Geo log i cal Quar terly, 2007, 51 (3): 285–294
Sul phur, ox y gen and stron tium iso tope com po si tions of Mid dle Mio cene (Badenian) cal cium sulphates from the Carpathian Foredeep, Po land:
palaeoenvironmental im pli ca tions
Alicja KASPRZYK, Juan J. PUEYO, Stanis³aw HA£AS and Jose M. FUENLABRADA
Kasprzyk A., Pueyo J. J., Ha³as S. and Fuenlabrada J. M. (2007) — Sul phur, ox y gen and stron tium iso tope com po si tions of Mid dle Mio - cene (Badenian) cal cium sulphates from the Carpathian Foredeep, Po land: palaeoenvironmental im pli ca tions. Geol. Quart., 51 (3):
285–294. Warszawa.
Sul phur, ox y gen and stron tium iso tope com po si tions have been mea sured in sul phate (gyp sum and anhydrite) sam ples from the Badenian evaporite com plex in the Carpathian Foredeep Ba sin (Po land) to de ter mine the or i gin of brines from which these sulphates were formed. Stud ied sam ples dis play the d val ues from +22.68 to +24.91‰ CDT for sul phur (ten sam ples) and from +12.26 to +13.63‰
SMOW for ox y gen (ten sam ples), and 87Sr/86Sr ra tios from 0.708915 to 0.716329 (six sam ples). Most sam ples show iso to pic val ues (both d34S and 87Sr/86Sr) higher than con tem po ra ne ous (Badenian) sea wa ter, and thus sug gest that these sulphates were formed (i) from brines with a sig nif i cant com po nent of non-ma rine wa ters, (ii) in a re stricted sys tem, where an im por tant role was played by me te oric wa ter in - puts as well as by bac te rial sul phate re duc tion. The re sults of this study show clear dif fer ences in the iso to pic sig na tures be tween sed i - men tary (gyp sum) and diagenetic (anhydrite) lithofacies. While sed i men tary gyp sum dis plays sul phur, ox y gen and stron tium iso tope ra tios close to con tem po ra ne ous (Badenian) sea wa ter, diagenetic anhydrite val ues are largely el e vated. The higher iso to pic val ues (d34S, d18O and 87Sr/86Sr) for anhydrite when com pared to gyp sum are in ter preted as re flect ing dif fer ent hy dro log i cal prov e nances of sul phate in the Badenian ba sin. Gyp sum was formed from brines ma rine in or i gin that were sub ject to an im por tant in flow of con ti nen tal wa ters and a lo cal bac te rial sul phate re duc tion in a re stricted, and there fore sul phate-lim ited ba sin, which is con sis tent with ear lier in ter pre ta - tions based on sedimentological and geo chem i cal stud ies. Our study shows that brines from which anhydrite was formed had a highly-ra - dio genic non-ma rine (riverine, ground wa ter) stron tium com po nent, which is a new con tri bu tion to the knowl edge on the Badenian sul phate for ma tion. The re sults re flect a lat eral compositional evo lu tion of par ent wa ters dur ing sul phate de po si tion and diagenesis in the Carpathian Foredeep Ba sin.
Alicja Kasprzyk, Pañstwowy Instytut Geologiczny, Oddzia³ Œwiêtokrzyski, Zgoda 21, PL-25-953 Kielce, Po land, e-mail:
alicja.kasprzyk@pgi.gov.pl; Juan J. Pueyo, Departament de Geoquímica i Petrologia, Universitat de Bar ce lona, 08028 Bar ce lona, Spain, e-mail: jjpueyo@ub.edu; Stanis³aw Ha³as, Instytut Fizyki, Uniwersytet Marii Cu rie-Sk³odowskiej, Pl. M. Cu rie-Sk³odowskiej 1, PL-20-031 Lublin, Po land, e-mail: halas@tytan.umcs.lublin.pl; Jose M. Fuenlabrada, CAI de Geocronologia y Geoquímica Isotópica, Facultad de Ciencias Geológicas, Universidad Complutense de Ma drid, 28040 Ma drid, Spain; e-mail: isotopo@geo.ucm.es (re ceived:
Sep tem ber 26, 2006; ac cepted: April 4, 2007).
Key words: Carpathian Foredeep; Badenian; sul phur, ox y gen and stron tium iso topes; sul phate de pos its.
INTRODUCTION
Iso to pic com po si tions (d34S, d18O) and 87Sr/86Sr of sul phate de pos its pro vide use ful in for ma tion about the or i gin and diagenetic evo lu tion of the source wa ters (e.g., Schreiber and El Tabakh, 2000; Lu et al., 2001; Palmer et al., 2004). In ter pre - ta tion of these data is, how ever, com plex due to the re stricted na ture of depositional set tings and the brine in ter ac tions upon de po si tion, which ob scures the com po si tion of mother brines (Denison et al., 1998; Kah et al., 2001; Lu and Meyers, 2003).
Thus, many an cient sul phate de pos its in ter preted as ma rine in or i gin may ac tu ally have a more com plex or i gin, in as much as it is com monly dif fi cult to dif fer en ti ate evaporites de pos ited from ma rine wa ter, non-ma rine wa ter, or their mix tures (Hardie, 1984; Horita et al., 2002; Palmer et al., 2004).
The Mid dle Mio cene Badenian sul phate de pos its in the Carpathian Foredeep (Po land) (Fig. 1) have been con ven tion - ally de scribed as formed in a ma rine ba sin. This in ter pre ta tion has been con firmed by the sul phur and ox y gen iso tope com po - si tion of sulphates (e.g., Ha³as et al., 1996; Kasprzyk, 1997;
Peryt et al., 1998; Rosell et al., 1998). Re cently Cendón et al.
(2004) ar gued, based on geo chem i cal data (fluid in clu sion
com po si tion and Br con tent in ha lite) and geo chem i cal mod el - ling, that the brine com po si tion in the Badenian ba sin might have been strongly mod i fied by fresh wa ter in flows and intrabasinal re cy cling of pre vi ously formed evaporites dur ing the evaporite de po si tion.
The Badenian sul phate de pos its in the Carpathian Foredeep ba sin have not been stud ied pre vi ously for their Sr iso tope geo - chem is try. In this pa per the first Sr iso tope data are pre sented and com pared with those of d34S and d18O, which per mits to re - cord the non-ma rine con tri bu tion to the ba sin, and to better con strain the or i gin and for ma tion of these de pos its.
SULPHATE FACIES DISTRIBUTION
Mid dle Mio cene Badenian evaporites oc cupy a large part of the Carpathian Foredeep, that de vel oped as a pe riph eral fore land ba sin in front of the Carpathian thrust ad vanc ing north wards (Oszczypko et al., 2005) (Fig. 1). In the Pol ish part of the foredeep, these evaporites cor re spond to the lower part of the NN6 zone, thus they are late Badenian in age, based on the re cent nannoplankton study and the ra dio genic dat ing of the tuff ho ri zon (Andreyeva-Grigorovich et al., 2003; Dudek et al., 2004), al though tra di tion ally they have been re lated to Wielician, i.e. mid dle Badenian. Evaporites are un der lain and over lain by deep-wa ter ma rine, mainly siliciclastic de pos its, and com prise sul phate and ha lite fa cies with as so ci ated siliciclastic and car bon ate de pos its. The pres ent-day ex tent of evaporites ap par ently rep re sents only a part of the broader depositional suc ces sion, be cause most of the mar ginal fa cies are allochthonous or have not been pre served.
The Badenian sul phate de pos its are wide spread and cor re - late over a large area (17500 km2) in the Carpathian Foredeep of Po land (Fig. 1) and they con tinue fur ther to wards SE to Ukraine, Moldova, Ro ma nia and Bul garia. In Po land sul phate de pos its form a mar ginal plat form that passes south ward to the sul phate ba sin, while the ax ial part of the foredeep is oc cu -
pied by lo cal salt bas ins. They show a reg u lar lat eral dis tri bu - tion of fa cies:
1. In the pe riph eral part of the foredeep the dom i nant sul - phate fa cies, both in out crop and in shal low subsurface, is up to 60 m thick pri mary gyp sum fill ing the pe riph eral troughs (Kubica, 1992; Kasprzyk, 1993). The pri mary gyp sum de pos its dis play a wide va ri ety of lithofacies. Two gyp sum mem bers are dis tin guished (Fig. 2): a lower mem ber of mostly autochtho nous, selenitic fa cies, and an up per mem ber com posed mainly of allochthonous, clastic de pos its (Kasprzyk, 1999; B¹bel, 1999).
2. To wards the south, in more bur ied parts of the ba sin, gyp sum is re placed by anhydrite (now in near-sur face as sec - ond ary gyp sum). A ver ti cal suc ces sion of lithofacies com prises nod u lar and mas sive anhydrite with pseudo morphs af ter selenitic gyp sum in the lower part (Kasprzyk, 2003). This lower part cor re lates with the lower (selenitic, autochthonous) gyp sum mem ber and are over lain by lam i nated anhydrite and brec cias, widely dis trib uted in the foredeep, which are equiv a - lent to the up per (clastic, allochthonous) gyp sum mem ber (Kasprzyk and Ortí, 1998) (Fig. 2). In the south ern part of the foredeep these anhydrite de pos its are up to 20 m thick and change lat er ally into ba sin cen tre sul phate laminites and ha lite de pos its (Garlicki, 1979).
The pres er va tion of pseudomorphic fea tures in her ited from the pre cur sor gyp sum rocks, both selenitic (lower mem ber) and clastic (up per mem ber), pro vides im por tant ev i dence for diagenetic anhydrite for ma tion by re place ment of the for mer gyp sum dur ing early to late diagenesis (Kasprzyk and Ortí, 1998; Kasprzyk, 2003, 2005). Kasprzyk and Ortí (1998) dis tin - guished two dif fer ent ge netic pat terns of anhydrite: (i) synsedimentary to early-diagenetic anhydritization of gyp sum de pos its in surficial to shal low-burial en vi ron ments (lower mem ber), and (ii) sev eral phases (syndepositional de novo growth, early diagenetic to late diagenetic re place ment of for - mer gyp sum) of anhydrite for ma tion dur ing pro gres sive burial (up per mem ber). All ge netic types of Badenian anhydrite dis - play par tic u lar sedimentological and petrographic fea tures re - cently de scribed in de tails by Kasprzyk (2003, 2005), and two
Fig. 1. Dis tri bu tion of Badenian sul phate fa cies in the Carpathian Foredeep of Po land
of these types have been con sid ered for pur poses of this study.
Syndepositional anhydrite of the lower mem ber (sam ples no. 4 and 6 in Ta ble 1) is char ac ter ized by the nod u lar fab rics and pseudomorphous re place ment growth. Early diagenetic anhydrite of the up per mem ber (sam ples no. 7–10 in Ta ble 1) dis play fea tures of dis place ment for ma tion in a soft, only partly lithified sed i ment (Kasprzyk, 2005). In some ar eas, shal low
burial and/or up lift and ex hu ma tion have al lowed the anhydrite to be partly or com pletely rehydrated into sec ond ary gyp sum.
De po si tion of Badenian evaporites in the Carpathian Foredeep of Po land took place in a re stricted ba sin, as a re - sponse to sea level fall (Oszczypko et al., 2005; Peryt, 2006), and was con trolled by cli ma tic and tec tonic changes which af - fected the in ter play be tween in flow, re flux and evap o ra tion in
Sulphur, oxygen and strontium isotope compositions of Middle Miocene (Badenian) calcium sulphates from the Carpathian Foredeep 287
Fig. 2. Badenian sul phate suc ces sions rep re sen ta tive of var i ous set tings, and lo ca tions of stud ied sam ples
this ma rine-fed ba sin. The lat eral and ver ti cal fa cies dis tri bu - tion, the pres ence of de tri tal sul phate fa cies and the re place - ment of gyp sum by anhydrite are a con se quence of drops in the brine level linked to the ba sin re stric tion and to changes in the ba sin hy drol ogy which were con trolled by the evo lu tion of the Carpathian orogen.
SAMPLE MATERIALS AND METHODS
The stud ied sam ples came from five bore holes lo cated in the east ern part of the Carpathian Foredeep in Po land and in ter - sect ing the Badenian sul phate de pos its at var i ous depths (from 414.0 to 2621.0 m), and from one sur face ex po sure (Borków quarry) in the north ern pe riph eral part of the Carpathian Foredeep (Fig. 1). Iso to pic anal y ses were per formed on ten (d34S, d18O) and six (87Sr/86Sr) whole-rock sam ples of gyp sum and anhydrite, as rep re sen ta tive of dif fer ent sul phate lithofacies and diagenesis (Figs. 2–4 and Ta ble 1).
Ini tially, all sam ples were eval u ated petro graphi cally to sep a rate gyp sum from anhydrite and pure frag ments with out non-sul phate phases (clay, car bon ate and quartz). El e men tal com po si tions of the sam ples were ex am ined by XRF anal y ses.
Microsampled pow ders were then pre pared by drill ing sep a - rated parts of sam ples with 1 mm di a mond drill bits. The same pow dered sam ples were used for sul phur, ox y gen and strontium isotope analyses.
The d34S and d18O anal y ses were car ried out at the Mass Spec trom e try Lab o ra tory, Maria Cu rie-Sk³odowska Uni ver sity in Lublin, Po land. For these anal y ses ca. 40 mg of each pow -
dered sam ple was dis solved in 100 ml of dis tilled wa ter. The wa ter was stirred from time to time dur ing dis so lu tion, which was ex tended up to 3 days. Af ter dis so lu tion of sulphates the sol utes were fil tered to small glass beak ers. BaSO4 was pre cip i - tated by means of the BaCl2 so lu tion acid i fied with HCl. The pre cip i tate was washed by dis tilled wa ter sev eral times un til dis ap pear ance of the chlo ride ion, tested by add ing a few drops of 10% AgNO3 so lu tion to the de canted so lu tion. The clean BaSO4 res i due was dried in small beak ers in an oven at 100°C and then sub jected to the pro ce dures for quan ti ta tive ex trac tion of sul phur and ox y gen for iso to pic anal y sis.
The iso to pic com po si tions, d34S and d18O, were an a lyzed by means of a dual in let and tri ple col lec tor mass spec trom e ter on SO2 and CO2 gases, re spec tively. SO2 was ex tracted di rectly from BaSO4 by the method de vel oped in the Mass Spec trom e - try Lab o ra tory in Lublin (Ha³as and Szaran, 2001, 2004), whereas CO2 was pre pared by the method de scribed by Mizutani (1971). In the last method a CO-to-CO2 con verter was mod i fied by in stall ing of 2 small mag nets to en hance the dis - charge cur rent. Typ i cally 8 to 12 mg of BaSO4 was used in each gas prep a ra tion. The reproducibility of both anal y ses in terms of stan dard de vi a tion (SD) was 0.07‰. Delta val ues were nor - mal ized to the V-CDT and V-SMOW scales by anal y sis of the NBS-127 stan dard, for which d34S = +21.14‰ and d18O = +9.30‰ were as sumed (Ha³as and Szaran, 2001; Boschetti and Iacumin, 2005). The an a lyt i cal precisions were 0.15‰ for both d34S and d18O, and all val ues have been ex pressed as ‰ CDT and ‰ SMOW, re spec tively.
The stron tium iso tope com po si tions were an a lyzed at the Geo chron ol ogy and Iso to pic Geo chem is try Lab o ra tory, Univ -
T a b l e 1 O, S and Sr iso tope data of Badenian sul phate sam ples
No. Bore hole/Ex po sure Depth [m]/sam ple Lithofacies/Mem ber I — lower, II — up per
Iso tope com po si tion d18O‰SMOW d34S‰CDT
87Sr/86Sr 1
Pysznica U-19 (sul phate plat form)
429.6 lam i nated clastic gyp sum/II 12.68 22.91 0.708915
2 429.6 lam i nated clastic gyp sum/II 12.94 22.07 n.a.
3 453.4 selenitic gyp sum/I 12.26 22.68 0.709157
4 453.4 anhydrite nod ule within selenitic gyp sum/I 13.63 24.52 0.709581
5 Borków
(sul phate plat form) sur face exposure mi cro bial lam i nated gyp sum/I 12.49 23.15 n.a.
6 Dzików 15
(sul phate plat form) 1083.65 anhydrite pseudomorph af ter selenitic
gyp sum/I 11.96 23.23 n.a.
7 Za³azie 2
(sul phate ba sin) 2620–2623/4-G lam i nated anhydrite/II 13.27 24.40 0.715231
8 Mirocin 56
(sul phate ba sin) 1500–1504/4-G lam i nated anhydrite — anhydrite pseudo -
morphs af ter len tic u lar gyp sum crys tals/II 12.36 24.47 0.710247 9 Ryszkowa Wola 7
(sul phate ba sin)
2410.5 lam i nated anhydrite — anhydrite pseudo -
morphs af ter len tic u lar gyp sum crys tals/II 12.86 24.91 0.716329
10 2410.65 lam i nated anhydrite with py rite/II 12.91 23.95 n.a.
x = 12.74 23.63 0.711577
SD = 0.39 0.82 0.002802
n.a. — not ana lysed, x — mean, SD — stan dard de vi a tion
ersidad Complutense de Ma drid in Ma drid. Pre vi ously wei - ghed in Tef lon® vi als pow dered sam ples of gyp sum and anhydrite (25 mg) were dis solved in 8 ml of ultrapure Milli-Q (Millipore®) wa ter (Lu et al., 1997; Denison et al., 1998; Ja - cob son et al., 2005), through a pe riod of 10 days at room tem - per a ture, shak ing the vi als once a day (Fuenlabrada et al., 2001). The XRD re sults showed that the gyp sum sam ple no. 1 (Ta ble 1) had got some im pu ri ties of anhydrite. There fore, the
dis so lu tion method of this sam ple was slightly changed to elim - i nate the pos si ble con tam i na tion in the fi nal ra tio. Tak ing into ac count that anhydrite is more sol u ble than gyp sum in pure wa - ter at 25°C (MÝller, 1988), 25 mg of pow dered sam ple was dis - solved in 8 ml of ultrapure wa ter dur ing two days, and then cen - tri fuged for 10 min utes to elim i nate the dis solved frac tion and as sum ing that the to tal anhydrite was dis solved. Then ultrapure wa ter was added again to the res i due, in or der to dis solve (through 10 days) the re main ing gyp sum sam ple. Af ter that time, sam ples were cen tri fuged for 10 min utes, in or der to sep a - rate the dis solved frac tion from the res i due. The dis solved frac - tion was heated at about 100°C, to reach a com plete evap o ra - tion of the dis so lu tion. The dry evap o rated sam ples were dis - solved in 2 ml of dis tilled and ti trated 2.5N HCl at room tem - per a ture, or by means of an ul tra sonic bath. Af ter such prep a ra - tion sam ples were ready to be passed through the chro mato - graphic col umns. For this in ter nal pro to col to sep a rate stron - tium (Sr) from the rest of el e ments, cat ion ex change resin DOWEX 50W-X12 200–400 mesh was used (Strelow, 1960;
Pankhurst and O’Nions, 1973). Pre vi ously, these chro mato - graphic col umns were cal i brated to de fine the Sr frac tion, and the vol ume of HCl 2.5N nec es sary to re cover the max i mum amount of this el e ment free from ru bid ium traces. The Sr sam - ples were col lected in clean vi als and dried at about 80°C. Dry stron tium sam ples were dis solved in 1 ml of phos pho ric acid (1M con cen tra tion), and the mix ture was loaded over a sim ple tan ta lum fil a ment (pre vi ously de gassed).
The sam ples were in tro duced into the Ther mal Ion iza tion Mass Spec trom e ter (TIMS) Micromass VG Sec tor-54 and an a - lyzed us ing the stan dard method of mea sure ment called dy - namic multicollection, with five Fara days cups. Stron tium anal y ses were cor rected from pos si ble 87Rb in ter fer ences. The ob tained 87Sr/86Sr ra tios were nor mal ized us ing the valor
88Sr/86Sr = 0.1194 as a ref er ence, in or der to cor rect the mass frac tion ation in the sam ple through the to tal anal y sis time.
NBS-987 was cho sen as an iso to pic stan dard of Sr to an a lyze at the same time with sam ples. This stan dard pro vided a cor rec - tion fac tor that let us to elim i nate or min i mize pos si ble trou bles in the sam ple anal y sis. An av er age 87Sr/86Sr value (11 anal y sis of NBS-987) was 0.710223 (SD = 0.00003), which fit ted quite well to the value 0.710253 (SD = 0.00004) ob tained through 582 anal y sis of the same stan dard. The an a lyt i cal er ror of the lab o ra tory in the 87Sr/86Sr ra tio, re ferred to two stan dard de vi a - tions, was 0.01%.
RESULTS
All re sults of iso to pic stud ies are sum ma rized in Ta ble 1.
The d34S, d18O and 87Sr/86Sr val ues for ana lysed sul phate sam - ples are cross-plot ted in Fig ures 6 and 7, and a com par i son of these val ues with pre vi ous data for ma rine sul phate de pos its in the Carpathian Foredeep is shown in Fig ures 5 and 6.
The d val ues are from +22.07 to +24.91‰ CDT for sul phur and from +11.96 to +13.63‰ SMOW for ox y gen, and the av er - age val ues are re spec tively +23.63‰ (SD = 0.82) and +12.74‰ (SD = 0.39) (Ta ble 1). Both iso to pic com po si tions are pos i tively cor re lated, show ing the d18O val ues in a smaller
Sulphur, oxygen and strontium isotope compositions of Middle Miocene (Badenian) calcium sulphates from the Carpathian Foredeep 289
Fig. 3. Selenitic gyp sum partly re placed by nod u lar anhydrite Borehole Pysznica U-19, depth 453.4 m
Fig. 4. Or ganic-rich claystone with anhydrite laminae and lenses com posed of pseudo morphs af ter len tic u lar gyp sum crys tals
Borehole Ryszkowa Wola 7, depth 2410.5 m
range of vari a tion than d34S (Fig. 6). It is worth not ing that the av er age d val ues for anhydrite sam ples are higher (by about 2‰ for sul phur and 0.5‰ for ox y gen) than for gyp sum. Over - all, the re sults co in cide with val ues ex pected for the Mio cene sulphates of the ma rine or i gin only for the ox y gen (Zak et al., 1980; Paytan et al., 1998) (Fig. 6).
The 87Sr/86Sr ra tios of gyp sum and anhydrite sam ples range from 0.708915 to 0.716329 (Ta ble 1). All sam ples yielded an av - er age 87Sr/86Sr ra tio of 0.711577 (SD = 0.002802). The gyp sum sam ples have a mean 87Sr/86Sr value (0.709036; n = 2) that is largely lower than the mean 87Sr/86Sr value of the anhydrite sam - ples (0.712847; n = 4). The d34S–87Sr/86Sr and d18O–87Sr/86Sr re la - tion ships of gyp sum and anhydrite are il lus trated in Fig ure 7. The
87Sr/86Sr for anhydrite sam ples shows a wide range of val ues (from 0.709581 to 0.716329), while gyp sum sam ples have
87Sr/86Sr val ues largely lower (0.708915 and 0.709157).
INTERPRETATION AND DISCUSSION
S AND O ISOTOPE COMPOSITION
The sul phur and ox y gen iso tope com po si tions of stud ied gyp sum and anhydrite sam ples vary within rel a tively nar row ranges. Over all, the re sults cor re spond well to the pre vi ously re ported iso to pic com po si tion of Badenian sul phate (gyp sum and anhydrite) de pos its in the Carpathian Foredeep (e.g., Kasprzyk, 1997, 2003; Peryt et al., 2002 and ref er ences therein) (Figs. 5 and 6). Re cently, Cendón et al. (2004) ar gued that sul phate iso tope val ues are not by them selves in dic a tive of the ma rine or non-ma rine or i gin of the sul phate and stressed the im por tance of ma jor con ti nen tal in puts and on go ing intrabasinal re cy cling pro cesses in for ma tion of Badenian sul - phate de pos its. Peryt et al. (2002) stressed that there was a lithological con trol on the d34S and d18O val ues. Those au thors, how ever, did not dif fer en ti ate be tween the gyp sum and anhydrite lithologies, and the palaeogeographic lo ca tion of stud ied sam ples. There are some reg u lar changes be tween sam - ples stud ied in our work, which show that d val ues for the gyp - sum sam ples are dis tinctly lower in sul phur and slightly lower in ox y gen when com pared to anhydrite sam ples. Our re sults in - di cate that there is a dis tinct lithofacies (gyp sum–anhydrite) and palaeogeographic (ba sin mar gin–ba sin cen tre) con trol on sul phur and ox y gen iso tope com po si tions, show ing an in crease of d val ues for sam ples com ing from more basinal set tings (Ta - ble 1 and Fig. 2).
Most of d val ues are lo cated far from the ma rine field (d34S
= +21.65±0.5‰, d18O = +12.5±0.5‰; Zak et al., 1980; Paytan et al., 1998) in di cated by the box in Fig ure 6. Hence the sul - phate with el e vated d val ues must ei ther arise from the ad di tion of dis solved sul phate to the ba sin from a non-ma rine source or re flect an iso tope frac tion ation pro cesses within the ba sin, such as dis so lu tion of the pre vi ous evaporites and reprecipitation of the sul phate (a pro cess termed “re cy cling”), or microbially me - di ated sul phate re duc tion. These geo chem i cal fac tors in volv ing the sul phate iso tope com po si tions are dis cussed be low.
Vari a tions in d val ues may have re sulted from a non-ma rine con tri bu tion to the ba sin. Dis solved sulphates in con ti nen tal
Fig. 5. Ox y gen and sul phur iso tope com po si tion of Badenian sulphates (gyp sum and anhydrite) in the Carpathian Foredeep (based on data from: Bukowski and Szaran, 1997; Kasprzyk, 1997,
2003; Peryt et al., 1998; Cendón et al., 2004) I — lower mem ber; II — up per mem ber
Fig. 6. Plot of d34S and d18O val ues in stud ied gyp sum and anhydrite sam ples
Iso to pic com po si tions of Mio cene ma rine sulphates (thick solid line; af ter Zak et al., 1980; Paytan et al., 1998) and Badenian sul phate de pos its in the Carpathian Foredeep (af ter Bukowski and Szaran, 1997; Kasprzyk, 2003;
Peryt et al., 2002; Cendón et al., 2004) are also shown; in di cated (G) are gyp sum sam ples and the oth ers are anhydrite
(e.g. riverine) wa ters are usu ally de rived from the dis so lu tion of for mer evaporite de pos its, the ox i da tion of py rite weath ered from shales or ig ne ous rocks, a mag matic source through ther - mal wa ters, and also vol ca nic re lated in puts. Con ti nen tal wa ters are gen er ally de pleted in 34S and 18O com pared to sea wa ter (Lu and Meyers, 2003; Palmer et al., 2004). Iso topic com po si tions of both el e ments can be very vari able, show ing com mon val ues –5 to +5‰ for d34S and –10 to +5‰ for d18O (Niel sen, 1972).
How ever, d34S and d18O of ma rine gyp sum are in sen si tive to mi nor non-ma rine con tri bu tions, be cause sea wa ter and sea wa - ter-evap o rated brines have much higher SO4-2 con cen tra tion than most freshwaters (Lu and Meyers, 2003; Palmer et al., 2004). For the Badenian evaporite ba sin, geo chem i cal stud ies and model cal cu la tions of the ba sin evo lu tion sug gest a ma jor in flow of con ti nen tal wa ters, up to 65–70%, with a ma rine in - put be ing less than 30% dur ing ha lite pre cip i ta tion (Cendón et al., 2004).
The iso to pi cally heavy sul phate may come from re cy cling of the for mer evaporites by con ti nen tal wa ters, as pre vi ously sug gested by Peryt et al. (2002) and Cendón et al. (2004) for Badenian sulphates. Sedimentological and geo chem i cal data in di cate re cy cling of evaporites through out most of the evaporite de po si tion, but es pe cially dur ing de po si tion of allochthonous sul phate fa cies. Our re sults show that the en rich - ment in 34S for some anhydrite sam ples is higher than ex pected from the sim ple dis so lu tion-reprecipitation of sul phate, as sum - ing that the Mio cene gyp sum (or anhydrite) was the orig i nal sul phate dis solved (Cendón et al., 2004). There fore, the high d val ues prob a bly im ply ei ther mul ti ple cy cles of dis so lu tion and reprecipitation of sul phate or, al ter na tively, anoxic con di tions fa vour ing sul phate-re duc ing bac te rial ac tiv ity in depositional en vi ron ments. Peryt (2006) con cluded that de po si tion of ha lite in the ba sin cen tre pre ceded the autochthonous sul phate de po - si tion (lower mem ber) in the mar ginal ba sin, while that of allochthonous sul phate fa cies (up per mem ber) was roughly co - eval in the en tire evaporite ba sin. Thus, the high d34S val ues of the basinal anhydrite sam ples il lus trated in Fig ure 6 in di cate that re stricted con di tions very likely oc curred in the ba sin cen - tre dur ing redeposition of evaporites.
It is more dif fi cult to es tab lish, how ever, whether en riched d34S com po si tions re flect ba sin-scale or lo cal compositional evo lu tion of par ent brines. Holser (1977) sug gested that large brine-ac cu mu lat ing bas ins with a lim ited con nec tion to the open sea could evolve highly en riched S-iso tope com po si tions, per haps via biogenic sul phate re duc tion and py rite de po si tion within euxinic basinal brines, or via “nor mal” sul phate re duc - tion in a ba sin that is sul phate lim ited from large-scale de po si - tion of evaporites. In the his tory of the Badenian sa lin ity cri sis, re cently sum ma rized by Peryt (2006), the evaporite de po si tion com menced in the deep est part of the ba sin in den sity-strat i fied brines, and was pos si bly pre ceded by the syndepositional sul - phate nod ule growth in the un der ly ing or ganic-rich siliciclastic de pos its. It is sug gested, that the oc cur rence of py ritic and or - ganic-rich de po si tion as well as py rite ag gre gate pseudo - morphs af ter gyp sum in basinal set tings of the Carpathian Foredeep Ba sin, co eval with evaporite de po si tion (Kasprzyk and Ortí, 1998; Kasprzyk, 2003, 200b; Oszczypko et al., 2005), in di cates that sul phate re duc tion was ac tive in a re - stricted, and there fore sul phate-lim ited ba sin. Thus, the el e -
vated d34S val ues as ob served by us could be at trib uted to closed sys tem con di tions with an im por tant role played by bac - te rial sul phate re duc tion in the ba sin partly sep a rated from the open sea.
On the ba sis of our study it is sug gested that ei ther sul phate re duc tion or non-ma rine con tri bu tion by intrabasinal evaporite re cy cling, or both, could have a great im pact on the d34S and d18O val ues be fore or dur ing gyp sum de po si tion in the Carpathian Foredeep Ba sin, and re sulted in vari a tion of iso - topic com po si tions of Badenian sul phate de pos its.
There is no sul phur and ox y gen iso tope frac tion ation dur ing the gyp sum-to-anhydrite trans for ma tion (Pi erre, 1988; Utrilla et al., 1992; Kasprzyk, 2003). Thus, the anhydrite (con sid ered to be a diagenetic prod uct) still pre serves the iso to pic sig na ture of the orig i nal (depositional) gyp sum, un less bac te rial re duc - tion has taken place. The oc cur rence of py rite pseudo morphs af ter gyp sum crys tals in Badenian an hyd rites ar gues for early (syndepositional and early diagenetic) stages of re dox pro - cesses ac tive in the evaporite ba sin (Kasprzyk, 2005). There - fore, the iso to pic dif fer en ti a tion be tween gyp sum and anhydrite re corded by us seems to re flect a lat eral compositional evo lu - tion of par ent wa ters dur ing sul phate de po si tion in the Carpathian Foredeep Ba sin.
Sr ISOTOPE COMPOSITION
The Sr iso tope com po si tions of evaporites re flect the com - po si tion of mother brines, which is a re sponse to chang ing in - puts and sources of dis solved stron tium, to gether with pos si - ble in ter ac tions be tween the brines and rocks within the evaporite ba sin (Brass, 1976; Kah et al., 2001; Lu and Meyers, 2003; Palmer et al., 2004). Sr iso tope stud ies are par - tic u larly use ful in mon i tor ing the con ti nen tal in puts into the ma rine ba sin. The Sr iso tope com po si tion of Neo gene sea wa - ter is well es tab lished (e.g., Koepnick et al., 1985; Hodell et al., 1991; McArthur et al., 2001), thus, the 87Sr/86Sr of Badenian sea wa ter is well known (0.708698–0.708817).
There are no avail able Sr iso tope data for non-ma rine flu ids (river wa ter or ground wa ter) in the study area. In gen eral, non-ma rine wa ters are char ac ter ized by higher 87Sr/86Sr val - ues and lower Sr con cen tra tions com pared to val ues of nor mal Mio cene sea wa ter (Palmer and Edmond, 1989; Lu and Meyers, 2003). Some geo chem i cal data for halites and model cal cu la tions for the Badenian ba sin evo lu tion re cord a ma jor con ti nen tal source for sol utes, sea wa ter be ing a mi nor in flow (less than 30%) to the ba sin dur ing the evaporite de po si tion (Cendón et al., 2004 and ref er ences therein). Our in ter est is whether the Sr iso tope data re cord this non-ma rine con tri bu - tion to the evaporite ba sin of the Carpathian Foredeep.
Most stud ied sul phate sam ples (both gyp sum and anhy - drite) show 87Sr/86Sr val ues (0.708915–0.716329; Ta ble 1) that are higher to much higher than con tem po ra ne ous Badenian sea wa ter (e.g., Hodell et al., 1991; McArthur et al., 2001), and thus dem on strate that these sulphates were formed from brines with a sig nif i cant com po nent of non-ma rine Sr.
Lu and Meyers (2003) stressed that a con tri bu tion of non-ma - rine wa ter could have been masked by the ma rine 87Sr/86Sr sig na ture be cause of a much higher Sr con cen tra tion in the
Sulphur, oxygen and strontium isotope compositions of Middle Miocene (Badenian) calcium sulphates from the Carpathian Foredeep 291
brine than in the con ti nen tal wa ters. In spite of this rea son, our re sults are un equiv o cal and point to a con tri bu tion of highly ra dio genic stron tium to the ba sin.
The 87Sr/86Sr ra tios of two gyp sum sam ples (no. 1 and 3 in Ta ble 1) are close to the Badenian sea wa ter Sr iso tope val ues (0.708698–0.708817; Hodell et al., 1991), sug gest ing a dom i - nantly ma rine or i gin. How ever anhydrite sam ples of the up per (clastic) mem ber have more ra dio genic 87Sr/86Sr ra tios than the gyp sum sam ples, strongly in di cat ing ra dio genic stron tium non-ma rine con tri bu tion, and also trend to wards higher d34S and d18O (Fig. 7). It is pos si ble that mix ing of ma rine and con ti - nen tal wa ters was re spon si ble for these re la tion ships. In deed, the mix ing of con ti nen tal and ma rine wa ters played a ma jor role in the vari a tion of stron tium iso topes in some evaporite de - pos its (Denison et al., 1998; Playa et al., 2000; Lu and Meyers, 2003; Palmer et al., 2004).
Sed i men tary and geo chem i cal ev i dence im ply that the wa - ter level fluc tu ated sig nif i cantly dur ing the sul phate de po si tion in the Badenian ba sin, which in turn was in ter rupted by in - fluxes of fresh wa ter (e.g. Kasprzyk, 2003; Cendón et al., 2004;
B¹bel, 2005). The redeposition of evaporites, es pe cially dur ing sed i men ta tion of the up per mem ber clastic de pos its, was im - por tant, and al though par ent brines were ma rine in or i gin, they were sub ject to sig nif i cant in flows of me te oric wa ters (Cendón et al, 2004; Peryt, 2006). The scat ter of stron tium iso tope re - sults in the sul phate sam ples is in ter preted here to re flect the con tri bu tion of me te oric stron tium to the ba sin. Thus, the Sr iso tope data con firm the above in ter pre ta tion sug gest ing that Badenian sulphates orig i nated from ma rine brines with a sig - nif i cant and vari able con tri bu tion of me te oric wa ters.
The re sults of this study show Sr iso to pic dif fer ences be - tween the sed i men tary (gyp sum) and diagenetic (anhydrite) lithofacies (Fig. 7). The lat ter are highly ra dio genic, sug gest - ing that be fore or dur ing anhydritization of gyp sum in ter sti tial brines un der went Sr iso tope ex change with other cir cu lat ing flu ids. The high 87Sr/86Sr ra tios in anhydrite sam ples can be in ter preted as re sulted from the mix ing of flu ids of two dif fer - ent iso to pic sig na tures, i.e., ma rine wa ters and con ti nen tal wa ters, dur ing sul phate de po si tion and diagenesis. The me te -
oric con tri bu tion is doc u mented by a pres ence of siliciclastic im pu ri ties and interbeds in anhydrite suc ces sions (Fig. 2). An in flu ence of interbedded siliciclastic de pos its as sources of highly ra dio genic stron tium could be im por tant by sim ple mix ing and in ter ac tions be tween the brines and rocks (Denison, pers. comm., 2007). Thus, the dif fer ent stron tium iso tope com po si tions of gyp sum and anhydrite seem to re flect two dif fer ent hy dro log i cal prov e nances of sul phate for ma tion in the Badenian ba sin.
Some au thors sug gested an im por tant in flu ence of the Carpathian orogen on the evaporite de po si tion by pro mot ing the ex pul sion of bur ied brines from the flysch sed i ments dur - ing Carpathian overthrusting (Liszkowski, 1989; Eastoe and Peryt, 1999; Peryt, 2006). Al though, it is dif fi cult to es tab lish the time re la tions of these pro cesses and the anhydritization of de tri tal gyp sum de pos its, the both could af fect the iso to pic com po si tions of the basinal sul phate fa cies close to the Carpathian front.
CONCLUSIONS
Iso to pic sig na tures of Badenian sulphates show that ma rine wa ter was the dom i nant source of sul phate and Sr, but that strong per tur ba tions from the orig i nal sea wa ter re sulted from the ma jor con tri bu tions of non-ma rine wa ters and sul phate re - duc tion re ac tions in depositional settings.
Vari a tions in iso to pic sig na tures of sul phate sam ples (d34S, d18O and 87Sr/86Sr) re flect ac tive re cy cling and biogeochemical (bac te rial) pro cesses dur ing sul phate de po si tion and in flows of con ti nen tal wa ters en riched in iso to pi cally light sul phur and ra - dio genic stron tium com pounds into the ba sin, and there fore may be re lated to en vi ron men tal changes along with an ep i - sodic iso la tion and re fresh ment of the ba sin, most prob a bly con trolled by tec tonic and eustatic changes.
The re sults also sug gest that gyp sum (sed i men tary fa cies) and anhydrite (diagenetic fa cies) were formed in dif fer ent hy - dro log i cal set tings in a ba sin af fected by im por tant and vari able
non-ma rine (riverine, ground wa ter) in puts. Gyp sum was formed from brines ma rine in or i gin that un der - went an im por tant in flow of con ti - nen tal wa ters and lo cal bac te rial sul - phate re duc tion. Anhydrite iso to pic sig na tures re flect highly ra dio genic non-ma rine in puts to the ba sin, most likely re lated to mix ing from terrigenous sources or ex pul sion of buried brines caused by the Carpathian orogeny.
Ac knowl edge ments. We would like to ex press our grat i tude to M.
B¹bel (War saw Uni ver sity, War saw), R. E. Denison (Uni ver sity of Texas, Dal las) and M. Narkiewicz (Pol ish Geo log i cal In sti tute, War saw) for their con struc tive com ments, which
Fig. 7. Re la tion ship be tween 87Sr/86Sr and d34S (A) and 87Sr/86Sr and d18O (B) of sul phate de pos its: gyp sum (G) and anhydrite (A)
Sam ple sym bols ex plained in Fig ure 6
have greatly im proved the ear lier ver sion of the pa per. Spe cial thanks go to C. Taberner (In sti tute de Ciencies de la Terra, CSIC, Bar ce lona) for in spir ing dis cus sions. Ac cess to and sam pling of cores were per mit ted by the The Pol ish Oil and Gas Ex plo ra tion
Com pany. The re search was sup ported by the Pol ish Com mit tee for Sci en tific Re search.
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