Sul phur iso topes in anhydrite from Badenian (Mid dle Mio cene) salts of the Hrynivka area (Ukrai nian Carpathian Foredeep)
Anatoliy R. GALAMAY1, Fanwei MENG2 and Krzysztof BUKOWSKI3, *
1 Na tional Acad emy of Sci ences of Ukraine, In sti tute of Ge ol ogy and Geo chem is try of Com bus ti ble Min er als, Naukowa 3A, 79060 Lviv, Ukraine
2 State Key Lab o ra tory of Paleobiology and Stra tig ra phy, Nanjing In sti tute of Ge ol ogy and Pa le on tol ogy, Chi nese Acad emy of Sci ences, Nanjing 210008, China
3 AGH Uni ver sity of Sci ence and Tech nol ogy, Fac ulty of Ge ol ogy, Geo phys ics and En vi ron ment Pro tec tion, Al. A. Mickiewicza 30, 30-059 Kraków, Po land
Galamay, A.R., Meng, F., Bukowski, K., 2014. Sul phur iso topes in anhydrite from Badenian (Mid dle Mio cene) salts of the Hrynivka area (Ukrai nian Carpathian Foredeep). Geo log i cal Quar terly, 58 (3): 439–448, doi: 10.7306/gq.1159
Ten new de ter mi na tions of the sta ble sul phur iso tope con tent of anhydrite from Badenian rock salt in the Hrynivka 525 bore - hole (Ukrai nian Carpathian Foredeep) show that d34S val ues in anhydrite range from +20.2 to +22.7‰ and the av er age value of d34S is +21.4 ± 0.3‰. Those val ues are sim i lar to those of the Neo gene ma rine sulphates. Com par i son to other geo chem i - cal data (chem i cal com po si tion of the brine con tained in fluid in clu sions and the bro mine con tent in ha lite) sug gests that the Badenian Carpathian Foredeep evaporite ba sin was sup plied pre dom i nately by sea wa ter sol utes where, at dif fer ent stages of salt ac cu mu la tion, the in flu ence of con ti nen tal wa ters with lighter iso to pic com po si tions of dis solved sul phate was im por - tant. The iso to pic com po si tion of sul phur (d34S) of Badenian sea wa ter, cal cu lated on the ba sis of sixty anal y ses of anhydrite re lated to ha lite of the Carpathian re gion, is ap prox i mately +20.3‰, this value be ing sim i lar to the sul phur iso to pic com po si - tion of pres ent-day sea wa ter. The d34S value for Badenian sea wa ter may have been slightly higher if we con sider po ten tial changes of the brine com po si tion of salt-bear ing bas ins caused by in flow of con ti nen tal wa ters en riched in light 32S iso topes.
Key words: anhydrite, sul phur iso topes, rock salt, Badenian, Mio cene, Carpathian re gion.
INTRODUCTION
The iso to pic sig nal of sta ble sul phur iso topes in anhydrite is an im por tant in di ca tor of the or i gin and the depositional en vi ron - ment of evaporites. Iso to pic com po si tion stud ies are help ful in the in ter pre ta tion of the phys i cal and chem i cal con di tions of sul - phate crystallisation, diagenetic evo lu tion, and sub se quent trans for ma tion in sul phate re duc tion and the ox y gen a tion cy cle (e.g., Lloyd, 1968; Longinelli, 1979; Pi erre, 1985; García-Veigas et al., 2011).
The sul phur iso tope con tent of anhydrite, co-oc cur ring with salt de pos its, is an im por tant source of in for ma tion about the or - i gin of salt and the con tri bu tion of dis so lu tion and recrystallisa - tion pro cesses of ear lier evaporite for ma tions (re cy cling; Niel - sen, 1972). The de ter mi na tion of sta ble sul phur iso topes d34S in the anhydrite orig i nat ing from the Badenian salt suc ces sion of the Carpathian area has been the topic of pre vi ous re search (e.g., Claypool et al., 1980; Galamay, 1997; Bukowski and Szaran, 1997; Parafiniuk and Ha³as, 1997; Peryt et al., 1997,
1998, 2002; CendÙn et al., 2004; Kasprzyk and Bukowski, 2009; Jasionowski and Peryt, 2010).
In the pres ent study, the re sults of new d34S de ter mi na tions are pro vided for anhydrite from the salt-bear ing de pos its of the Hrynivka area (the cen tral part of the Ukrai nian Carpathian Foredeep; Fig. 1). This re search was car ried out on the same sam ples of rock salt that have pre vi ously been used for anal y - ses of fluid in clu sions (Galamay, 2010), bro mine con tent (Gala - may, 2003) and stron tium iso topes (Peryt et al., 2010). The aim of our study was to iden tify a cor re la tion be tween the sul phur iso to pic com po si tion of the Hrynivka anhydrite and other re - gional geo chem i cal data. In our dis cus sion of the re sults, we com pare the de ter mi na tion of the sta ble sul phur iso tope con - tent (d34S) in the Hrynivka anhydrite with the iso to pic com po si - tion (d34S) of anhydrite orig i nat ing from other parts of the Badenian ba sin of the Cen tral Paratethys in the Carpathian re - gion (Fig. 1). Our re sults are com pared to the iso to pic com po si - tion of dis solved sul phate orig i nat ing from mod ern seawaters.
GEOLOGICAL SETTING
The Carpathian Foredeep Ba sin was formed north-east of the overthrust Carpathian nappes in the Early Mio cene. It is filled with Mio cene de pos its, more than 3000-m-thick, in the
* Corresponding author: e-mail: buk@agh.edu.pl Received: April 29, 2013; accepted: January 10, 2014; first published online: March 25, 2014
area ad ja cent to the Carpathians. In the Ukrai nian part of the Carpathian Foredeep, three tec tonic zones are dis tin guished:
outer (Bilche-Volytsia), cen tral (Sambir Nappe thrust over the fore land), and in ner (Boryslav-Pokuttya Nappe) thrust over the Sambir Nappe and the un der ly ing fore land (Vul et al., 1989;
Oszczypko et al., 2006).
The Badenian evaporites oc cur in the Bilche-Volytsia Zone, as well as lo cally on the Sambir Zone (e.g., in the ar eas of Drohobych, Hrynivka, and Lopushna). Those evaporites (sul - phate-car bon ate, and sul phate and rock salt) be long ing to the Tyras Suite (For ma tion) are cor re lated with the Wieliczka For - ma tion in the Pol ish part of the Carpathian Foredeep (Andre - yeva-Grigorovich et al., 2003), as well as other salt for ma tions in Ro ma nia and Slovakia (Khrushchov, 1980). The evaporites of the Tyras Suite over lie the de pos its of the Bohoro dchany Suite, oc cur ring in the cen tral Sambir Zone of the Carpathian Foredeep, or the Baraniv beds in the Bilche- Volytsia Zone (Peryt, 2006) and other older de pos its (Stupnitskiy et al., 1978), and are over lain by the lam i nated clays and siltstones of the Kosiv Suite de pos its (Korenevskii et al., 1977; Khrushchov, 1980) and lo cally by the Ratyn Lime stone (Peryt et al., 2012 with ref er ences therein).
Thir teen bore holes were drilled dur ing ex plo ra tion for pot - ash salts in the fron tal part of the Sambir Zone in the Hrynivka area (ca. 12 km SE of Kalush) in 1975–1978 (Fig. 2). Our stud - ies in volved the sam ples col lected from the Hrynivka 525 bore - hole lo cated in the NW part of the area.
MATERIALS AND METHODS
Rock salts were drilled to depth of 272 m in the Hrynivka 525 bore hole. The lower part of the salt suc ces sion was not
reached due to drill ing rig mal func tion at 541 m.
In to tal, 22 sam ples were col lected for lab o ra - tory tests of which new de ter mi na tions of sta ble sul phur iso tope con tent were car ried out on ten sam ples. The anhydrite col lected for tests oc - curred in the form of white-blue nod ules (of di - am e ter 1–10 mm) found on the bound aries of coarse crys tal line ha lite and claystone (Fig. 3).
Only one sam ple (no. 1350) came from mas - sive anhydrite in the rock salt.
The de ter mi na tions of the iso to pic com po - si tion of sul phur in the anhydrite of the Hrynivka salt suc ces sion were per formed in the In sti tute of Ge ol ogy and Geo phys ics, Chi nese Acad emy of Sci ences (IGGCAS), us ing a Finnigan Delta S gas source mass spec trom e ter. The sul phur iso tope anal y sis method was mod i fied with re - spect to that of Halas and Szaran (1999). Ap - prox i mately 15 mg of CaSO4 was mixed with NaPO3 (150 mg) and combusted in the pres - ence of cop per turn ings (150 mg) un der vac - uum, for con ver sion to sul phur di ox ide at 750°C, for 15 min utes. Sul phur iso tope re sults (V-CDT, Vi enna-Can yon Diablo Troilite) are gen er ally re pro duc ible within ±0.3‰.
In this study, we also sum ma rize pre vi ously pub lished de ter mi na tions of the d34S val ues of anhydrite orig i nat ing from var i ous parts of the Badenian salt ba sin. Those stud ies were mostly con ducted with the use of a three-col lec - tor mass spec trom e ter, with a two-chan nel dos - ing sys tem, at the Lab o ra tory of the In sti tute of Phys ics of the Maria Cu rie-Sk³odowska Uni ver sity in Lublin, Po - land. The method was de scribed in de tail by Halas and Szaran (1999). The val ues of d34S, ob tained with an ac cu racy of
±0.05‰, rep re sented a rel a tive dif fer ence in ‰ be tween the iso tope pro por tions (34S/32S) of the sam ple and those of the stan dard V-CDT.
RESULTS
Con sid er able quan ti ties of anhydrite nests and overgrowths (up to 1.5 m) within rock salt were found in the bore hole pro file in ves ti gated. Those overgrowths of ten oc curred in the form of anhydrite-ha lite rock in which anhydrite cre ated a frame work with cell spaces filled by ha lite (Fig. 3).
All sul phur iso to pic com po si tions (d34S) were quite sim i lar within a nar row range vary ing from +20.2 to +22.7‰ (Ta ble 1), with the low est val ues be low +21‰ found in sam ples 1357, 1354, and 1352 (Fig. 4). The av er age value of d34S amounted to +21.4 ± 0.3‰. A cer tain change in the reg u lar ity of d34S was ob served as a trend but the num ber of anal y ses (10) was in suf - fi cient to spec ify such changes (Fig. 4).
INTERPRETATION
The main pro cesses that lead to frac tion ation of sul phur iso - topes in dis solved sul phate in clude pri mar ily the fol low ing:
– crystallisation fractioning dur ing sul phate pre cip i ta tion;
– sul phate dis so lu tion and reprecipitation (chem i cal re cy - cling);
– bac te rial re duc tion of sul phates.
Fig. 1. Palaeogeographic map of the Badenian salt-bear ing bas ins in the Carpathian re gion (af ter Bukowski et al., 2007) with an in di ca tion
of salt de pos its that were ana lysed for d34S in anhydrite Salt de pos its: 1 – Hrynivka, 2 – Zabolotiv, 3 – Slanic-Prahova, 4 – Barycz,
5 – Wieliczka, 6 – Bochnia, 7 – Wojnicz, 8 – Zbudza
Dur ing crystallisation of sulphates (gyp sum, anhydrite, or pot ash-mag ne sium sulphates) from evap o rated seawa ter, lim - ited sul phur iso to pic frac tion ation oc curs. Ca-sul phate min er als be come en riched with heavy sul phur iso tope (1.65 ± 0.12‰) in com par i son to par ent brine (e.g., Thode and Mon ster, 1965;
Holser and Kaplan, 1966; Niel sen, 1972; Holser, 1979). Ex per i -
men tal stud ies have shown that the frac tional crystallisation (Dd34Sgyp sum-SW) in sea wa ter con cen trated to the be gin ning of ha - lite crystallisation amounts to 1.5 ± 0.3‰ (Raab and Spiro, 1991).
The pro cess of dis so lu tion of pre vi ously de pos ited sul phate does not lead to iso to pic frac tion ation. Sul phate redeposition causes fur ther fractionating. De tailed stud ies of the Badenian Fig. 2. Geo log i cal map of the Carpathian Foredeep in Kalush and Hrynivka ar eas,
with a geo log i cal cross-sec tion along line I–I (Stupnitskiy et al., 1978) Tec tonic sub di vi sion of the Fore-Carpathian Ba sin af ter Vul et al. (1989)
Fig. 3. Anhydrite nod ules at the bound ary of clay ma te rial and ha lite
A – coarse crys tal line rock salt with inter gra nu lar thin con cen tra tions of claystone ma te rial and nod ules of anhydrite; B – sin gle crys tal of ha lite with white nod u lar anhydrite; Hrynivka, bore hole 525,
sam ple 1362 (depth 454–456 m)
T a b l e 1 The iso to pic com po si tion of sul phur in anhydrite, Hrynivka 525 bore hole
Sam ple Depth [m]
Con tent in so lu tions [g/l]
(mean in brack ets) Jänecke Unit [%]
Anhydrite Br con tent in ha lite
[ppm] d34S‰CDT
K+ Mg2+ SO42+ 2K Mg SO4
1341 286 8.1, 10.4, 7.9
(8.8)
26.8, 33.1 (30.0)
26.1, 27.9; 26.5, 21.9 (25.6)
7.0 76.5 16.5 nod u lar 50 22.7
1342 304 8.5, 7.0, 7.4, 6.7, 9.0, 7.7, 6.9, 9.2
(7.8)
22.1, 31.7, 25.4,
24.7, 31.9 (27.2) 21.4, 22.5, 23.1,
22.9, 21.6 (22.3) 6.9 77.1 16.0 nod u lar 40 21.7
1345 314 6.1, 5.7
(5.9)
20.6, 23.8 (22.2)
17.7, 16.6, 18.3
(17.6) 6.4 77.9 15.6 nod u lar 40 21.2
1350 342–343 mas sive 22.22
1352 362 8.3, 8.8, 8.1
(8.4)
28.5, 27.6, 23.3, 32.5, 28.6, 30.7
(28.1)
18.9, 20.4, 18.9, 19.3, 22.3, 19.0
(19.8)
7.2 78.9 13.9 nod u lar 50 20.9
1353 366 4.6, 4.8, 6.3
(5.2)
20.2, 20.8 (20.5)
14.3, 13.4, 13.6
(13.8) 6.3 80.0 13.6 nod u lar 30 21.6
1354 376 5.2, 6.1
(5.7)
20.9, 23.2 (21.7)
13.6, 17.6, 14.0, 13.3, 15.6, 19.6
(15.6) 6.5 79.1 14.4 nod u lar 40 20.2
1357 410–411 7.7, 8.2, 6.5, 8.8, 8.7, 8.3 (8.0)
27.7, 28.3, 25.5 (27.2)
23.0, 21.4, 20.3
(21.6) 7.1 77.4 15.6 nod u lar 30 20.5
1362 454–456 6.3, 7.1, 7.8, 7.9 (7.3)
26.8, 25.0 (25.9)
23.8, 22.2, 20.0,
24.9, 21.5 (22.5) 6.7 76.5 16.8 nod u lar 20 21.58
1365 480 8.5, 9.2
(8.9)
32.0, 33.8, 25.3 (30.4)
23.1, 22.9, 25.0
(23.7) 7.1 77.6 15.3 nod u lar 40 21.8
Mod ern ocean wa ter sat u rated to the be gin ning of crys tal li sa tion of:
68
200 21.53–21.77
ha lite 3.9 12.6 17.6 6.6 69.0 24.3
epsomite 26.1 85.9 115.0 6.6 69.8 23.6
The com po si tion of pri mary fluid in clu sions in ha lite (Galamay, 2010) and bro mine con tent in ha lite (Galamay, 2003) for the same sam ples;
the con tent of ions in mod ern sea wa ter (af ter McCaffrey et al., 1987); bro mine con tent in pri mary ha lite af ter Holser (1979), bro mine con tent in ha lite at the be gin ning of crystallisation of K-salts af ter Holser (1966), iso to pic com po si tion of mod ern sea wa ter d34S‰CDT +20‰ en riched to 1.65 ± 0.12‰ (Raab and Spiro, 1991), iso to pic com po si tion for sam ples no. 1350 and 1362 (af ter Galamay, 1997)
gyp sum in the Carpathian Foredeep (Peryt et al., 2002) showed a large vari a tion of d34S (by 4.5–7.7‰), which was in ter preted as redeposition of pre vi ously de pos ited ma rine gyp sum.
The bac te rial re duc tion of dis solved sul phate is sup pressed in well-aer ated wa ters (Grinenko and Grinenko, 1974) and the sul phur-re duc ing bac te ria (Desulfovibrio) de velop best at pH 6.3–8.6 (Postgate, 1960). Ac cord ing to Petrichenko (1988) and Petrichenko et al. (1997) evaporite bas ins of the Carpathian re - gion and other salt-bear ing bas ins were char ac ter ized by two fac tors: they were well-aer ated and slightly acid con di tions (Eh from +150 to +450 mV; pH 4.6–6.6) pre vailed in the bas ins, which def i nitely lim ited the sul phate re duc tion. Only pe ri od i - cally, brine Eh dropped be low 150 mV (Petrichenko, 1988). The iso tope de ter mi na tions pro vided in this study were car ried out on anhydrite nod ules gen er ally found on the bound ary of ha lite chev ron crys tals and clay ma trix in chev ron ha lite (Fig. 3). That means that anhydrite de vel oped as a re sult of re dis tri bu tion of mat ter (or par tial recrystallisation of the cryptocrystalline gyp -
sum mass of sed i men tary or i gin) even at the stage of ear lier diagenesis, in non-lithified de pos its (Lobanova, 1956; Ivanov and Voronova, 1972). Thus, based on the d34S data, we do not as sume any ex ten sive de vel op ment of bac te rial sul phate re - duc tion pro cesses dur ing early diagenesis.
When pass ing from early to late diagenesis of salt de pos its, the Eh po ten tial nat u rally shifted to wards be low zero val ues (Petrichenko, 1988). Sul phate re duc tion was in di cated by the pres ence of very small (up to 50 mm) ball-shaped py rite framboids (Hrynivka, bore hole 525, sam ple 1354). Such fram - boids were found in the diagenetic ha lite and silt lay ers ac com - pa ny ing the rock salt. A con stant pres ence of py rite in the Hrynivka rock salt was also con firmed by X-ray anal y sis of the in sol u ble part of salt (Yaremchuk and Galamay, 2009). Be - sides, chem i cal re cy cling dur ing diagenesis caused in crease of d34S in anhydrite. The de crease of d34S in anhydrite was pos si - bly due to in flux of wa ter with a high con tent of the light 32S iso - tope (Makhnach, 1999).
The iso to pic com po si tion of dis solved sul phate in mod ern sea wa ter is d34S = 20.0 ± 0.25‰, based on nu mer ous wide- range anal y ses (from +19.3 to +21.4‰; Raab and Spiro, 1991) and it is sim i lar to the de duced com po si tion of Mio cene sea wa - ter (Thode et al., 1961; Posokhov, 1975; Claypool et al., 1980;
Cendón et al., 2004).
The av er age value of d34S in anhydrite of +21.4 ± 0.3‰ ob - tained in this study sug gests that the iso to pic com po si tion of dis solved sul phate in the salt-bear ing ba sin of the Hrynivka area amounted to d34S = 19.8‰ (21.4‰ – 1.65 ± 0.12‰), which ap prox i mately cor re sponds to the iso to pic com po si tion of pres - ent-day seawa ter. Our re sults in di cate that the main pro cess of sul phur iso tope frac tion ation in form ing the Hrynivka anhydrite oc curred dur ing gyp sum crys tal li sa tion from the ba sin brine.
Other frac tion ation of sul phur iso topes only slightly af fected d34S anhydrite (as dis cussed be low).
In the Hrynivka area, the chem i cal com po si tion of brine and the to tal con cen tra tion did not change sig nif i cantly dur ing the salt ac cu mu la tion pro cesses. That in di cated pe ri odic in flows of ma rine wa ters into the ba sin (Galamay, 2010). The chem i cal com po si tion of fluid in clu sions in ha lite (in ten sam ples stud ied) gen er ally in di cated a ma rine or i gin for the sed i men tary brine (Fig. 5). The av er age ra tio be tween 2K, Mg, SO4 was 6.9, 77.4, and 15.7%, re spec tively (Jänecke unit) (Galamay, 2010).
Those re sults were sim i lar to the chem i cal com po si tion of the Badenian sea wa ter sat u rated to ha lite pre cip i ta tion: 2K – 7.8%;
Mg – 77.2%, and SO4 – 15.0% (Jänecke unit; Kovalevich and Vovnyuk, 2010).
In the in ter val 362–410 m of the Hrynivka 525 bore hole, the chem i cal com po si tion of pri mary fluid in clu sions in ha lite was char ac ter ized by the low est con tent of sul phate ions (Ta ble 1, sam ples 1352, 1353, 1354, and 1357). There fore, the points cor re spond ing to the chem i cal com po si tion of fluid in clu sions in sam ples 1352, 1353, and 1354 were placed in the up per part of the Jänecke di a gram (Fig. 6). The re duc tion of SO42- ion con tent in brine was an ef fect of the nu cle ation of a large num ber of small gyp sum crys tals, ow ing to the in ter ac tion of sul phate brine with wa ters con tain ing Ca (HCO3)2 (Valyashko and Pelsh, 1952; Valyashko, 1962).
The lo ca tion of points in dic a tive of the chem i cal com po si tion of fluid in clu sions from sam ple 1357 on the di a gram (sit u ated be low 1352, 1353 and 1354 point lo ca tions) is a re flec tion of the fact that the lo cal re duc tion of mag ne sium ion con tent oc curred with re spect to sul phate in brine (for ma tion of a jelly mass, whose com po si tion is close to the for mula of 2MgO · CO2 · 4H2O, and fine rhombohedral crys tals of do lo mite). It is known that mix ing sul phate-rich brine with wa ters con tain ing Ca(HCO3)2 (so-called desulfuration, or metamorphisation of Fig. 4. Lithological pro file of the Hrynivka 525 bore hole,
with the lo ca tions of sam ples and of d34S value de ter mi na tions
sul phate-rich brine) causes mass crys tal li sa tion of fine crys tals of gyp sum, do lo mite, and 2MgO · CO2 · 4H2O (Valyashko and Pelsh, 1952). At the same time, in tense pre cip i ta tion of 2MgO · CO2 · 4H2O takes place ow ing to high al ka lin ity of the brine. In the de pos its, 2MgO · CO2 · 4H2O turns into do lo mite. A high do - lo mite con tent (ca. 7.5%) was an other char ac ter is tic fea ture iden ti fied in the mud frac tion of sam ple 1357 (Galamay, 2012).
Many small crys tals of gyp sum, anhydrite, and bassanite were ob served in the fluid in clu sions in ha lite of some sam ples (Fig. 6B). We could also ob serve anhydrite crys tals, con cen - trated along the growth zones of sed i men ta tion ha lite (Galamay, 2012). Quite of ten, such multi-phase fluid and sta ble in clu sions were de pos ited only on one of the chev ron edges (Fig. 7).
In the inter-crys tal line space of the chev ron crys tals and be - tween ha lite growths, clay ma te rial was of ten ob served (sam - ples 1352, 1353, 1354, and 1357). Sam ples 1352 and 1354 were char ac ter ized as the rich est in terrigenous clay ma te rial. In our opin ion, the de creased d34S val ues in anhydrite in three of four sam ples from in ter val 410–362 m (sam ples 1352, 1354, and 1357) are due to the in flow of con ti nen tal wa ters, which were rich in the light 32S iso tope. There fore, we con clude that the salts from the in ter val 410–362 m (Ta ble 1 and Fig. 4) were crys tal lised from ma rine sul phate brine dur ing in tense in flow of con ti nen tal wa ters into the ba sin.
Palaeogeographic re con struc tions (Fig. 1) sug gest that the de po si tion of salts in the Hrynivka area re sulted from crys tal li sa - tion from seawa ter. Sea wa ter was mostly de void of Ca(HCO3)2
(be cause of cal cium car bon ate and cal cium sul phate pre cip i ta - tion in the outer parts of the evaporite ba sin). The in flu ence of con ti nen tal run off re sulted in terrigenous ma te rial in put, metamorphisation of the sul phate-rich brine, and de crease of d34S in the anhydrite.
Dis solved sul phate from fresh wa ter and rain fall (as com - pared to sea wa ter) con tained sig nif i cantly more of the light 32S iso tope, as dem on strated by other au thors (e.g., Vinogradov et al., 1962; Yeremenko and Pankina, 1971). For ex am ple, con ti - nen tal run off had a pro found ef fect on the wa ter of the mod ern Black, Azov, and Cas pian seas. So, the sea wa ter near the coast of the Black Sea has d34S = +18.9‰, while the iso to pic com po si tion of dis solved sul phate of the Black Sea in gen eral is d34S = +19.3‰. The sea wa ter of the Azov Sea near Kerch has a value of d34S = +15.5‰ (Yeremenko and Pankina, 1971).
The iso to pic com po si tion of dis solved sul phate in the Cas pian Sea, which has no con nec tion with the ocean, is +8.6‰.
The typ i cal bro mine con tent in a ma rine-de rived ha lite at the be gin ning of its crys tal li sa tion is ca. 68 ppm (Holser, 1979), or 50–60 ppm (Valyashko and Mandrykina, 1952). In the in ves ti - gated sed i men tary ha lite bro mine con tent was quite low (20–50 ppm, Ta ble 1). A low bro mine con tent in the ha lite of the Fig. 5. The sed i men ta tion struc ture of ha lite (chev ron),
formed with pri mary fluid in clu sions
There are fluid in clu sions (con tain ment fail ure along a crack) on the left-hand side of the struc ture which con tains a gas phase;
Hrynivka, bore hole 525, sam ple 1361 (depth 444–448 m)
Fig. 6. Chem i cal com po si tion of brine in pri mary in clu sions in ha lite shown on a Jänecke di a gram (for sea wa ter, at a tem per a ture of 25°C)
Chem i cal com po si tion of brine in pri mary fluid in clu sions in ha lite; Hrynivka, bore hole 525 (Galamay, 2010), 1 – chem i cal com po si tion points of fluid in clu sions, 2 – chem i cal com po si tion point of mod ern sea wa ter sat u rated to the be gin ning of ha lite crys tal li sa tion (McCaffrey et al., 1987); small crys tals of anhydrite be tween zones of sed i men tary ha lite and gyp sum, bassanite and anhydrite in pri mary fluid in clu sions in ha lite for each of the sam ples (Galamay, 2012); 3 – a con sid er able amount of crys tals; 4 – a small amount, or an ab - sence of crys tals
sam ples stud ied in di cates that redeposition of ha lite oc curred in the salt-bear ing ba sin and that con tri bu tions of both ma rine and con ti nen tal wa ters a ef fected Br con cen tra tions in the pre cip i - tated ha lite.
The stron tium iso tope ra tio (87Sr/86Sr) in one anhydrite sam - ple from the Hrynivka 525 bore hole (no. 1354) (Peryt et al., 2010) gave a value of 0.708902. That ra tio is slightly higher than the ra tios ex pected for Badenian sea wa ter (0.708800–0.708809; McArthur et al., 2001). The rel a tively slightly ra dio genic 87Sr/86Sr ra tio of anhydrite sam ple 1354 may have been de rived from clay in ter ca la tions in the rock salt (Peryt et al., 2010), and so ev i dence of con ti nen tal wa ter in flow to the salt-bear ing ba sin.
DISCUSSION
The av er age sul phur iso to pic com po si tion (d34S) of the anhydrite from the Carpathian Foredeep and East Slo vak bas - ins ranges be tween +21.5 and +22.5‰ (Ta ble 2). The de ter mi - na tion of d34S for the anhydrite of the salt suc ces sion shown on the di a gram (Fig. 8) in di cates a nar row range of the val ues for sixty sam ples. In the case of five de ter mi na tions, the val ues
were clearly di verse. The low est of these were ob tained from nod u lar anhydrite orig i nat ing from zubers of the Bochnia Salt Mine (+18.78‰, sam ple 1; Bukowski and Szaran, 1997) and the Zbudza salt de posit in the East Slo vak Ba sin (18.28‰, sam - ple P7/2; Kasprzyk and Bukowski, 2009). Those low val ues (d34S) prob a bly re sulted from the de liv ery of sul phate ions to the ba sin, en riched with light sul phur iso topes, orig i nat ing from me - te oric wa ters and con tain ing ox i dised sul phur com pounds. This was con firmed by the pres ence of car bon ised plant mat ter in the Zbudza anhydrite sam ple, as well as by very low bro mine con tent (5.8 ppm) in the ha lite oc cur ring di rectly above the anhydrite (Bukowski et al., 2007).
Then, the val ues of d34S amount ing to +24.4‰ (Zbudza, sam ple P-6/24; Kasprzyk and Bukowski, 2009), +25.4‰ (Bo - chnia, sam ple 23; Bukowski and Szaran, 1997), and +24.0‰
(Wieliczka, sam ple A-8-W; Bukowski and Szaran, 1997) were char ac ter is tic of late diagenetic va ri et ies of gyp sum and anhy - drite (sul phate dis so lu tion and re-pre cip i ta tion; bac te rial re - duc tion of sulphates). Those sam ples were also litholo gically dif fer ent from the re main ing ones (fi brous gyp sum fill ing crev - ices, in ner anhydrite fill ing the layer shear planes, and anhydrite ag gre gates with small crys tals of xenomorphous ha - lite in the silty ma trix).
The ex tremely high val ues and ex tremely low val ues were not taken into ac count in cal cu lat ing the d34S in dis solved sul - phates of the Badenian sea wa ter of the Cen tral Paratethys.
Based on sixty de ter mi na tions of d34S in anhydrite (av er age
34S = +22.0‰) and tak ing into ac count iso to pic frac tion ation dur ing Ca-sul phate crystallisation (22.0‰ –1.65 ± 0.12‰), we could de ter mine that the av er age d34S of dis solved sul phate in sea wa ter of the Cen tral Paratethys was +20.3‰. This com po - si tion is com pa ra ble to the iso to pic com po si tion of dis solved sul phate in pres ent-day sea wa ter and the val ues es tab lished for the Badenian evaporite ba sin brine of the Carpathian Foredeep (d34S = +20.6‰) (Kasprzyk, 1997). The d34S value for the Badenian sea wa ter may ac tu ally have been slightly higher if we con sider po ten tial changes to the brine com po si tion of salt- bear ing bas ins caused by in flow of con ti nen tal wa ters en - riched in light 32S iso topes.
The re sults pre sented here are gen er ally con sis tent with the ma jor ity of chem i cal com po si tion de ter mi na tions of fluid in clu - sions in ha lite ob tained by the ultramicrochemical method de - vel oped by Petrychenko (1973). In the ma jor ity of the Badenian evaporite bas ins, the com po si tion and the pro por tions of main Fig. 7. Multi-phase fluid in clu sions with gyp sum, bassanite,
and anhydrite crys tals, or terrigenous ma te rial Ar rows in di cate large fluid in clu sion, with gyp sum crys tals;
Hrynivka, bore hole 525, sam ple 1354
T a b l e 2 Sul phur iso to pic com po si tion in anhydrite from the Badenian salt-bear ing de pos its of the Carpathian re gion
Ba sin Lo ca tion Num ber
of sam ples
Range Mean
Ref er ences
34S‰CDT 34S‰CDT
Carpathian Foredeep
Hrynivka, borehole 525 8 20.20–22.70 21.32 New data
2 21.58–22.22 21.90 Galamay (1997)
Zabolotiv, bore hole 4038 1 21.60 21.60 Galamay (1997)
Slanic Prahova 3 20.27–21.12 20.78 Galamay (1997)
Barycz, bore hole 962 2 21.47–22.36 21.91 Bukowski and Szaran (1997)
Wieliczka 8 21.45–24.03 22.62 Bukowski and Szaran (1997)
Wieliczka 4 21.90–22.80 22.40 Parafiniuk and Halas (1997)
Wieliczka 3 21.6–21.9 21.77 Claypool et al. (1980)
Bochnia 7 18.78–25.36 21.75 Bukowski and Szaran (1997)
Wojnicz, bore hole IG 4 14 22.01–23.20 22.61 CendÙn et al. (2004) East Slovakian
Ba sin
Zbudza, well Ep-2 3 21.77–21.98 21.85 Galamay (1997)
Zbudza, well P-6, P-7 10 18.28–24.45 22.22 Kasprzyk and Bukowski (2009)
ions in the fluid in clu sions in di cated a ma rine or i gin for the brines (Bukowski, 2011 with ref er ences therein). How ever, lo - cal in flows of con ti nen tal wa ters were also iden ti fied (Kovale - vich and Petrichenko, 1997; Galamay, 2001; Galamay and Bukowski, 2011).
Stud ies of the chem i cal com po si tion of fluid in clu sions, bro - mine con tent in ha lite, and the iso to pic com po si tion of sul phur and ox y gen in anhydrite were made on rock salt of the Wojnicz area in the Pol ish Carpathian Foredeep by Cendón et al. (2004).
Mod el ling based on the re sults of those stud ies in di cated that, dur ing ha lite pre cip i ta tion in the Carpathian Foredeep, con ti nen - tal wa ters amounted to as much as 65–70%, with only 20–30%
sea wa ter and 5–10% brine orig i nat ing from pre vi ously dis solved ha lite (Cendón et al., 2004). The chem i cal com po si tion of fluid in - clu sions in the ha lite was the ba sis of mod el ling. The data were ob tained with a mod ern pre cise method (Cryo-SEM-EDS) and stud ies of fluid in clu sions in ha lite. Those data in di cated that the av er age ra tios of 2K, Mg, and SO4 in brine (sam ples WJ-3, WJ-13, WJ-18, WJ-41; Cendón et al., 2004) were 6.9, 75.2 and 17.9%, re spec tively (Jänecke unit). This chem i cal com po si tion was typ i cal of Badenian ma rine brine (Galamay and Bukowski, 2011; Bukowski, 2011). How ever, the chem i cal com po si tion of the fluid in clu sions of other sam ples (WJ-22, WJ-26, WJ-3B, WJ-36; Cendón et al., 2004) was dif fer ent from those pre sented above. In some of the sam ples, we ob served an oma lously low con cen tra tions of K+ ions. For ex am ple, in sam ple WJ-22, the po tas sium con tent was be low the limit of quan ti fi ca tion, which was in ter preted as a re sult of a lo cal re ac tion of brine with cal - cium sul phate to pre cip i tate polyhalite (Cendón et al., 2004).
That hy poth e sis was cor rob o rated by the lo cal pres ence of polyhalite at var i ous lev els through out the bore hole (Cendón et al., 2004). In that case, anhydrite or gyp sum were trans formed into polyhalite through re ac tion with ma rine brine of high con cen - tra tion. Con se quently, the chem i cal com po si tion of the par ent brine could be changed un der lo cal con di tions and the ion ra tios in pri mary fluid in clu sions not re flect “typ i cal Badenian brine”
(e.g., Kovalevich and Petrichenko, 1997; Galamay, 2001;
Galamay and Bukowski, 2011).
The sul phur iso tope com po si tions of anhydrite from Wojnicz (Cendón et al., 2004) were sim i lar to the data avail able from other parts of the salt ba sin (Ta ble 2). The re sults were al most con stant with a range of d34S = +22.0‰ to +23.2‰, and on av er - age of d34S = +22.6‰. To ex plain that iso to pic com po si tion cor - re spond ing to the iso to pic com po si tion of ma rine or i gin, Cendón et al. (2004) sug gested that the iso to pic val ues of d34S were not al ways ex plicit in di ca tions of the sul phate or i gin. In con di tions of
sea wa ter mix ing with me te oric wa ters sat u rated with ha lite, sulphates could crys tal lise and pro duce iso to pic val ues sim i lar to d34S = 22‰, be ing ba si cally not very dif fer ent from typ i cal ma - rine-or i gin sulphates (Ayora et al., 1994; Cendón et al., 2004).
Such in ter pre ta tion would re quire con fir ma tion for in stance by chlo rine iso tope stud ies of ha lite (Eastoe and Peryt, 1999;
Eastoe et al., 2007, though see e.g., García-Veigas et al., 2009).
CONCLUSIONS
The d34S val ues in the Hrynivka anhydrite range from +20.2‰ to +22.7‰. Those val ues are con sis tent with the re - sults of chem i cal com po si tion stud ies of pri mary fluid in clu sions in ha lite, per formed by ultramicrochemical method (Petry - chenko, 1973) and in di cate that sea wa ter had been the main source of sol utes in the ba sin.
The sul phur iso tope con tent of the anhydrite in di cates a ma - rine or i gin for the sul phate, though this not syn on y mous with a ma rine ba sin. At dif fer ent stages of salt ac cu mu la tion, we could in fer in flows of con ti nen tal wa ters in to the ba sin, with a lighter iso to pic sul phate com po si tion (as sup ported by data from the Hrynivka, Bochnia, and Zbudza de pos its).
The d34S value of the Badenian sea wa ter of the Cen tral Paratethys was cal cu lated from sixty val ues and the de ter mi na - tions of sul phur iso to pic com po si tion for anhydrite of the Carpa - thian re gion was ap prox i mately +20.3‰. The d34S value for the Badenian ocean wa ter may ac tu ally have been slightly higher if we con sider po ten tial changes of the brine com po si tion of salt-bear ing bas ins caused by in flow of con ti nen tal wa ters en - riched in light 32S iso topes.
Ac knowl edge ments. This in ves ti ga tion was sup ported by the Ma jor State Ba sic Re search De vel op ment Pro gram (973 no. 2011CB403007), Na tional Nat u ral Sci ence Foun da tion of China (No: 40703018; 41173051; 41172131) and The Bu reau of In ter na tional Co-op er a tion of the Chi nese Acad emy of Sci - ences as well as through stat u tory funds of the AGH Uni ver sity of Sci ence and Tech nol ogy (pro ject No. 11.11.140.320). The de ter mi na tions of the iso to pic com po si tion of sul phur were made by Dr. Feng Lianjun in the Nanjing In sti tute of Ge ol ogy and Geo phys ics, Chi nese Acad emy of Sci ences (IGGCAS).
We also sin cerely thank Dr. D. I. Cendón, Prof. T. Peryt, and in par tic u lar an anon y mous re viewer for their com ments and sug - ges tions which im proved the text.
Fig. 8. Sul fur iso to pic com po si tion in anhydrite from the Badenian salt de pos its of the Carpathian re gion The di a gram shows new and pre vi ously pub lished data (Claypool et al., 1980; Galamay, 1997; Bukowski and Szaran, 1997;
Parafiniuk and Halas, 1997; Cendón et al., 2004; Kasprzyk and Bukowski, 2009)
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