GeolCarp_Vol53_No6_391

GEOLOGICA CARPATHICA, 53, 6, BRATISLAVA, DECEMBER 2002

391 — 398

S AND O ISOTOPE COMPOSITION OF THE BADENIAN (MIDDLE

MIOCENE) SULPHATES IN THE CARPATHIAN FOREDEEP

TADEUSZ MAREK PERYT

, JANINA SZARAN

, MAREK JASIONOWSKI

, STANISŁAW HALAS

DANUTA PERYT

, ANDRIY POBEREZHSKYY

, STANISLAV KAROLI

and ARTUR WÓJTOWICZ

1,2

Polish Geological Institute, Rakowiecka 4, 00-975 Warszawa, Poland; tperyt@pgi.waw.pl, mjas@pgi.waw.pl

Mass Spectrometry Laboratory, Institute of Physics, Maria Curie-Skłodowska University, 20-031 Lublin, Poland;

jszaran@tytan.umcs.lublin.pl, halas@tytan.umcs.lublin.pl, wujek@tytan.umcs.lublin.pl

Institute of Paleobiology, Polish Academy of Sciences, Twarda 51/55, 00-818 Warszawa, Poland; d.peryt@twarda.pan.pl

Institute of Geology and Geochemistry of Combustible Minerals, National Academy of Sciences of Ukraine, Naukova 3A,

79053 Lviv, Ukraine; igggk@ah.ipm.lviv.ua

Geological Survey of Slovak Republic, Jesenkého 8, 040 01 Košice, Slovak Republic; karoli@gssr-ke.sk

(Manuscript received January 29, 2002; accepted in revised form June 18, 2002)

Abstract: A study of 333 samples from eight sulphate sections of the Badenian (Middle Miocene) from the marginal
part of the Carpathian Foredeep basin and one section from its central part proved that the isotopic compositions of both
oxygen and sulphur show a similar trend of evolution throughout the sections. In some cases, in the lower part of gypsum
sections a gradual decrease of

S and

O is observed. In turn, the upper part of the section shows fluctuations of quite

high amplitude, but within a clearly defined interval. The variation of

O values in the whole area is similar to that of

S values although in particular facies the variation ranges are different. Clastic gypsum shows the greatest spread of

S and

O values. 39 % of all

S values and 46.5 % of all

O values are higher than those characteristic for the

marine sulphate values, and these higher values are mostly characteristic for clastic gypsum. Selenitic gypsum shows
relatively narrow ranges of

S and

O values and hence is especially useful for analyses of depositional conditions.

The isotopic composition of Badenian sulphates reflects the marine origin of brines. The recorded great spread of

and

O values in the Badenian sulphates is related to the recycling of previously formed evaporites already during

gypsum precipitation in the Carpathian Foredeep basin.

Key words: Carpathian Foredeep, Badenian, sulphates, isotopic composition, facies.

Introduction

S and

O are very helpful tools to investigate the origin

of sulphate deposits for a number of reasons (Pierre 1989).
One of them is that the

S and

O values are very insensi-

tive to nonmarine contribution. On the other hand, redox pro-
cesses of sulphur species during gypsum deposition have
great impact on the sulphate

S and

O (Lu & Meyers

1997).

Our preliminary study of one section (Borków quarry –

Halas et al. 1996) from the Badenian (Middle Miocene)
evaporite basin of Carpathian Foredeep suggested that there is
a lithological control on the

S and

O values. However,

this was questioned by the results of study of another section
(Wiązownica 1 – Kasprzyk 1997). Therefore, it was decided
to  gather  a  larger  set  of  new  data,  which  should  help  in  the
evaluation  of  the  importance  of  lithological  variation  (being
the  reflection  of  sedimentary  conditions)  on  changes  of  the

S and

O values.

The depositional environments of the Badenian sulphate

deposits have been the subject of detailed research (e.g. Bąbel
1999;  Kasprzyk  1999;  Kasprzyk  &  Orti  1998;  Peryt  1996,
2000, 2001). These studies have shown that although the gyp-
sum  originated  mainly  from  marine  water,  nonmarine  water
and  mixtures  of  both  marine  and  nonmarine  water  could  be
important in some areas and times of gypsum deposition. This

was additionally supported by geochemical evidence based on
study of roughly coeval halite deposits: the chemical compo-
sition of major solutes trapped in the halite, the Br content in
halite and the modelling of the brine evolution (Cendón et al.
1999). The aim of this paper is to ascertain the origin of the
parent brines and the depositional conditions of the Badenian
gypsum on the basis provided by

S and

O data.

Geological setting

The Carpathian Foredeep basin is a typical peripheral fore-

deep  basin  filled  with  Miocene  synorogenic  molasse  sedi-
ments (Fig. 1). Evaporites are related mostly to the Badenian
and  they  form  an  excellent  correlation  marker.  The  nanno-
plankton  study  showed  that  the  Badenian  gypsum  corre-
sponds  to  the  lower  part  of  NN6  Zone  (cf.  D.  Peryt  1997,
1999).

Badenian evaporites show a regular spatial pattern of

evaporite facies. Primary gypsum forming a wide (20—60 km)
sulphate platform (with gypsum sections a few tens of meters
thick) occurs in the most marginal, northern part of the Car-
pathian Foredeep (Fig. 1). The sedimentological studies of the
Badenian gypsum (e.g. Bąbel 1999; Kasprzyk 1999; Peryt
1996, 2001; see also the review of earlier studies there) have
shown that autochthonous gypsum facies (crystalline gypsum,

392 PERYT et al.

stromatolitic  gypsum  and  massive  alabastrine  gypsum)  were
deposited  in  a  vast  brine  pan,  in  extremely  shallow-water  to
subaerial environments on broad, very low relief areas of neg-
ligible brine depth. Giant gypsum intergrowths originated by
continual precipitation from a brine body. Allochthonous sul-
phate  (encompassing  clastic  gypsum  and  gypsum  breccias)
originated  in  generally  deeper  environments.  In  more  buried
areas the sulphate platform sections are built of anhydrite, but
in most cases it is possible to relate the anhydrite textures to
the primary gypsum ones.

In the basinward part of the Badenian evaporite basin, an-

hydrite  usually  10—30  m  thick  occurs  in  a  zone  20—60 km
wide (Fig. 1). The sulphates are laminated with sulphate brec-
cia,  nodular  sulphate  and  siltstone  intercalations.  The  petro-
graphic study showed that those anhydrite deposits were orig-
inally composed of detrital gypsum (Kasprzyk & Orti 1998).
A  great  deal  of  redeposition  within  the  basin  centre  of  the
Badenian  evaporite  basin  combined  with  the  in  situ  breccia-
tion  suggests  that  the  triggering  mechanism  for  redeposition
could  be  earthquakes  (Peryt  2000).  They  generated  mass
flows  and  eventually  turbidites,  so  that  earlier  deposited
grains could be redeposited.

In the southern part of the sedimentary basin, in the narrow

axial part of the basin, halite deposits (up to 110 m thick) oc-
cur in local salt basins.

Material and methods

Our data set comprises 333 samples (compared to 70 analy-

ses done by other authors: Claypool et al. 1980; Parafiniuk et
al. 1994; Bukowski & Szaran 1997; Kasprzyk 1997; Parafini-
uk & Halas 1997; Rosell et al. 1998) coming from 9 sections.
Five outcrop gypsum sections are located in the marginal part
of the basin in Ukraine (Mamalyga, Potochishche and Veren-
chanka – Peryt 2001), Poland (Borków – Halas et al. 1996)
and the Czech Republic (Kobeřice – Peryt et al. 1997). From
the same, marginal part comes one anhydrite section (Wola
Różaniecka 7 borehole in Poland). One anhydrite section
(Ryszkowa Wola 7 borehole in Poland – Peryt et al. 1998) is

from the central part of basin. In addition, 25 samples from
two gypsum exposures (Pisky and Palahychi in Ukraine) have
been taken from a part of the gypsum section where earlier a
distinctive isotopic anomaly was recorded in the Borków gyp-
sum section in southern Poland (Halas et al. 1996). When
sampling the crystalline sulphate types, the pieces for analy-
ses were taken from crystals.

Each sample was first powdered and dissolved in distilled

water, then the solution was filtrated and acidified with HCl,
to pH = 1, and then a 10% solution of BaCl

was added

to pre-

cipitate BaSO

. The precipitate was washed with water to

eliminate Cl

—

ions, centrifuged, and dried at 110

C. Barium

sulphate was then treated with different analytical procedures
to study sulphur and oxygen isotopes. SO

was produced by

the reduction of barium sulphate by NaPO

in a Cu-boat at

700

C (Halas & Szaran 1999). CO

was produced using the

method of Mizutani (1971) in a separate vacuum line, where
BaSO

was quantitatively reduced by spectrally pure graphite

in a thin platinum boat at 1000

C to BaS and CO, which was

subsequently converted to CO

by glow discharge between

platinum electrodes. The SO

and CO

gases were collected

into glass ampoules and analysed on a dual inlet and triple
collector mass spectrometer (reconstructed MI 1305) with a
precision of 0.05 to 0.08 ‰. The reproducibility of

O and

S measurement was 0.08 ‰.

Results

O and

S changes with stratigraphic location are

shown in Figs. 2—4, and plots of

S versus

O of gypsum

in the studied sections are shown in Fig. 5A. All results are
summarized in Tables 1 and 2. In Fig. 5, the box indicates the
range of values for Miocene gypsum deposited from normal
marine brines (

S = 21.65 ‰±0.5 ‰,

O = 12.5 ‰±0.5 ‰;

Zak et al. 1980; Paytan et al. 1998).

In general, the isotopic compositions of both oxygen and

sulphur show a similar trend of evolution throughout the sec-
tions. In a few cases (Borków – Fig. 2; Mamalyga and Veren-
chanka – Fig. 3), in the lower part of the sections a gradual

Fig. 1. Location map.

S AND O ISOTOPE COMPOSITION OF SULPHATES IN THE CARPATHIAN FOREDEEP 393

Fig. 2. Studied sulphate sections in the Czech Republic (Kobeřice – gypsum; composite isotope section after Peryt et al. 1997) and Poland
(Borków – gypsum, after Halas et al. 1997, Wola Różaniecka 7 – anhydrite, and Ryszkowa Wola 7 – anhydrite, after Peryt et al. 1998)
and the

O and

S values of sulphates.

n–1

whole area

333 12.95 12.92 17.67 10.08

1.00

22.13 21.96 25.70 18.04 0.94

Kobeřice

50 12.27 12.23 14.01 10.39 0.71 21.77 21.92 23.90 18.04 1.12

Borków

65 12.49 12.19 17.67 10.08 1.44 22.00 21.77 25.67 20.46 1.01

Wola Różaniecka 7

20 13.68 13.58 16.45 12.43 0.97 23.44 23.14 25.70 21.88 1.07

Ryszkowa Wola 7

51 12.98 12.82 15.15 11.26 0.75 22.68 22.73 24.18 20.92 0.75

Pisky

11 12.91 13.02 13.40 12.14 0.40 21.77 21.76 22.20 21.15 0.33

Palahychi

14 13.22 13.30 13.67 12.65 0.32 21.61 21.59 22.15 21.01 0.38

Potochishche

28 12.87 12.89 14.30 12.01 0.45 22.06 22.08 22.65 21.29 0.30

Verenchanka

46 13.53 13.29 15.83 11.93 0.84 22.08 21.90 24.79 20.83 0.89

Mamalyga

48 13.34 13.47 14.19 11.75 0.59 21.90 21.79 23.42 21.16 0.51

decrease of

S and

O is observed. In turn, in the lower

part of other sections as well as in the upper part of the sec-
tions, fluctuations of quite high amplitude, but within a clear-
ly defined interval are recorded (Figs. 2, 3). The exceptions
from this general trend are: a rapid change of the

S and

O values in the middle part of the Borków section (Figs. 2,

4) and a rapid, regular decrease of

O values and a concur-

rent slight increase of

S values in the lowermost part of the

Ryszkowa Wola 7 section (Fig. 2).

The variation of

O in the whole area is similar to that of

S (Fig. 5A), although in particular facies the variation

ranges are different (Fig. 5B—F).

In the giant intergrowth facies, the isotopic composition

shows values close to those characteristic for precipitates from
normal marine brines (Fig. 5C). Fig. 5C also shows the

and

O values of the nodular anhydrite from the Wola

Różaniecka 7 borehole, which is regarded as pseudomorphing
giant gypsum intergrowths. This anhydrite shows a major ex-
cursion from the marine values (Fig. 5C).

In the selenitic facies, total variation of

O (4.94 ‰) is al-

most twice as large as that of

S (2.89 ‰) (Fig. 5D). 70 % of

the values are outside the marine field. Within this field, some
selenites from Borków, Kobeřice, Palahychi, Potochishche,
and Verenchanka are located. Other selenites from Borków

Table 1: Isotopic composition (

O [SMOW],

S [CDT]) of undifferentiated sulphate facies in studied Badenian (Middle Miocene) sections

of the Carpathian Foredeep. X – mean: X – median; X

– maximum; X

– minimum;

n—1

– standard deviation; n – number of samples.

394 PERYT et al.

and Kobeřice are slightly lighter in O. Selenites from Veren-
chanka show higher

O (by 1—2 ‰) and sometimes

similar higher values have been found in the Wola
Różaniecka 7 borehole.

In the stromatolite facies, the total variation of

O is simi-

lar to that of

S and only 30 % of the values are located

within marine field (Fig. 5F). Results for some samples from
Potochishche, Mamalyga, Verenchanka and Borków fall into
the marine field. However, stromatolites from Verenchanka
show values lying mostly outside the field that are up to 3 ‰
heavier in O and S. Stromatolitic facies of the Wola
Różaniecka 7 borehole is heavier in S (1—4 ‰).

In the alabastrine facies, less than half the values are located

within the marine field, and others are very slightly higher in
O and/or slightly heavier in S (Fig. 5E).

In contrast to the autochthonous facies, the allochthonous

facies show values that are mostly located outside the marine
field (Fig. 5B). They also show the greatest range of values

(

O – 7.28 ‰;

S – 7.66 ‰). Only values recorded in

Pisky are located within the marine field or very close to it.

Interpretation

54 % of the

S values and 38.5 % of the

O values are

located within the marine box, whereas 7 % of the

S values

and 15 % of the

O values are below the marine sulphate

values. Lighter data are interpreted as reflecting the reservoir
effect – the special case of isotopic evolution in small-sized
reactant  reservoirs  which  diminish  continuously  as  the  reac-
tion  proceeds  (Pierre  1988) –  in  gypsum  precipitation.  The
greater  drop  in  the

O values is related to almost twice

greater oxygen fractionation when compared to that of sul-
phur during gypsum precipitation (3.6 ‰ and 1.65 ‰, respec-
tively – Lloyd 1968; Thode & Monster 1965). The slightly
regressive curves for O and S are due to progressive crystalli-

Fig. 4.

O and

S values of gypsum near the autochthonous gypsum-allochthonous gypsum boundary in Borków and in two sections

in Ukraine (Pisky and Palahychi). Lithology as explained in Fig. 2.

Fig. 3. Studied gypsum sections in Ukraine (Mamalyga, Verenchanka, and Potochishche) and

O and

S values of gypsum (after

Peryt 2001). Lithology as explained in Fig. 2.

S AND O ISOTOPE COMPOSITION OF SULPHATES IN THE CARPATHIAN FOREDEEP 395

zation of gypsum. 39 % of the

S values and 46.5 % of the

O values are higher than those characteristic for marine

sulphate values. Clearly higher

S values could result from

the bacterial reduction of a part of the sulphate ion or from the
supply of heavier sulphate ion from dissolution of the earlier
deposited Badenian gypsum or from the combination of both
factors. The dissolution of previously precipitated sulphate
leads to enrichment of sea-water sulphate in

S and

O. In

contrast to the precipitation process, dissolution does not lead
to isotope fractionation. Hence a repetitive precipitation of
sulphates may lead to a double fractionation, that is to 3.3 ‰
in

S and 7.2 ‰ in

O. A major excursion from the marine

values recorded in the anhydrite and interpreted as pseudo-
morphing giant gypsum intergrowths in the Wola Różaniecka
7 borehole is also interpreted as the result of a sulphate repre-
cipitation process.

A rapid change of the

S and

O values in the middle

part  of  the  Borków  section  (Figs.  2,  4)  could  be  related  to  a
considerable  environmental  change  that  occurred  at  the  au-
tochthonous-allochthonous gypsum boundary, but as no such
change occurs in other sections in the same paleogeographical
setting (Fig. 4), it could have resulted from repetitive precipi-
tation  of  sulphate  and/or  bacterial  reduction  processes.  The
lowermost portion of the sulphate sequence in the Ryszkowa
Wola  7  borehole  showing  also  high

S and

O values is

interpreted in the same way.

In Ryszkowa Wola 7, the

O values range from 11.26 to

15.15 ‰, and the

S values range from 20.92 to 24.18 ‰

(Fig. 5A). In the Wieliczka and Bochnia mines, the

O val-

ues usually range from 11.7 to 13.2 ‰ while the

S values

range from 20.7 to 24.0 ‰ (Bukowski & Szaran 1997). Ac-
cordingly, the

S values in anhydrite from the Ryszkowa

Wola 7 well are very slightly higher when compared to those
from the halite facies in Wieliczka and Bochnia mines and the

O values are slightly higher when compared to those from

the halite facies. This trend may reflect a reservoir effect, if
halite precipitation post-dates sulphate crystallization.

Discussion

The modeling done by Lu & Meyers (1997) demonstrated

that O isotopes can have larger variations than S because in-
corporation of water oxygen and dissolved free oxygen in-
creases

O of the reoxidized sulphate, while reoxidization of

sulphide to sulphate decreases

S. However, in the Bade-

nian sulphates the O and S variations are similar (Table 2).
The largest impact of bacterial oxidation-reduction of sulphur
compounds on the variations of

S and

O values of sul-

phate  is  because  microorganisms  select  preferentially  light
isotope  species  during  metabolic  activity  (Pierre  1988).  Re-
dox  between  sulphur  species  during  and/or  before  sulphate

Fig. 5. Plot of

O and

S values in studied sulphate sections (A) and in the particular sulphate facies (B – allochthonous facies; C –

giant intergrowth facies; D – selenitic facies; E – alabastrine facies; F – stromatolitic facies). The box shows the range of values for Mi-
ocene gypsum deposited from normal marine brines.

396 PERYT et al.

precipitation could result in significant variations of

S and

O values especially in deep-water basins (Lu & Meyers

1997), and this corresponds to large variations of

S and

O values as observed in the clastic facies (Fig. 5B, Table

2). Reducing conditions have been envisaged by Petrichenko
et al. (1997) and Kasprzyk (1997) for the Badenian gypsum as
it typically abounds in organic matter, bitumens and reduced
iron species, and these conditions favoured anaerobic micro-
bial activity and continuous production of H

S during the sul-

phate-reduction reaction, and simultaneous

O and

S en-

richments in residual sulphate.

The data on the isotopic composition of 70 samples of Bad-

enian  gypsum  and  anhydrite  earlier  published  by  other  au-
thors (Claypool et al. 1980; Parafiniuk et al. 1994; Bukowski
&  Szaran  1997;  Kasprzyk  1997;  Parafiniuk  &  Halas  1997;
Rosell et al. 1998) fit our results, although our data set differs
in  its  larger  spread  of

values (especially

S values) and

different pattern of

values (cf. Fig. 6A,B).

In general, the isotopic composition of sulphate reflects the

marine origin of the brines as found in the marginal basins of
the  Messinian  in  SE  Spain  (Playà  et  al.  2000).  The  bromine
content (e.g. Garlicki & Wiewiórka 1981; Galamay 1997) and
the composition of primary fluid inclusions in Badenian halite
(Kovalevich & Petrichenko 1997) suggest a marine origin for
brines from which the Badenian evaporites have precipitated.
However, Cendón et al. (1999) have deduced from the study
of  solute  concentrations  and  the  different  evaporation  sce-
narios modelled, that during halite precipitation in the Car-
pathian  Foredeep  basin,  there  was  recycling  of  previously
formed evaporites with an important input of water of conti-
nental origin.

The redeposition of Badenian evaporites is a common fea-

ture during both halite (e.g. Ślączka & Kolasa 1997) and gyp-
sum deposition (e.g. Peryt 2000). Therefore, it is possible that,
already during gypsum precipitation in the Carpathian Fore-
deep basin, the recycling of previously formed evaporites was
of great importance. It is recorded in the great spread of

and

O values as observed not only in the allochthonous

gypsum unit (Fig. 5B), which could be expected taking into
account the redeposited nature of that unit, but also in the
most gypsum facies (Fig. 5A,C—F).

Relatively narrow ranges of

S and

O values are re-

corded in giant gypsum intergrowth, selenitic, and alabastrine
gypsum facies. The selenitic facies also shows an important

part of

S and

O values within the marine box (Fig. 5D),

as well as the logical spatial occurrence of higher

O values

(sections Verenchanka and Potochishche from the facies zone
II after Peryt 2001) and lower

O values (sections: Palahy-

chi, Borków and Kobeřice from the more basinward-located,
facies zone III after Peryt 2001). Therefore, selenitic gypsum
facies is especially useful for paleoenvironmental analyses.

The recorded great spread of

S and

O values in the

Badenian sulphates is related to the recycling of previously

Fig. 6. Histogram of

S values (A) and

O values (B) of the

Badenian sulphate rocks of the Carpathian Foredeep based on our
study and the data of earlier workers (Claypool et al. 1980;
Parafiniuk et al. 1994; Bukowski & Szaran 1997; Kasprzyk 1997;
Parafiniuk & Halas 1997; Rosell et al. 1998).

Table 2: Isotopic composition (

O [SMOW],

S [CDT]) of particular sulphate facies in studied Badenian (Middle Miocene) sections

of the Carpathian Foredeep.

Facies

giant intergrowths

stromatolitic

alabastrine

selenitic

clastic

mean

12.94 22.00 13.26 22.05 12.89 22.11 12.73 21.86 12.89 22.30

median

13.02 21.92 13.20 21.87 13.01 22.06 12.67 21.77 12.76 22.19

maximum

16.45 25.10 15.83 25.32 13.48 23.07 15.02 23.90 17.67 25.70

minimum

11.48 20.18 11.31 20.83 12.26 21.52 10.08 21.01 10.39 18.04

standard deviation

1.03 0.99 0.72 0.74 0.41 0.44 0.89 0.58 1.17 1.16

number of samples

136

S AND O ISOTOPE COMPOSITION OF SULPHATES IN THE CARPATHIAN FOREDEEP 397

formed evaporites already during gypsum precipitation in the
Carpathian Foredeep basin. This recycling was earlier proved
by Cendón et al. (1999) for the Badenian halite precipitation.
As  indicated  by  Taberner  et  al.  (2000),  the  information  pro-
vided by the isolated use of one geochemical marker (such as
the  isotopic  composition  of  sulphates)  should  be  used  with
caution;  however,  the  interpretation  of

S and

O values

in the Badenian sulphates is supported by interpretation of
their depositional environments.

Conclusions

1. The isotopic composition of Badenian sulphates reflects

the marine origin of brines but the recycling of previously
formed evaporites was of great importance. It is recorded in a
great spread of

S and

O values as observed not only in

the allochthonous gypsum unit but also in the most gypsum
facies.

2. There is no essential isotopic difference between various

depositional facies of sulphate rocks although they differ in
respect of the mean

S and

O values as well as their stan-

dard deviation, and hence lithological variation (being the re-
flection of sedimentary conditions) influences changes in the

S and

O values.

3. Selenitic gypsum shows relatively narrow ranges of

and

O values and hence it is especially useful for analyses

of depositional conditions.

Acknowledgments: The research was supported by the Polish
Committee for Scientific Research (Grant No. 6 P04D 009 11
to T. Peryt) and the National Fund for Environmental Protec-
tion  and  Water  Management  (Project  No.  2.14.0100.00.0).
Gypstrend  s.r.o.  and  the  Polish  Oil  and  Gas  Company  gave
permission  to  study  the  Kobeřice  quarry  and  two  borehole
sections, respectively. We thank all colleagues for comments
and  suggestions  during  the  research,  and  A.  Kasprzyk,  O.
Lintnerová and J.M. Rouchy for remarks on the final script of
the paper.

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