing sand stones from the Pieniny Klippen Belt and of the cy clic na ture of so lu tions that gave rise to crys tal li za tion of min er als within the frac -tures. The larg est quan tity and thick ness of veins was observed in the rocks from:

– the sur round ings of the Piekie³ko stream (3 km west of Kroœcienko);

– the re gion be tween Szczawnica and the Homole ra -vine.

The thick ness and fre quency of oc cur rence of veins from the Haligovce and Spiëská Stara Ves re gion (Slovakia) is sim i lar to the same fea tures ob served in Piekie³ko re gion in Po land.

Bas ing only on vein min er al iza tion and the ef fects of tec tonic ac tiv ity ob served within the stud ied rocks, the above men tioned re gions seem to be pro spec tive for the oc -cur rences of geo ther mal wa ters. How ever, the pre sented stud ies should be treated as pre lim i nary. More ad vanced geo log i cal and drill ing in ves ti ga tions should be ap plied in the near fu ture to solve the prob lem in ques tion. The rec og -ni tion of deep-seated geo log i cal struc tures and geo ther mal gra di ent are the fac tors which could con firm the selected areas as geothermally prospective.

Ac knowl edge ments

The au thors are grate ful to Prof. K. Birkenmajer and un known re viewer for crit i cal read ing of the manu script and valu -able cor rec tions as well as to Prof. W. Narêbski for his care ful re vi sion and friendly com ments.

The pa per is the re sult of sci en tific co op er a tion of the Fac ulty of Ge ol ogy, Geo phys ics and En vi ron men tal Pro tec tion (AGH-Uni ver sity of Sci ence and Tech nol ogy), the Min eral and En ergy Econ omy Re search In sti tute (Pol ish Acad emy of Sci -ences) in Kraków with the In sti tute of Geo-sci ences (the Tech ni cal Uni ver sity of Kosice).

This work was sup ported by the AGH-Uni ver sity of Sci ence and Tech nol ogy (Kraków, Po land)re search pro ject no 10.10. 140.482.

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