Annales Societatis Geologorum Poloniae (2013), vol. 83: 229–242.
NEE DLE-FI BRE CAL CITE AND NANOFIBRES AS COM PO NENTS
OF HO LO CENE FIS SURE-FILL ING CAR BON ATES
IN SOUTH ERN POLAND
Micha³ GRADZIÑSKI, Renata JACH & Edyta GÓRNIKIEWICZ
In sti tute of Geo log i cal Sci ences, Jagiellonian Uni ver sity, Oleandry 2a, 30-063 Kraków, Po land; e-mails: michal.gradzinski@uj.edu.pl, renata.jach@uj.edu.pl, edytag89@gmail.com
Gradziñski, M., Jach, R. & Górnikiewicz, E., 2013. Nee dle-fi bre cal cite and nanofibres as com po nents of Ho lo cene fis sure-fill ing car bon ates in south ern Po land. Annales Societatis Geologorum Poloniae, 83: 229–242.
Ab stract: The ar ti cle deals with the car bon ates, fill ing fis sures in lime stone bed rock and pres ently ex posed in a south-fac ing rock wall of Kramnica hill (Pieniny Klippen Belt, south ern Po land). The car bon ates are com posed of (i) nee dle-fi bre cal cite crys tals, (ii) car bon ate nanofibres, (iii) car bon ate nanoparticles, and (iv) micrite and sparite cal cite crys tals. De tri tal grains from the car bon ate bed rock oc cur subordinately. The spa tial re la tion ships of the com po nents give doc u men ta tion that the nanofibres were formed si mul ta neously with or slightly later than the nee dle-fi bre cal cite crys tals. There ex ists a con tin u ous chain of forms from nanoparticles to elon gated nanofibres. This, in turn, in di cates that all the above mor pho log i cal forms are re lated ge net i cally. In rel a tively wide fis sures, the car bon ates stud ied formed stepped microterracettes, sim i lar to those of speleothems, mainly of moonmilk type. Con versely, nar row fis sures are com pletely filled with car bon ates, which dis play par al lel lam i na tion. The car bo-n ates were formed ibo-n the late Ho lo cebo-ne. How ever, “dead car bobo-n ef fect” pre cludes the pos si bil ity of abo-ny pre cise dat ing of them. Their d13C and d18O val ues are in ranges from 5.1‰ to 3.8‰ and from 6‰ to 4.7‰, re spec -tively. The car bon ates stud ied bear a strong re sem blance to soil and spelean, moonmilk-type car bon ates. This in di cates that con ti nu ity ex ists be tween the depositional en vi ron ments of soil and spelean car bon ate.
Key words: speleothems, caliche, sta ble iso topes, ra dio car bon dat ing, Pieniny Klippen Belt, West ern Carpathians. Manu script re ceived 25 No vem ber 2013, ac cepted 23 De cem ber 2013
IN TRO DUC TION
Nee dlefi bre cal cite is a ubiq ui tous com po nent of var i -ous con ti nen tal car bon ates. It was first rec og nized in soils and the un der ly ing weath ered car bon ate bed rock in Po land (Iwanoff, 1905–1906). Morozewicz (1907, 1911) coined the term “lublinite” for such elon gated car bon ate crys tals, with ref er ence to the name of the city of Lublin, east ern Po land. How ever, fur ther stud ies re vealed that it is not an in -de pend ent min eral phase, but rather rep re sents a spe cific habit of low-mag ne sium cal cite (Thugutt, 1929; Stoops, 1976; Bernasconi, 1981; see also Jones and Kahle, 1993 for dis cus sion). Al though nee dle-fi bre cal cite was at first described in a tem per atecli mate area, it at tracted close at ten tion as a com mon com po nent of mod ern calcretes, de vel -oped in arid or semi-arid re gions (James, 1972; Phillips and Self, 1987; Jones and Ng, 1988; Verrecchia, 1990; Alonso-Zarza, 2003; Alonso-Zarza and Jones, 2007; Wright, 2007; Zhou and Chafetz, 2009; Alonso-Zarza and Wright, 2010). More over, it oc curs in fos sil calcretes of var i ous ages (Wright, 1984, 1986; Wright et al., 1995; Kabanov et al., 2010). The com mon oc cur rence of nee dle-fi bre cal cite in the soil en vi ron ment of a tem per ate cli mate was fully con -firmed at many sites in Eu rope (e.g., Kowalinski et al.,
1972; Strong et al., 1992; Becze-Deák et al., 1997; Loisy et
al., 1999; £¹cka et al., 2009; Barta, 2011; MilliÀre et al.,
2011a, b). It was also de tected in the soils of trop i cal Af rica and Asia (e.g., Cailleau et al., 2005; Owliaie, 2013). Be -sides its oc cur rence in soils, nee dle-fi bre cal cite is known also from caves. It is an im por tant com po nent of some spe-leothems al most all around the world. It was doc u mented mostly in moonmilk-type de pos its (e.g., Gradziñski and Ra- domski, 1957; Stoops, 1976; Bernasconi, 1981; Gradziñski
et al., 1997; Borsato et al., 2000; Northup and Lavoie, 2001;
CaÔaveras et al., 2006; Rich ter et al., 2008; Curry et al., 2009; Jones, 2010), but also in cave pisoids (cave pearls; Jones, 2009; Gradziñski et al., 2012a). Thus, the most com -mon modes of oc cur rence for nee dle-fi bre cal cite are in the weath er ing zone and in caves lo cated some metres be low it.
How ever, in for ma tion about nee dle-fi bre cal cite within shal low parts of its host rocks is scarce. In arid cli ma tic con di tions, this kind of cal cite acts also as ce ment in young, po -rous car bon ates (e.g., Supko, 1973; Ward, 1973; Sherman et
al., 1999). Dullo and Tietz (1984) an a lyzed the dif fer en ti a
-tion of the cal cite, form ing coat ings within fis sures in Stei-ermark, Aus tria. They noted the pres ence of nee dle-fi bre
cal cite of var i ous hab its. Some pa pers, pub lished at the be -gin ning of the 20th cen tury, prob a bly also de scribed nee dle-fi bre cal cite from dle-fis sures, but there is no clear state ment of whether the ma te rial an a lyzed was col lected from soils and the weath er ing zone or from be low them (e.g., Iwanoff, 1905–1906).
The study of nee dlefi bre cal cite, us ing a scan ning elec tron mi cro scope (SEM), al lows rec og ni tion of its con sid er -able mor pho log i cal vari a tion (Dullo and Tietz, 1984; Jones and Ng, 1988; Jones and Kahle, 1993; Verrecchia and Ver-recchia, 1994; Bajnóczi and Kovács-Kis, 2006; Cailleau, 2009a). This also showed that nee dlefi bre cal cite is com -monly as so ci ated with smaller car bon ate fibres, var i ously termed mi cro-rods, nee dles and nanofibres (e.g., Philips and Self, 1987; Gradziñski et al., 1997; Borsato et al., 2000; Zhou and Chafetz, 2009; Bindschedler et al., 2010, 2012). Nanofibres, which are anal o gous in shape, can be also com -posed of or ganic mat ter (Bindschedler et al., 2010).
Nee dle-fi bre cal cite grows typ i cally in the vadose zone. None the less, there are dif fer ent opin ions as to its or i gin. Sev eral au thors drew at ten tion to the di rect or in di rect in flu -ence of mi cro-or gan isms, mainly fungi, on its for ma tion (Wright, 1984, 1986; Olszta et al., 2004; CaÔaveras et al., 2006; Blyth and Frisia, 2008; Rich ter et al., 2008; Cailleau
et al., 2009a, b; Bindschedler et al., 2010, 2012; Baskar et al., 2011). Oth ers re gard nee dle-fi bre cal cite as a prod uct of
purely physico-chem i cal pro cesses (Onac, 1995; Borsato et
al., 2000).
The pres ent pa per fo cuses on the spe cific oc cur rence of nee dle-fi bre cal cite crys tals and nanofibres, which form the car bon ate fill ings of fis sures in lime stones be low the weath er ing zone. It em pha sizes the sim i lar ity of the above com po nents to those known from soils and some spelean car bon -ates. On the ba sis of the ex am ple de scribed, some mea sure of con ti nu ity be tween the depositional en vi ron ments of soil and spelean car bon ate is in ferred.
EN VI RON MEN TAL SET TING
Fis sure-fill ing car bon ates were found in a south-fac ing wall of a rocky hill, called Kramnica (50°04.140' 19°55.919'),
tonized suc ces sion of mainly Ju ras sic rocks (Birkenmajer, 1979). Crinoidal and nod u lar lime stones are ex posed in rock cliffs. The south-fac ing wall of Kramnica is built of crinoidal lime stone, which rep re sents the Smolegowa Lime -stone For ma tion of Bajocian age (Birkenmajer, 1977). The lime stone dips south ward at an an gle of 75°. The soil cover on the top of Kramnica is rel a tively thin. It con sists of early- formed rendzina-like soils (Grodziñska, 1979).
The mean an nual pre cip i ta tion for the re gion ranges from 690–860 mm and the mean an nual tem per a ture var ies from 5–5.5°C (Kostrakiewicz, 1982). How ever, dif fer en ti a tion of the mi cro cli mate is a typ i cal char ac ter is tic of this re -gion. Thus, higher mean an nual tem per a tures reach ing 8°C might be ex pected on the south ern slopes (Kostrakiewicz, 1982). The Bia³ka River wa ter gap abounds in var i ous vas cu -lar plants. The top of Kramnica is cov ered with a rel ict pine for est, whereas epilithic and xerothermic grass form iso lated patches on the south-fac ing rock wall (Grodziñska, 1979).
MA TE RIAL AND METH ODS
Car bon ates were doc u mented on the south-fac ing rock wall of Kramnica. The sam pling of the car bon ates was kept to an ab so lute min i mum, be cause the area is un der pro tec -tion. The in ter nal struc tures of the car bon ates stud ied were ob served un der a stan dard petrographic op ti cal mi cro scope and a field emis sion SEM Hitachi S-4700, equipped with a NORAN Van tage en ergy dispersive spec trom e ter (EDS). SEM an a lyzes were per formed, us ing a work ing dis tance of 15 mm, a 10 kV ac cel er a tion volt age, and a semi-con duc tor Si (Li) de tec tor. The sam ples were mounted on SEM hold -ers with sil ver glue and coated with C or Au. The min eral com po si tion was an a lyzed by pow der X-ray diffractometry (XRD), us ing a ver ti cal XPert APD Philips goniometer (PW 1830).
The car bon and ox y gen sta ble-iso tope com po si tion of eight sam ples was ana lysed at the War saw Iso tope Lab o ra -tory for Dat ing and En vi ron ment Stud ies of the Pol ish Aca-demy of Sci ences. The cal cite sam ples were dis solved in 100% phos pho ric acid at 70°C, us ing a Kiel IV on line car -bon ate prep a ra tion de vice, con nected to a Thermo-Finnigan Delta Plus mass spec trom e ter. The qual ity of the anal y sis was con trolled by NBS19 in ter na tional stan dard mea sure -ments. The d13C and d18O val ues are pre sented rel a tive to the V-PDB. An a lyt i cal reproducibility was ver i fied on the ba sis of the re peat abil ity of the NBS19 re sults, with an ob
served de vi a tion of less than 0.07‰ for d13
C and less than 0.12‰ for 18O mea sure ments.
One sam ple of car bon ates was dated by the ra dio car bon method at the Lab o ra tory of Ab so lute Dat ing (Ska³a, Po land). Car bon di ox ide, ob tained by acid treat ment, was con verted to ben zene. Mea sure ments of ra dio car bon con cen tra -tion were car ried out, us ing the scin til la -tion tech nique by means of a new gen er a tion of lowback ground liq uid scin -til la tion coun ters, the HIDEX 300 SL (Kr¹piec and Wala-nus, 2011). The ra dio car bon date ob tained was cal i brated, us ing the OxCal pro gram (Bronk Ramsey, 2009) and Int-Cal13 cal i bra tion data (Reimer et al., 2013).
RE SULTS
Field oc cur rence and in ter nal struc ture
The car bon ates are white to very light grey in col our; only oc ca sion ally they are very pale pink, ow ing to a re sid uum weath ered from the lime stone. They are hard, but fri a -ble, and in some places pow dery. The car bon ates oc cur on the sur face of the rock wall and within the fis sures cut ting it (Fig. 2B). In the for mer case, they form patches ex clu sively in places where larger slabs of lime stone had been dis placed, which had re sulted in the open ing of fis sures and ex
-po sure of the fis sure-fill ing de -pos its (Fig. 2A). Thus, the car bon ates grew in the fis sures and sub se quently were ex -posed at the sur face. The patches are ver ti cally elon gated; they reach around 3 m in height and 0.5 m in lat eral ex tent. The car bon ates reach a thick ness of 1.5 cm. The same car -bon ate ma te rial fills fis sures, sec tions of which are vis i ble in the rock wall (Fig. 2B). Fis sures with open ings reach ing a few milli metres now are filled com pletely with car bon ates.
On the rock wall, car bon ates form stepped, over hang -ing microterracettes, com posed of crests in the form of mi-croims, which line micropools lo cated be hind them (Fig. 2C). The microrims dip out ward in such a man ner that their low er most points are at their out er most parts. The mi crorims are smooth, whereas the micropools have a rougher re -lief, which is vis i ble also un der SEM (Fig. 2D).
The ver ti cal dis tance be tween neigh bour ing microterra- cettes ranges from 3 to 13 mm. There is a clear ten dency for the microteracettes to change shape with changes in the in -cli na tion of the un der ly ing rock wall (Fig. 3A). The mi croterracettes cov er ing the ver ti cal wall are lat er ally more ex -ten sive, whereas the ver ti cal dis tance be tween neigh bour ing microterracettes is rel a tively small (Fig. 3B). The hor i zon tal di men sion of the microterracettes de creases with in creas ing an gle of the sub strate. Ac cord ingly, when the in cli na tion of the rock wall changes to the point of over hang ing, the mi
-NEE DLE-FI BRE CAL CITE AND NANOFIBRES AS COM PO NENTS OF HO LO CENE FIS SURE-FILL ING
231
Fig. 2. Out crop of fis sure-fill ing car bon ates. A. South-fac ing rock wall of Kramnica, whit ish patches de note the po si tion of car bon ates stud ied, ar row in di cates sam pling area. B. Car bon ates fill ing fis sures (ar rows) and ex posed on the rock wall (right hand side of photo). C. Microterracettes cov er ing the rock wall. D. SEM im age of a microterracette; the lin ing microrim (R) is smooth, whereas the micropool (P) is rel a tively rough
croterracettes are shorter, their rims are more curved and the pools are nar rower.
The car bon ates stud ied dis play lam i na tion, vis i ble as a re sult of changes in po ros ity. Opaque laminae are more compact and made up of tightly packed com po nents. The
intervening trans lu cent laminae are more po rous and for-med by loosely packed com po nents. The car bon ates seal ing the fis sures are char ac ter ized by lam i na tion that is roughly par al lel to the fis sure walls. Con versely, the laminae form -ing the microterracettes are curved and mimic the ex ter nal re lief (Fig. 4). The thick ness of some laminae is greater in the lower parts of the microterracettes, with small mi cro-stalactites de vel oped there.
Com po nents
The car bon ates are com posed of the fol low ing com po -nents: (i) nee dle-fibre cal cite crys tals, (ii) cal cite nanofi-bres, (iii) nanoparticles, and (iv) micrite and sparite crys tals, which oc cur ex cep tion ally. On the ba sis of the EDS re sults, all of the above com po nents are in ter preted as be ing com -posed of cal cium car bon ate with sub or di nate Mg con tent. XRD anal y ses de tected cal cite as the only autochthonous car bon ate phase (Fig. 5). In ad di tion to the above listed components, the car bon ates stud ied com prise some car bon -ate grains, de rived from the host rock, and small clumps of siliciclastic ma te rial (Fig. 4). The lat ter are prob a bly a wea-thered re sid uum.
Nee dle-fi bre cal cite crys tals
Nee dlefi bre cal cite crys tals are the most com mon com -po nent of the car bon ates stud ied (Figs 6, 7, 8A, B, H). They rep re sent two types of mor phol ogy: (i) com pos ite fi brous crystals, which are the most com mon type, and (ii) polycry-stalline chains.
The length of com pos ite fi brous crys tals var ies from 2 µm to >100 µm, whereas their width falls within the range 0.4 µm to 2 µm. Such crys tals are straight and are formed by four jux ta posed sin gle fi brous crys tals (Fig. 6D–F). They cor re spond to 4-lobed fi bre crys tals and paired rods (MA3 and MA4), dis tin guished by Jones and Kahle (1993) and Verrecchia and Verrecchia (1994), re spec tively. The jux ta -posed fi brous crys tals be tween 0.2 µm and 0.5 µm across are aligned along their long axes. The com pos ite fi brous cry-stals dis play X-shaped or dumb bell-shaped cross-sec tions. The jux ta posed fi brous crys tals seem to have pri mar ily round
Fig. 3. Re la tion ships be tween rock-wall in cli na tion, ver ti cal distance be tween microterracettes and their hor i zon tal di men sion; each point is mean of 10 mea sure ments. A. Rock-wall in cli na tion ver sus ver ti cal dis tance of microterracettes. B. Ver ti cal dis tance of microterracettes ver sus their hor i zon tal di men sion
Fig. 4. Ver ti cal cross sec tion through a microterracette; ar rows in di cate trapped de tri tal grains, com posed of Ju ras sic bed rock lime stone, M – microstalactite, thin sec tion, plane po lar ized light
Fig. 5. XRD pat tern of the fis sure-fill ing car bon ate. All peaks are re lated to cal cite, and la belled with dhkl value and rel a tive in -ten sity in %
or ex cep tion ally hex ag o nal cross-sec tions and smooth faces. Many of them are cov ered with nanofibres, nanoparticles or min ute cal cite crys tals, which partly or com pletely oblit er ate the pri mary shape. Only in one sam ple stud ied, ag glom er ates of sev eral straight fi brous crys tals were found (Fig. 6F). The ag glom er ates are cir cu lar in cross-sec tion and reach 1.5 µm across. They are akin to the crys tals il lus trated by Cailleau et
al.. (2009b, figs 3.2, 9.2).
The com pos ite fi brous crys tals show rare im per fec -tions, sim i lar to those rec og nized by Bindschedler et al.. (2012). Be tween the ma jor ity of crys tals, which dis play blunt ter mi na tions, some crys tals with acute, ir reg u lar ter -mi na tions oc cur (Fig. 7A). Other crys tals are turned at an an gle of be tween 140° and 160° (Fig. 7B) or slightly twisted along their long axes (Fig. 7C). Branch ing of some com pos -ite fi brous crys tals was also noted (Fig. 7D).
NEE DLE-FI BRE CAL CITE AND NANOFIBRES AS COM PO NENTS OF HO LO CENE FIS SURE-FILL ING
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Fig. 6. In ter nal struc ture of fis surefill ing car bon ates; SEM im ages. A. Densely packed nee dlefi bre cal cite crys tals. B. Ran domly ori -ented nee dle-fi bre cal cite crys tals, as so ci ated with nanofibres. C. Par al lel ori -ented nee dle-fi bre cal cite crys tals. D. Nee dle-fi bre cal cite crys tals of com pos ite fi brous type. E. Nee dle-fi bre cal cite crys tals of com pos ite fi brous type, ar rows in di cate their dumb bell-shaped cross-sec tion. F. Ag glom er ate com posed of sev eral straight fi brous crys tals (A) and nee dle-fi bre cal cite crys tals of com pos ite fi brous type, ar row in di cates their X-shaped cross-sec tion
Nee dle-fi bre cal cite crys tals are ran domly or par al lel dis trib uted (Fig. 6A–C). The for mer pat tern is def i nitely the more com mon. How ever, even in these cases there are some do mains, in which the neigh bour ing crys tals dis play a par al lel or subparallel ori en ta tion. The par al lel dis trib uted nee -dle-fi bre crys tals are tightly packed, whereas the ran domly dis trib uted ones show var i ous types of pack ing, rang ing from loose to tight.
Nanofibres
The nanofibres are curved and curled; they are 0.1– 0.2 µm across (Figs 6B, 7B, D, 8A, B, G). Their di am e ters, with some rare ex cep tions, ap par ently have the same or der of mag ni tude. Their lengths vary be tween 0.8 µm and >20 µm; it is im pos si ble to as cer tain the up per limit. Un com monly, some of the nanofibres have bul bous ter mi na tions. The nanofibre sur face ap pears to be smooth; an over
growth of youn ger cal cite crys tals is ex cep tional. EDS ex -am i na tion sug gests that nanofibres are com posed of cal cium car bon ate. How ever, bear ing in mind their min ute sizes, this can not be con firmed with cer tainty.
As a rule, the nanofibres form (i) clumps or (ii) a three-di men sional, pierced struc ture. Each clump con tains sev eral, curved nanofibres, which are wo ven and in ter -twined (Fig. 8B). They are closely packed, form ing a dense mat with a fit ted fab ric. The pierced struc tures are com -posed of loosely ar ranged nanofibres, which are ran domly dis trib uted or ar ranged subparallel (Fig. 8A). The con tact be tween neigh bour ing nanofibres is concavo-con vex.
The nanofibres co-oc cur with the nee dle-fi bre cal cite crys tals (Figs 6B, 7D, 8A, B). They stretch be tween neigh -bour ing nee dle-fi bre cal cite crys tals or cover them, which can re sult in the com plete oblit er a tion of their re lief.
Fig. 7. Im per fec tions in nee dle-fi bre cal cite crys tals; SEM im ages. A. Crys tal with acute, ir reg u lar ter mi na tion (ar row). B. Turned crys tal as so ci ated with nanofibres, in sert pres ents as an ex am ple a solid twisted in the same man ner. C. Crys tal twisted (ar rows) along its long axis. D. Branch ing crys tals (ar rows) as so ci ated with dense mat of nanofibres
Fig. 8. Nanofibres and nanoparticles; SEM im ages. A. Loosely ar ranged nanofibres as so ci ated with nee dle-fi bre crys tal of com pos ite fi brous type. B. Dense mat of nanofibres cooc cur ring with and cov er ing a nee dlefi bre crys tal of com pos ite fi brous type. C. clump com -posed of nanoparticles with var i ous shapes. D. Spher i cal, el lip soi dal, and rod-shaped nanoparticles. E. Clumps com -posed of spher i cal and el lip soi dal nanoparticles, as so ci ated with ir reg u lar micrite crys tal (ar row). F, G. Rodshaped nanoparticles and nanofibres. H. Nanopar ti -cles cov er ing a nee dle-fi bre cal cite crys tal
Nanoparticles
Par ti cles less than 1 µm across are named nanoparticles, fol low ing the ter mi nol ogy of Jones and Peng (2012). The ma jor ity of them are be tween 0.1 µm and 0.2 µm across (Fig. 8C–H). Such par ti cles dis play var i ous shapes: flat spheres, spheres, el lip soids, and short rods. Sev eral tightly packed nanoparticles form ir reg u lar clumps up to 15 µm across (Fig. 8E). The nanoparticles in one clump have dif -fer ent shapes and sizes (Fig. 8C). The nanoparticles are also spa tially as so ci ated with nanofibres or cover the sur face of the nee dle-fi bre cal cite crys tals (Fig. 8G, H). Like the
nanofibres, the nanoparticles most prob a bly are com posed of cal -cium car bon ate, as in ferred from EDS ex am i na tion.
Micrite and sparite crys tals
Ir reg u lar, plate-shaped crys tals of micrite, up to 10 µm across, oc cur within the other com po nents (Figs 8E, 9A). Their faces are poorly de vel oped. Such crys tals com prise nee dle-fi bre cal cite crys tals and in par tic u lar, nanofibres or nanoparticles fused to gether.
Sparite crys tals with in com plete faces rep re sent an other com po nent (Fig. 9B, C). They have a habit of trigonal prisms with flat or acute ter mi na tions and elon gated, spiky subcrystals vis i ble on in com plete side faces. The sparite crystals are up to 100 µm in length. They line and in some cases fill com pletely the larger pores within the car bon ates discussed.
Sta ble iso tope com po si tion
The sta ble iso tope com po si tions of the bulk sam ples of carbonates stud ied are listed in Ta ble 1 and pre sented in Fig. 10. The d13C and d18
O val ues of the fis surefill ing car bon -ates form a sep a rate clus ter. The d13C and d18
O val ues fall within the range from -5.1‰ to -3.8‰ and from -6‰ to -4.7‰, re spec tively.
Ra dio car bon dat ing
One sam ple of car bon ates was dated. The con ven tional age of the car bon ates is 4740 ± 110 years BP. The cal i brated age is pre sented in Ta ble 2. How ever, the age of the car bon ates stud ied can not be de ter mined pre cisely. The ra dio car -bon age ob tained most prob a bly was mod i fied by the socalled “res er voir ef fect” (“deadcar bon ef fect”), which re -sults from the in cor po ra tion of in ac tive car bon from the
Fig. 9. Cal cite crys tals; SEM im ages. A. Ir reg u lar micrite crys -tals. B. Trigonal prisms with flat ter mi na tions, acicular subcrystals are vis i ble. C. Trigonal prisms with acute ter mi na tions, acicular subcrystals are vis i ble
Fig. 10. Sta ble iso to pic com po si tion of fis sure-fill ing car bon ates and Ju ras sic lime stone bed rock
bedrock into the grow ing car bon ates (e.g., Pazdur et al., 1988 and ref er ences therein). This ef fect also was con -firmed from moonmilk speleothems in the Ital ian Alps, which were com posed of nee dle-fi bre cal cite crys tals and nanofibres (Borsato et al., 2000) in a sim i lar man ner to the car bon ates stud ied. In those speleothems, the socalled “ap -par ent age”, that is the dif fer ence be tween the true age and the con ven tional age, equalled ~1.1 ka and ~3 ka. Thus, it may be ac cepted only that the car bon ates studied were for-med between about 3500 cal years BP and 1950.
DIS CUS SION
Re la tion ship be tween com po nents
The main com po nents of the car bon ates stud ied are nee dlefi bre cal cite crys tals and nanofibres. Such an as so ci a tion, com posed of anal o gous com po nents, com monly oc -curs in soils and speleothems (Jones and Ng, 1988; Loisy et
al., 1999; Rich ter et al., 2008; Cailleau et al., 2009a;
Bindschedler et al., 2010, 2012). Some au thors pos tu lated a ge -netic re la tion ship be tween these two com po nents, whereas oth ers sug gest that they owe their or i gins to dif fer ent pro -cesses. The ex am ple de scribed does not shed light on whether there re ally ex ists a ge netic re la tion ship be tween these two com po nents; it sim ply con firms their cooc cur rence in the vadose zone. None the less, the spa tial re la tion -ship be tween the nanofibres and the nee dle-fi bre cal cite crys tals in di cates that the for mer are not older than the lat ter (Figs 6B, 8A, B). Both com po nents could have orig i nated si mul ta neously or the nanofibres can slightly post date the nee dlefi bre cal cite crys tals. More over, the shape and spa -tial ar range ments of the nanofibres con firm the pre vi ous opin ions of Borsato et al. (2000), Cailleau et al. (2009a) and Bindschedler et al. (2010) that the nanofibres or their pre -cur sors, if any, must have be haved in a plas tic man ner.
Forms that were sim i lar in shape and size to the nano-pa rticles de scribed here were re ported by Zhou and Chafetz
(2009) from Texas caliche and by Jones and Peng (2012) from hot-spring de pos its in China. An a logues nanoparticles also were pro duced ex per i men tally in lab o ra tory con di tions and in ter preted as an amor phous phase of cal cium car bon ate (Bontognali et al., 2008; Xu et al., 2008). The oc cur rence of amor phous car bon ate as a prod uct of biomineralization pro cesses was noted in the cal car e ous skel e tons of many or gan -isms (e.g., Addadi et al., 2003). Such a phase is trans formed rel a tively quickly into vaterite, ar agon ite or cal cite (e.g., Ro dri guez-Blanco et al., 2011). Thus, it seems prob a ble that the nanoparticles dis cussed were com posed of amor phous cal cium car bon ate. It is im pos si ble to state if they are still com posed of an amor phous phase or rep re sent a spe cific type of calcitic pseudomorph. The nanoparticles com prise only one com po nent that is mixed with the oth ers. Ac cord -ingly, the XRD anal y ses, in di cat ing the presence of calcite, provide information only about a bulk sample.
It is in ter est ing to note that the for ma tion of the nano-pa rticles de scribed so far com monly re sults from ei ther the pres ence of sev eral ad di tives in a par ent so lu tion, many of them or ganic com po nents, or the ac tiv ity of (mi cro)or gan -isms (Xu et al., 2005; Bontognali et al., 2008). There fore, there is an im pli ca tion that the nanoparticles de scribed were formed un der the di rect or in di rect in flu ence of mi croor gan isms. This seems to be in line with the pos tu lated or -ganic ef fect in the for ma tion of nee dle-fi bre cal cite crys tals and nanofibres (e.g., Blyth and Frisia, 2008; Rich ter et al., 2008; Cailleau 2009a, b; Bindschedler, 2010, 2012), which co-oc cur with the nanoparticles in the carbonates discussed.
Nanoparticles are as so ci ated with nanofibres in the sam ples stud ied (Fig. 8G). The anal y sis of their sizes and shapes adds a new di men sion to the dis cus sion of nanofibre or i gin. Nanoparticles dis play a wide spec trum of shapes, from tightly packed flat tened spheres, show ing sig nif i cant com pac tion, to elon gated rods (Fig. 8C–F). The rods are jux ta posed with nanofibres, which also is the case for re cent caliche from Texas (Zhou and Chafetz, 2009). Both com po -nents share the same di am e ter, a cir cu lar cross-sec tion and a smooth sur face. Some rods have also bul bous ter mi na tions, sim i lar to those of some nanofibres. All these facts lead to the con clu sion that there is no clear-cut bound ary be tween the two cat e go ries. In fact, they can rep re sent a con tin u ous chain of forms, which owe their or i gin to sim i lar pro cesses or even the same pro cess. The so lu tion-pre cur sor-solid me-chanisms ex per i men tally con firmed by Olszta et al. (2004) and the in flu ence of an or ganic tem plate pos tu lated by Bindschedler et al.. (2010, 2012) are plau si ble. The mor -pho log i cal vari abil ity of nanoparticles and nanofibres could
NEE DLE-FI BRE CAL CITE AND NANOFIBRES AS COM PO NENTS OF HO LO CENE FIS SURE-FILL ING
237
Ta ble 1
Sta ble iso tope com po si tion of the car bon ates stud ied (bulk sam ples)
Sample d18O d13C KR1_1 -5.5 -4.3 KR1_2 -4.7 -3.8 KR1_3 -5.4 -4.4 KR3_1 -5.6 -5.1 KR3_2 -5.3 -4.9 KR4_1 -5.8 -4.9 KR5_1 -6.0 -4.9 KR11_1 -5.6 -4.8 KR11_2 -5.5 -4.4 KR1_4 * -2.0 1.3 KR1_4 * -0.2 2.1 KR1_4 * -1.0 2.0
* Ju ras sic bed rock lime stone
Ta ble 2
Ra dio car bon dat ing re sults
Sample Labora-tory number Radio-carbon age [yr BP]
68.2% conf. interval 95.4% conf. interval Cal. age range [yr BP] Prob. [%] Cal. age range [yr BP] Prob. [%] H3.4 MKL-1824 4740±110 3638–3496 3460–3376 43.9 24.3 3775–3326 3231–3174 3161–3119 91.8 2.0 1.6
bon ates com pris ing cal cite of this type have been re ported from many lo cal i ties (Bajnóczi and Kovács-Kis, 2006; Cailleau et al., 2009a, b; MilliÀre, 2011a, b). The sta ble iso -tope com po si tion of the car bon ates dis cussed falls within the same range as the com po si tion of nee dle-fi bre cal cite from the soils of Reims and Bur gundy, France (Cailleau et
al., 2009b), Benasque, Spain (MilliÀre, 2011b). It is also
similar to the com po si tion of bulk sam ples of pedogenic car bon ates and moonmilk speleothems. The for mer were stud -ied from Várhegy, in Bu da pest, Hun gary (Bajnóczi and Kovács-Kis, 2006), whereas the lat ter were from Tun nel Cave, Ger many (Rich ter et al., 2008).
A com par i son be tween the d13C val ues of the car bon -ates stud ied and other Ho lo cene car bon -ates from the re gion shows a sim i lar ity to some speleothems from the Tatra caves. The Ho lo cene sta lag mite SC2, crys tal lized in Szcze-lina Chocho³owska cave, lo cated 30 km to south west of Kramnica at an al ti tude of 1050 m, can serve as an ex am ple (Gradziñski et al., 2009). How ever, these val ues are higher than those ob tained for the re cent tufa stromatolites, grow -ing at a dis tance of about 20 km to the east, at an al ti tude of about 650 m (Szulc and Smyk, 1994).
The d13C val ues of the car bon ates dis cussed are lo cated slightly above the up per limit of this pa ram e ter for car bon -ates re ceiv ing wa ter charged with soil CO2, as so ci ated with
C3 path way plants (Baker et al., 1997). This might in di cate that: (i) in tense de gas sing of CO2 pre ceded the crys tal li za
-tion of the car bon ates, (ii) rel a tively heavy at mo spheric CO2
con trib uted to the so lu tion, (iii) car bon ate mol e cules de -rived from lime stone bed rock sub stan tially con tam i nated the so lu tion, (iv) small car bon ate par ti cles of lime stone bed -rock were in tro duced into the sam ples studied (Fig. 4), or (v) crys tal li za tion pro ceeded out of iso to pic equi lib rium. It is im pos si ble to sup port un equiv o cally any of the above pos si bil i ties. How ever, the third one is in di rectly sup ported by the dat ing re sult pre sented above.
It is pos si ble to dis cuss the con di tions of crys tal li za tion, us ing an equa tion for mu lated by O’Neil et al. (1969) and later mod i fied by Fried man and O’Neil (1977):
103 2 78 106 2 89 lnac w- = . ( T )- .
-2
(1) where T is the tem per a ture of crys tal li za tion (ab so lute scale) and ac-w is the ox y gen equi lib rium frac tion ation fac
-tor be tween cal cite and wa ter ac cord ing to the for mula:
a d d c w- = + + 1000 1000 18 18 O O c w (2)
the car bon ates stud ied con tain some de tri tal ad mix tures, the autochthonous crys tals def i nitely pre dom i nate and the sec -ond pos si bil ity can be ruled out. The third pos si bil ity may be at trib uted to the fast de gas sing of CO2, which might be
plau si ble. How ever, the weak cor re la tion of d18O and d13C (r2 = 0.56) does not strongly sup port such a sce nario. In tense de gas sing is hardly ex pected in poorly ven ti lated fis sures (see Gradziñski et al., 2012b). How ever, crys tal li za tion out of iso to pic equi lib rium can also re sult from mi cro -bial in flu ence (Gradziñski, 2003).
The cal cite grew in the vadose zone, above the wa ter ta -ble. Thus, a higher d18
O of the pa ren tal wa ter than that of the ground wa ter in the re gion can be ex plained in a two fold man ner. The grow ing cal cite may have been sup plied with wa ter pre cip i tated only in the warm sea sons, that is, wa ter with a higher d18
O than the an nual weighted mean in the re -gion. In the Tatras, at an al ti tude of 1100 m, the d18O of sum mer pre cip i ta tion is around 3.5‰ higher than the an nual weighted mean (Rozanski and Dulinski, 1988). The dif fer -ence is slightly smaller in Kraków, at an al ti tude of 205 m, where it equals around 2.5‰ (Duliñski et al., 2001). As -sum ing the above val ues, the d18
O of the pa ren tal wa ter in the warm sea sons may have equalled -7.31‰ V-SMOW and -8.31‰ V-SMOW in the study area. Ap pli ca tion of these val ues in the cal cu la tions leads to tem per a ture ranges of 4.9°C – 10.1°C and 1.0°C – 6.1°C, re spec tively. These val ues can be ac cepted, as they are close to the mean an nual tem per a ture in the re gion (Kostrakiewicz, 1982). Pre cip i ta -tion of the cal cite stud ied in the warmer sea sons seems to be in line with the con clu sions reached by MilliÀre et al.. (2011b), who dem on strated sea sonal growth of nee dle-fi bre cal cite in the soils in Swit zer land.
An other pro cess that can re sult in higher val ues of the d18
O of the pa ren tal wa ter is evap o ra tion, which pref er en -tially re moves light ox y gen from the so lu tion. On the one hand, evap o ra tion can be ex pected to oc cur on the south-fac ing rock wall. How ever, on the other hand, this pro cess should not be very ef fi cient in fis sures that are at least partly iso lated. On the as sump tion that evap o ra tion had an in flu -ence on the iso to pic com po si tion of the pa ren tal wa ter and the grow ing cal cites, the growth of the cal cites in the warm sea sons is in di cated. There fore, this leads to the con clu sion that the cal cites stud ied were formed mainly in the warmer sea sons. This con clu sion is closely anal o gous to the mode of or i gin, dis cussed in the pre ced ing para graph.
Con di tions of growth
Microterracettes, sim i lar to those found at Kramnica, are typ i cal of car bon ates formed from a thin film of flow ing wa ter in the con di tions of the vadose zone. They are found in travertines (e.g., Julia, 1983; Pen te cost, 2005; Ham mer et
al., 2010) and speleothems, mainly those de vel oped on overhang ing walls (Hill and Forti, 1997). They are es pe cially com mon in moonmilk speleothems, where their mi -crorim is in clined down ward, in a sim i lar man ner to those in the ex am ples stud ied (Gradziñski et al., 2010). It is in ferred that this shape re sults from the plas tic con sis tency of fresh moonmilk, which al lows it to creep down the cave wall (Gradziñski and Radomski, 1957). In the case dis cussed, the de vel op ment of microterracettes is prob a bly lim ited to the wider fis sures, which di rect the film of wa ter seep ing into the vadose zone. This would ex plain their patchy oc cur -rence. The wa ter-soaked car bon ates be haved in a plas tic man ner, as in the case of moonmilk speleothems. The nar -row fis sures prob a bly were not oc cu pied by seep ing wa ter, which re sulted in the fill ing of them by car bon ates with out microterracette re lief, in stead dis play ing lam i na tion par al lel to the fis sure walls.
Al though sim i lar microterracettes can orig i nate, as a re -sult of mi cro bial sta bi li za tion of de tri tal grains flushed with per co lat ing wa ter (Gradziñski et al., 2010), this is not the case for the Kramnica car bon ates. If the car bon ate com po -nents were trans ported from the over ly ing weath er ing zone, frag men ta tion might be ex pected, ac com pa nied by mix ing with other noncar bon ate com po nents and lime stone frag -ments, as a re sult of dis in te gra tion of the host rock. Conver-sely, only a sub or di nate amount of allochthonous de tri tal particles, de rived from the weath er ing zone or the host lime-stones, con trib uted to the car bon ates in ques tion and the fine car bon ate com po nents do not show sig nif i cant dis in te gra tion.
If each of the above dis cussed ar gu ments is taken into ac count, it might be ac cepted that the car bon ates stud ied grew within fis sures in the lime stone hostrock. They orig i -nated most prob a bly un der the di rect or in di rect in flu ence of mi croor gan isms. Sub se quently, some voids within the car -bon ates were filled with late sparry ce ments. The lack of any macro- or micro struc tures, con nected to root sys tems, in di cates that their for ma tion took place with out any di rect con tact with roots. The depth be low the soil cover is hard to as cer tain, since the for mer to pog ra phy of Kramnica may have dif fered from the pres ent one. None the less, it is likely that the dis tance to the soil cover lo cated at the top of Kram- nica was more than 15 m. Some patches of the ini tial soils as so ci ated with rocky shelves and clumps of plants may have been lo cated a smaller dis tance away. There fore, in terms of their growth within a host rock, the car bon ates dis -cussed bear a strong re sem blance to pen e tra tive caliche (Rossinsky et al., 1992) and fis sure calcretes (endostroma-tolites) (Lauriol and Clark, 1999; Lacelle et al., 2009). The car bon ates de scribed from Steiermark by Dullo and Tietz (1984) seem to be their closest recognized counterparts.
The fis surefill ing car bon ates de scribed are the next ex am ple of con ti nen tal car bon ates, in which nee dlefi bre cal cite and nanofibres are the ba sic com po nents. The car bon -ates dis cussed are formed in a spe cific en vi ron ment, lo cated
be tween the two de scribed pre vi ously and the widely dis -cussed ones, namely the weath er ing zone, in clud ing soil and caves. These en vi ron ments so far have been re garded as two sep a rate en ti ties. Thus, the fis sure-fil ing car bon ates are a “miss ing link”, which in di cates that a ge netic con nec tion ex ists be tween pedogenic and spelean carbonate depositio-nal environments.
CON CLU SIONS
1. The car bon ates fill ing fis sures in a south-fac ing rock wall of Kramnica hill are com posed of nee dle-fi bre cal cite crys tals, car bon ate nanofibres, car bon ate nanoparticles, and subordinately by micrite and sparite cal cite crys tals. De tri tal grains from the car bon ate bed rock oc cur as a minor ad mix-ture.
2. There ex ists a con tin u ous chain of forms from flat -tened, spher i cal nanoparticles through rod-shaped ones to elon gated nanofibres. This sug gests that all of the above morphological forms are ge net i cally related.
3. The nanoparticles and nanofibres could have been pre cip i tated as amor phous car bon ates. The nanofibres were formed si mul ta neously with or slightly later than the nee -dle-fi bre cal cite crystals.
4. The car bon ates stud ied are autochthonous com po -nents, which most prob a bly owe their or i gin to an or ganic in flu ence. They grew within fis sures, cut ting the car bon ate bed rock. Their ox y gen iso to pic com po si tion sug gests they grew in the warm sea sons, whereas their car bon iso to pic compo si tion doc u ments the dom i nance of soil CO2, con
-nected with C3 plants in the carbonate system.
5. In rel a tively wide fis sures, the car bon ates stud ied formed stepped microterracettes and thus bear a strong re -sem blance to speleothems of moonmilk type. Con versely, nar row fis sures are com pletely filled with car bon ates, which dis play par al lel lamination.
6. The car bon ates dis cussed are re lated in or i gin to some soil and spelean car bon ates. They were formed in fis sures, that is, in a spe cific en vi ron ment lo cated be tween soils and caves. This in di cates that a con tin uum ex ists be tween the car bon ates de pos ited in these two en vi ron ments, so far con sid -ered sep a rately in terms of their modes of or i gin.
Ac knowl edge ments
The au thors are in debted to the Re gional Di rec tor ate for En vi -ron men tal Pro tec tion in Kraków for giv ing per mis sion for the fieldwork. Thanks go also to Marek Duliñski and Hel ena Hercman for stim u lat ing dis cus sion, to Anna Lewandowska for her help with XRD, as well as to Anna £atkiewicz and Beata Zych for op -er at ing the SEM. The pa p-er has greatly bene fited from the re views by Guillaume Cailleau and Tadeusz Peryt, and from ed i to rial work by Bartosz Budzyñ and Frank Simpson.
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