GeolCarp_Vol53_No4_257

GEOLOGICA CARPATHICA, 53, 4, BRATISLAVA, AUGUST 2002

257—268

GEOLOGICAL AND ISOTOPIC EVIDENCE OF DIAGENETIC WATERS

IN THE POLISH FLYSCH CARPATHIANS

NESTOR OSZCZYPKO

and ANDRZEJ ZUBER

Jagiellonian University, Institute of Geological Sciences, Oleandry 2a, PL-30063 Kraków, Poland; nestor@geos.ing.uj.edu.pl

Institute of Nuclear Physics, Radzikowskiego 152, PL-31342 Kraków, Poland; zuber@novell.fjt.agh.edu.pl

(Manuscript received June 21, 2001; accepted in revised form December 13, 2001)

Abstract: The origin of CO

-rich chloride waters in the Polish Flysch Carpathians is the subject of controversies. They

often contain a non-meteoric component, with isotopic composition characteristic for dehydration waters released in
metamorphic processes, that is

≅

+6.5 ‰ and

≅

—25 ‰. However, comparison with other known occurrences of

waters of a similar isotopic composition suggests that they mainly result from the transformation of smectites to illities
during the burial diagenesis of flysch sediments. These waters are characterized by high chloride contents (up to about
14 g/l), which differ in different regions, and remain difficult to explain as the

O and

H values are slightly scattered

and do not show any distinct contribution of marine water. It is shown that such waters are also characterized by high
ratios of Na

/Cl

—

and B/Cl

—

, which can be useful in their identification. Particularly interesting waters occur in the four

deepest wells of the Krynica Spa, which undoubtedly contain a non-meteoric chloride component. Their positions on

O-

H diagrams are scattered to the left from a typical mixing line of meteoric waters with dehydration waters, which

makes it difficult to determine their origin. However, they can be regarded as containing different percentages of a
dehydration component because their Cl

—

H relation is linear and similar to typical mixing lines of dehydration waters

with meteoric waters. The untypical positions of these waters on the

O-

H diagram can be explained by isotopic

shifts of

O from a typical mixing line to more negative values, supposedly caused by isotopic exchange of oxygen

between CO

and water. In that process, small volumes of water are involved, as deduced from very slow flow rates in

rocks of a low porosity, and a large amount of CO

, as deduced from very high pressures measured at well heads, and an

eruption of CO

, which occurred during drilling one of the wells.

Key words: Western Carpathians, flysch, burial diagenesis, metamorphic water, diagenetic water, carbon dioxide, chloride
water, hydrogen isotopes, oxygen isotopes.

Introduction

The presence of increased chloride contents in mineral waters
of the Polish Outer Carpatians (POC) was generally thought to
be the remnant of marine sedimentation water (e.g. Dowgiałło
1976). First isotope determinations of CO

rich chloride wa-

ters from Wysowa and several other sites indicated the pres-
ence of water resulting probably from the dehydration of clay
minerals in metamorphic processes (Dowgiałło 1980; Leśniak
1980; Dowgiałło & Leśniak 1980). That hypothesis was based
on the works of White et al. (1973) and Taylor (1974). Howev-
er,  contrary  to  White  et  al.  (1973),  Leśniak  (1980)  and
Dowgiałło  (1980)  assumed  the  dehydration  waters  to  be  by
definition  fresh,  and  the  salt  component(s)  to  result  from  an
admixture of connate water. In some cases, the chloride com-
ponent was related to sedimentation water migrating from Mi-
ocene formations covered by the Carpathian overthrust. That
two-component primary mixing was supposed to take place in
the  past  on  a  regional  scale,  whereas  the  secondary  mixing
with local meteoric water was shown to be a modern process
(Leśniak 1980). A contribution of paleoinfiltration water with
an isotopic composition different than that of the modern pre-
cipitation  was  also  suggested  (Dowgiałło  1980;  Leśniak
1980).  Zuber  &  Grabczak  (1985a,  1986,  1987)  were  critical
about  the  hypothesis  on  the  regional  mixing  of  dehydration
and marine waters, because there are no physical mechanisms
of regional mixing which would yield the same

O—

H val-

ues at different sites with large differences in chloride content.
The similarity of the isotopic composition of dehydration wa-
ters in the POC to dehydration waters known in other world
regions is also difficult to explain by the mixing hypothesis. It
is highly improbable that waters in different regions of the
world mix in such a way that the same isotopic composition is
produced. In addition, for the hypothesis of regional mixing
with marine water, it was necessary to assume the initial

value of the dehydration water to be equal to +25 ‰ (Leśniak
1980; Dowgiałło & Leśniak 1980). Such a high

O value

would require a high-grade metamorphism, as can be deduced
from the isotopic composition of bound water in clay minerals
(Taylor 1974) and from fractionation factors given by Fried-
man & O’Neil (1977). No evidence for either such metamor-
phism or such high

O values exists in the POC.

In the Krynica Spa, four deep wells (670—919 m) withdraw

-rich waters of HCO

—Na type, with increased Cl

—

and

contents. They are called the Zuber waters after the

name of their discoverer, Prof. Rudolf Zuber, or chloride CO

rich waters to distinguish them locally from other CO

-rich

waters with low Cl

—

contents. The Zuber waters were general-

ly thought to be of connate origin mainly due to the presence
of elevated contents of chlorides, the large depths of their oc-
currences, and very low outflow rates (Świdziński 1972;
Pazdro 1983). However, preliminary stable isotope determina-
tions yielded values close to the world meteoric line and far
from the value of SMOW, suggesting a meteoric origin with a

258 OSZCZYPKO and ZUBER

possible  replenishment  (Dowgiałło  1973).  Later  Dowgiałło
(1980) regarded the Zuber waters as the result of three-compo-
nent  mixing  between  connate  water  of  the  flysch  sediments
with the dehydration water of metamorphic origin, later dilut-
ed by very old meteoric water of a distant recharge area. Ac-
cording  to  that  hypothesis,  their  replenishment  ability  was
rather  questioned.  Zuber  &  Grabczak  (1985a,  1986)  were  in
favour of a dominant role of an old meteoric component, with-
out  explaining  the  origin  of  the  elevated  chloride  contents.
Zuber  (1987)  was  in  favour  of  two-component  mixing  be-
tween dehydration and old meteoric waters, with diagenesis as
a possible source of the chloride water component.

Within the present work it will be shown that none of the

above mentioned hypotheses related to the origin of dehydra-
tion waters in the Polish Outer Carpathians (POC) in general,
and to the Zuber waters in particular, was quite correct. The
isotope and hydrochemical data of typical chloride waters in
Poland will be recalled, and against that background the char-
acteristic features of dehydration waters in the POC indicated.
For a more complete comparison, selected examples of well-
known world occurrences of dehydration waters will also be
given. It will be shown that the dehydration of clay minerals in
diagenetic transformations is possible considering the maxi-
mal depths of sediments obtained by the reconstruction of the
burial history of the flysh basin in the Krynica area.

Geological setting

The Polish part of the Outer Carpathians (POC) are mainly

composed of the flysch sediments deposited through the Late
Jurassic to the Early Miocene. They were deposited by gravi-

tational flows in a deep-sea environment. The flysch sequenc-
es  consist  of  sandy-clayey  deposits,  which  derive  from  mar-
ginal  and  intra-basinal  tectonic  lands  intermittently  uplifted
and  eroded.  The  flysch  sedimentation  took  place  in  several
sub-basins,  which  were  transferred  during  the  Late  Eocene
through  to  Early  Miocene  tectonic  movements  into  separate
tectono-stratigraphic  units.  The  POC  were  built  up  from  a
stack  of  nappes  and  thrust-sheets,  completely  uprooted  from
their  basement.  From  the  south  to  the  north  there  are:  the
Magura  Nappe,  the  Fore-Magura-Dukla  group  of  units,  the
Silesian  Nappe,  the  Sub-Silesian  Unit,  and  the  Skole  Nappe
(Fig. 1).

The POC are flatly overthrust onto the Middle Miocene de-

posits of the Carpathian Foredeep. As a consequence, a narrow
zone of folded Miocene deposits developed along the frontal
Carpathian thrust (Fig. 1). The thickness of the Carpathian ac-
cretionary wedge is documented by boreholes and varies from
a few hundred metres at the front of the orogeny to more than
7 km in the Kuźmina-1 borehole (S of Przemyśl). The extent
of  the  Carpathian  overthrust  varies  from  about  60  km  at  the
Kraków meridian (Figs. 2 and 3) to about 100 km at the Kros-
no meridian (Oszczypko 1998). In areas where mineral waters
with a non-meteoric component occur the thickness of the Car-
pathian nappes is as follows: 2.5—3 km in Słona and Bieśnik;
4—4.5 km in Ciężkowice and Sól; 5—6 km in Sidzina, Rabka,
Poręba  Wielka  and  Szczawa;  and  8—10  km  in  Krościenko,
Szczawnica, Złockie, Krynica, Wysowa, Lubatówka, Iwonicz
and Rymanów (Figs. 1 and 2). In Ciężkowice, Poręba Wielka,
Złockie,  Krynica,  Lubatówka  and  Iwonicz  such  waters  were
found only in deep wells (up to about 1000 m), whereas in oth-
er  locations,  they  occur  in  both  springs  and  shallow  wells.
Chloride  waters  rich  in  CO

also outflow at the areas where

Fig. 1. Geology of the Polish Carpathians (after Oszczypko et al. 1999, supplemented). 1 – crystalline core of the Tatra Mts, 2 – High Tatra
and sub-Tatra units, 3 – Podhale flysch, 4 – Pieniny Klippen Belt, 5 – Magura Nappe, 6 – Grybów Unit, 7 – Dukla Unit, 8 – Fore-
Magura Unit, 9 – Silesian Nappe, 10 – Sub-Silesian Unit, 11 – Skole Nappe, 12 – Sambor-Rożniatov Unit, 13 – Miocene deposits upon
the Carpathians, 14 – Zgłobice Unit, 15 – Miocene deposits of the Carpathian Foredeep, 16 – andesites, 17 – area of Krynica Spa, 18 –
cross-section, 19 – occurrences of discussed waters, 20 – state border.

DIAGENETIC WATERS IN THE POLISH FLYSCH CARPATHIANS 259

Fig. 2. Sketched map of the platform basement of the Polish Outer Carpathians (after Oszczypko 1998, supplemented). 1 – Proterozoic ig-
neous rocks, 2 – Lower Cambrian and Vendian slates, 3 – Lower Cambrian, 4 – Devonian to Upper Carboniferous, 5 – Triassic, 6 – Ju-
rassic, 7 – Upper Cretaceous, 8 – depth to magneto-telluric basement, 9 – zero line of Wises vectors, 10 – axis of gravimetric minimum,
11 – southern extent of area recognized by boreholes, 12 – Carpathian overthrust, 13 – faults, 14 – occurrences of discussed waters.

Fig. 3. Deep geological cross-section through the Polish Carpathians. 1 – upper trench, 2 – lower crust, 3 – upper crust, 4 – Paleozo-
ic, 5 – Mesozoic, 6 – Paleogene and Lower Miocene, 7 – Badenian and Sarmatian, 8 – Sub-Silesian and Silesian Units, 9 – Dukla
and Grybów Units, 10 – Siary and Rača Subunits of Magura Nappe, 11 – Bystrica Subunit of Magura Nappe, 12 – Krynica Subunit of
Magura Nappe, 13 – Pieniny Klippen Belt, 14 – Vahicum, 15 – Tatricum, 16 – Fatricum, 17 – Podhale flysch, 18 – high resistivity
basement (after Żytko 1997), 19 – low-resistivity horizon (after Żytko 1997), 20 – isotherms, 21 – faults and overthrusts, 22 – bore-
holes, 23 – CO

ascension, M – Moho, KD – Krynica dislocation.

260 OSZCZYPKO and ZUBER

the present thickness of flysch sediments is not more than 3
km (springs in Słona and Bieśnik, artesian deep well in
Ciężkowice, see Fig. 2).

Numerous andesite dykes and sills occurring in the Czorsz-

tyn-Szczawnica area at the front of the Pieniny Klippen Belt
(Fig. 1) cut the Upper Cretaceous-Paleogene rocks of the
Magura Nappe (Birkenmajer 1986). These small intrusions are
of Middle Miocene age, 11—13 Ma (Birkenmajer & Pécskay
1999), and were formed in the course of the Late Badenian/
Sarmatian subduction event. During the post-Sarmatian under-
plating of the European Platform beneath the Slovak-Pannon-
ian Block, these andesites were probably uprooted from their
basement. According to some opinions the CO

occurrence in

Szczawnica could be related to the presence of the andesite
dykes, suggesting its mantle origin. However, both the uproot-
ing of the intrusions and the hydrochemistry of mineral waters
in Szczawnica, which show no relation to andesites (Leśniak
1998), contradict that hypothesis.

The basement of the POC represents the epi-Variscan plat-

form and its cover (Fig. 2). The magneto-telluric soundings in
the POC revealed a high resistivity horizon (Fig. 3) at the top
of  the  consolidated-crystalline  basement  (Ryłko  &  Tomaś
1995;  Żytko  1997).  On  the  Bochnia-Krynica  geotravers  the
magneto-telluric  basement  is  inclined  to  the  south  from  the
depths  of  5—6  km  in  the  northern,  marginal  part  of  the  Car-
pathians, to the depths of 10—12 km south of Nowy Sącz. The
depth of the Krynica basement varies from 15 to 20 km, and
rises to 8—10 km at the Polish-Slovak boundary (Figs. 2 and
3). The magneto-telluric soundings also reveal a low resistivi-
ty zone (0.5—4.0 ohm), which is located south of the gravity
minimum. In the Krynica area, this zone has the thickness of
about 2.5—3 km and is located in two buried grabens, a few km
above the consolidated basement (Fig. 3). According to Jan-
kowski et al. (1985), the low resistivity anomaly indicates the
occurrence  of  highly  mineralized  waters  at  great  depths,
whereas according to Żytko (1997) it results from the graphiti-
zation  on  the  contact  between  the  North  European  Plate  and
the Slovak Microplate.

A similar anomaly was found at depths of 10—20 km be-

neath the Island of Taiwan, and was supposed to correlate with

the inferred depth of dehydration reactions at the top of the
aseismic lower crust (Chen & Chen 1998).

The Krynica Spa is located in the south-eastern part of the

Magura Nappe at the boundary between the Bystrica and
Krynica Subunits (Figs. 1 and 4). The Bystrica Subunit is built
up of the Middle to Upper Eocene Magura Formation (Figs. 4
and 5). The Magura Formation consists of thick-bedded sand-
stones (Maszkowice Member), variegated shales and thin-bed-
ded turbidites (Mniszek Member), and the Poprad Sandstone
Member known only from the deep boreholes (Zuber I—IV).
The Krynica Subunit is composed of Upper Cretaceous to Up-

Fig.  4.  Geological  map  of  the  Krynica  area  (after  Oszczypko  et  al.
1999). Krynica Subunit: 1 – Szczawnica Formation, 2 – Zarzecze
Formation, a – Krynica Sandstone Member, 3 – Magura Formation,
Piwniczna  Sandstone  Member;  Bystrica  Subunit:  Magura  Forma-
tion,  4  –  Maszkowice  Sandstone  Member,  5  –  Mniszek  Shale
Member,  6  –  Poprad  Sandstone  Member,  visible  only  in  the  cross-
section, 7 – Pleistocene, 8 – faults, 9 – cross-section, 10 – select-
ed boreholes.

Fig. 5. Geological cross-section (after Oszczypko et al. 1999). Krynica Subunit: 1 – Szczawnica Formation, 2 – Zarzecze Formation,
a – Krynica Sandstone Member, 3 – Magura Formation, Piwniczna Sandstone Member; Bystrica Subunit: Magura Formation, 4 –
Maszkowice Sandstone Member, 5 – Mniszek Shale Member, 6 – Poprad Sandstone Member, 7 – faults, 8 – selected boreholes,
KD – Krynica dislocation, TD – Tylicz dislocation.

DIAGENETIC WATERS IN THE POLISH FLYSCH CARPATHIANS 261

per Eocene deposits (Birkenmajer &   Oszczypko 1989; Osz-
czypko et al. 1999). The oldest deposits are known from the
Muszyna-Zlockie area, 5 km west of Krynica. They consist of
the  Turonian-Maastrichtian,  deep-water  variegated  shales
(Malinowa  Formation)  with  sporadic  intercalations  of  thin-
bedded  sandstones  (Oszczypko  et  al.  1990).  That  formation
passes upwards into strongly tectonized, medium to thin-bed-
ded turbidites of the Paleocene and Lower Eocene (Szczawni-
ca  Formation),  which  are  rich  in  calcite  veins  (Figs.  4,  5).
Higher up in the succession, thin-bedded turbidites occur, with
intercalations  of  thick-bedded  sandstones  and  conglomerates
of  the  Lower-Middle  Eocene  (Zarzecze  Formation).  In  the
Krynica Spa the youngest deposits of the Krynica Subunit be-
long to the thick-bedded sandstones of the Magura Formation
(Middle-Upper  Eocene).  The  stratigraphic  thickness  of  the
Magura  Nappe  reaches  at  least  2.6  km.  During  overthrust
movements and tectonic repetitions, the total thickness of the
flysch  deposits  in  the  Krynica  Subunit  increased  up  to  5.5—

7.5 km, as is shown by magneto-telluric investigations
(Fig. 3). The Bystrica and Krynica Subunits contact along the
sub-vertical thrust fault, which dips to NE (Figs. 4 and 5).
Three NE-SW trending transversal faults cut both the Bystrica
and Krynica Subunits into several blocks.

The Late Cretaceous to the Upper Eocene flysch formations

of the Krynica succession were deposited in a deep-water ba-
sin (Oszczypko 1992). Since the Early Eocene, in the southern
part of the Magura Basin the sedimentary processes were ac-
companied by the growth of the accretionary wedge (Osz-
czypko 1999). Gradual shallowing of the basin started during
the Late Eocene. This was followed by the folding and uplift-
ing of the basin after the Late Oligocene—Early Miocene, and
prior to the Late Miocene.

The Late Cretaceous-burial history of the Krynica succession

of the Magura Basin has been reconstructed using the proce-
dures developed by Angevine et al. (1990) and Allen & Allen
(1992). The subsidence plot (Fig. 6) shows the fluctuation of pa-

Fig. 6. Backstripped burial diagram of the Krynica succession of the Magura Basin (partly after Oszczypko 1999). 1 – basinal and hemi-
pelagic deposits, 2 – pelagic marls, 3 – thin-bedded turbidites, 4 – thick-bedded turbidites, 5 – eroded part of section (minimal
amount), 6 – paleobathymetry, 7 – tectonic subsidence, 8 – strata with mineral waters.

262 OSZCZYPKO and ZUBER

leobathymetry and tectonic subsidence (see also Oszczypko
1999). During the Middle Eocene time the basal portion of the
Krynica succession could have been buried at a depth of 6 km
beneath the sea level with temperatures of 150—200 °C and pres-
sures of about 100 MPa. The present temperatures at the base of
the Magura Nappe in the Krynica area are probably similar to
those of the Krynica succession during the maximal burial (Fig.
3), whereas the pressures are probably higher (120—160 MPa).
The Krynica Subunit probably covers relatively younger sedi-
ments of the Dukla—Grybów Units. These deposits may per-
haps still undergo dehydration processes.

Contrary to other tectonic units of the Outer Carpathians,

the  Magura  Nappe  is  free  of  hydrocarbons  (Karnkowski
1999). Only traces of hydrocarbons were discovered in the sa-
line  fluid  inclusions  of  the  quartz  overgrowths  in  the  Szcza-
wnica  Formation  (Świerczewska  et  al.  1999).  This  suggests
that  Magura  Nappe  deposits  were  buried  beneath  the  lower
limit of the main oil generation zone (oil window), with labile
kerogen cracked to gas at the temperature exceeding 150  °C
(compare Allen & Allen 1993).

The burial depths of the Magura Nappe deposits was proba-

bly greater than those of the more external units as it can be as-
sumed from a higher illite to smectite ratio in the Magura
Nappe (Dudek & Świerczewska 2001). According to the latter
studies the Magura Nappe deposits were affected by the strong
diagenesis at temperatures higher than 165 °C in the middle
part and about 120—165 °C in other areas of the unit. The ad-
vanced diagenesis of the Oligocene deposits of the Grybów—
Dukla Units exposed in the tectonic windows in the Magura
Nappe was also reported (Dudek & Świerczewska 2001).

The present temperatures at the base of the flysch nappes

vary from about 100 °C in the Bochnia area to about 300 °C in
the Krynica area (Fig. 3), as deduced from the geothermal gra-
dient of 26

°C/km (Leško et al. 1987).

Hydrogeological setting

Mineral waters discussed within the present work are locat-

ed  along  two  belts  in  the  Silesian  and  Magura  Nappes.  The
mineral waters of the Silesian Nappe area occur in the follow-
ing  locations:  Słona,  Bieśnik,  Ciężkowice,  Lubatówka,
Iwonicz, and Rymanów (Fig. 1). The occurrences of mineral
waters  in  the  Magura  Nappe  can  be  subdivided  into  two
groups.  Waters  of  Szczawa,  Poręba  Wielka,  Rabka,  Sidzina
and  Sól  are  strongly  related  to  the  tectonic  windows  of  the
Dukla—Grybów  Units,  whereas  the  waters  of  Szczawnica,
Krościenko, Złockie, Krynica and Wysowa occur in the south-
ern, deep-seated part of the Magura Nappe (Figs. 2, 3 and 5).

In the southern part of the Magura Nappe, abundant carbon

dioxide occurrences are observed in both mineral waters and
dry exhalations. As discussed further, these CO

occurrences

are supposed to result from the thermal decomposition of car-
bonate rocks, which begins at temperatures of 185—190 °C
(Mason 1990). The migration of dehydration waters and CO

to the surface is enhanced by numerous faults. The upward
flow of water results from pressures higher than hydrostatic.
No changes in the flow rates of dehydration waters and CO

are observable. Therefore, their supply can be regarded as con-
stant in terms of human generations.

In the Krynica Spa particularly favourable conditions exist

for the relatively deep penetration of meteoric waters due to
many faults and strong folding of the Szczawnica Formation
(Paleocene to Lower Eocene, see Figs. 4 and 5). Most proba-
bly the faults also play a dominant role in the migration of CO

and dehydration waters to the surface. A large amount of CO

is also trapped in the Poprad Sandstone Member of the Magu-
ra Formation at the depths of 400—1000 m at the tectonic con-
tact of the Bystrica and Krynica Subunits (Fig. 5). In 1938
there was a strong eruption of CO

during the drilling of the

Zuber II well at the depth of 950 m (Świdziński 1972). In the
Krynica area, during the post-nappe time, the long-lasting in-
teraction (around 10 Ma, see Oszczypko 1998) between CO

rich waters and rocks caused dissolution of the sandstone ce-
ment and an increase of the porosity of sandstones in
comparison with other areas. This can be observed in the ex-
posures, where the sandstones and conglomerates of the
Krynica Member are weakly consolidated or fully disintegrat-
ed to sands and gravels (Oszczypko et al. 1999).

Isotope and chemical data of selected waters of

dehydration origin

The typical isotopic composition of CO

-rich chloride wa-

ters from several spas in the POC is shown in Fig. 7. The theo-
retical ranges of the isotopic composition of metamorphic wa-
ters given in Fig. 7 are taken from Taylor (1974) and Kerrich
(1987), though Sheppard (1986) reports somewhat wider val-
ues to include possible occurrences of dehydration waters of
the oceanic crust. CO

-rich dehydration waters also occur in

Slovakia, though to the best knowledge of the authors, their
end members with

≥

+5.5 ‰ have not been found so far

in that country. However, on the basis of similarity of the Slo-
vak waters to those of the Pacific tectonic belt of the west
coast of the United States, Barnes & O’Neil (1976) thought
that they contained a metamorphic component.

The Cl

—

O relationships for waters shown in Fig. 7 are

given in Fig. 8 (similar relations exist for Cl

—

H). As men-

tioned above, in spite of similar isotopic composition of the
dehydration component, highly different Cl

—

contents are ob-

served in different regions, which is difficult to explain by any
mixing hypothesis.

In Table 1 chemical and isotope data of selected mineral wa-

ters are given. The first group represents examples of the non-
Carpathian  waters,  which  are  supposed  to  be  of  dehydration
origin.  The  second  group  represents  similar  waters  from  the
POC. The third group represents chosen examples of oil-field
waters in the Polish Carpathians, which most probably contain
a  dehydration  component.  The  next  three  groups  represent
mineral waters of different origin in Poland. They are given to
demonstrate typical differences from dehydration waters both
in isotopic composition and hydrochemistry. An example from
Krosno is also included just to demonstrate the occurrences of
chloride  waters  of  other  origin  in  the  POC.  The  last  group
(VII)  represents  the  chloride  waters  of  Krynica,  called  the
Zuber  waters,  which  are  supposed  to  contain  different  frac-
tions of a dehydration component as shown further.

In the California Coast Ranges, White et al. (1973) regarded

as metamorphic waters only those with a relatively low Cl

—

DIAGENETIC WATERS IN THE POLISH FLYSCH CARPATHIANS 263

content (up to about 700 mg/l) in the end component (Sulphur
Bay Springs, see Table 1). In spite of the same isotopic com-
position, waters from Wilbur Springs, with Cl

—

content close

to 10,000 mg/l were supposed to be related to marine waters
diluted by ancient meteoric waters. Following White et al.
(1973) and Taylor (1974), waters with their end component
close to about

O = +6 ‰ and

H = —25 ‰ are often re-

garded as being of metamorphic origin (e.g. Sheppard 1986;
Kerrich 1987). However, contrary to these opinions, in an ex-
cellent  review,  Longstaffe  (1987)  indicates  the  possibility  of
diagenetic origin for such waters. That opinion is mainly based
on the results of Yeh & Savin (1976, 1977), and Yeh (1980),
obtained for samples taken from deep drill cores of shales and
mudstones in the Gulf Coast, and of Suchocki & Land (1983)
for samples from the Great Valley sequence in northern Cali-
fornia.  Findings  of  these  authors  can  be  summarized  as  fol-
lows.  The  dehydration  of  argillaceous  units  mainly  results
from the transformation of smectite to illite during burial di-
agenesis at depths of about 3—6 km. Most probably the late-
stage dehydration of smectite to illite buffers the oxygen and
hydrogen  isotope  composition  of  the  formation  water  from
that similar to seawater (0 ‰) at shallow depths to values of

about  +7  ‰  and  —25  ‰,  respectively,  at  large  depths.  The
buffering  mainly  results  from  dehydration  and  isotopic  ex-
change,  and  perhaps  also  from  membrane  filtering  effects
when pore water is pushed out upwards by dehydration water.
The dehydration leads to dilution of the pore waters whereas
the membrane effects cause the enrichment of the residual wa-
ter in dissolved constituents as Kharaka & Berry (1973) report.
Water-rock  interaction  undoubtedly  also  leads  to  the  enrich-
ment  in  dissolved  constituents,  especially  in  the  presence  of
CO

. In the case of smectite-illite transformation, modelling of

formation water in temperatures from 75 to 175

°C yields the

O values from about +5 ‰ to about +9 ‰ (Suchocki &

Land 1983; Longstaffe 1987). As no isotopic signatures of the
original pore waters (marine or meteoric) are preserved, the fi-
nal formation water can be regarded as being of dehydration
origin. Dehydration waters resulting from diagenesis or meta-
morphic processes are called within this work diagenetic and
metamorphic waters, respectively.

Dehydration waters should not be regarded as free of chemi-

cal components because during the smectite illitization not
only large amounts of water and OH

—

groups, but also Na

, Mg

and other ions are released (Boles & Franks 1979).

In clay minerals Cl

—

, Br

—

, and I

—

occupy some positions of OH

—

ions, and most probably they can also be released. As a conse-
quence, diagenetic waters are mineralized even if the chemical
components of the original pore water are not preserved. In
any case, the illitization process contributes to the hydrochem-
istry of diagenetic waters, and high Na/Cl ratios can be expect-
ed. In fact the molar ratio of Na

to Cl

—

is larger than 1 for

chloride waters of diagenetic origin, and can serve as a criteri-
on helpful in the identification of such waters (see Table 1).
However, caution is needed because that criterion is not unam-
biguous as values somewhat larger than 1 can also be observed
for chloride waters resulting from leaching of salts (see exam-
ples of the V group in Table 1). The weight ratio of B to Cl

—

shown in Table 1 also seems to be a useful criterion for the
identification of chloride waters of diagenetic origin. Its value
is larger than 2 ‰ in the case of dehydration waters, and usual-
ly below 2 ‰ in other cases. Most probably some amount of
boron is also released in the smectite to illite transformation.

In spite of large differences in chemical composition, espe-

cially in Cl

—

content, all the waters regarded within this work

as being of dehydration origin have similar isotopic composi-
tion  of  the  non-meteoric  end  members  (Table  1  and  Fig. 7).
These  end  members  fall  within  the  ranges  of  the  theoretical
isotopic  composition  of  metamorphic  waters,  and,  as  shown
above,  are  also  typical  for  waters  released  during  burial  di-
agenesis of clay minerals. Such waters also include mixed wa-
ters from the South German Molasse Basin, with the non-me-
teoric  end  member  represented  by  water  from  Bad  Endorf
(Table 1),  which  results  from  diagenesis  of  shales  (Stichler
1997). Similarly, no evidence of any regional metamorphism
has been found in the POC (deep borehole Kuźmina 1), even
at  depths  of  up  to  6842  m  (Żytko 1989).  However,  as  men-
tioned  above,  deep  geomagnetic  soundings  performed  in  the
Western Carpathians suggest the presence of highly mineral-
ized waters in a belt related to two deep grabens seen in Fig. 3.
Therefore,  the  presence  of  metamorphic  processes  at  large
depths  cannot  be  excluded,  though  it  is  not  regarded  as  the
main source of the discussed waters.

Fig. 8. Cl

—

O relations for selected Carpathian sites showing the

mixing of dehydration and local meteoric waters in springs or
shallow wells. Note distinctly different Cl

—

contents of the end

members.

Fig. 7. Isotopic composition of selected Carpathian dehydration wa-
ters mixed with local meteoric waters. Note similar compositions of
end members. Regional infiltration line after Ciężkowski & Zuber
(1995).

Table

Major

and

selected

minor

components

and

the

isotopic

compositio

selected

examples

highly

mineralized

waters

comparis

with

the

Zuber

waters

Krynica

Spa

(except

for

the

samples

group

Połczyn

and

Krosno

all

the

other

data

based

several

determinations

characterized

low

scatter

s).

TE,

LL o

SPR

mg/

‰

I gr

e o

f end co

nts

non-

pat

hia

n de

n water

ain

ilb

8500

440

9700

390

7130

1255

+5.

-2

phur

, I

nk Sp

-2

phur

, Ge

Spr

ing

1190

644

598

3290

2510

963

+3.

-2

ad E

ndor

7286

239

8732

12.

372

385

150

+5.

-1

up.

nd co

nts

f s

llo

w C

pat

hia

n de

n water

wa,

Ale

ndr

a we

6900

314

3850

13110

990

1690

+6.

-3

Szczawni

ca, Magda

7500

125

111

241

5886

race

11850

753

890

+5.

-3

Szczawa, S

zczawa I

I wel

7670

116

430

6524

11532

528

1740

+6.

-3

abka,

18 well

9300

13852

race

1525

395

+6.

-2

III

arpa

thi

il-

ith

uppos

n c

icz, L

ubat

ów

6470

7938

4132

308

-28

icz, L

ubat

ów

6250

7850

3713

142

139

-32

anów,

tyn

a s

ing

2745

3608

1600

190

1030

-5

-6

anów,

a s

ing

2565

176

3563

1525

176

790

-5

f connate water

e M

ioce

ne ocean

ębow

iec,

D-

7 well

14900

110

1616

715

28106

170

116

149

bł

, T

ade

z well

17100

110

1908

863

32534

184

103

142

-1

rou

xam

Mat

eczny

, wel

l M-

318

142

134

346

794

366

-10.

-78

ko,

ll 16

4250

110

401

243

6431

1944

422

-9

-6

f pr

ter

eteor

water

s a

nd water

s o

ear

igin

ko,

ll 15

7750

155

305

379

12800

930

628

-6.

-52

oń

, w

l U

-3

22400

405

7791

2410

55593

293

380

122

-1.

-22

Gocza

łk

ice,

well

-1

23250

245

4104

1557

47994

248

117

-1.

-17

cho

l X

14500

155

1292

470

25978

365

-6.

-49

amie

ń P

i, E

ard

12400

667

260

20913

130

317

-8.

-58

łc

ell

-1

24400

3178

848

43323

192

3245

-3.

-26

16350

413

190

25734

1472

-13

I g

up.

uber

water

s in

rynica

r II

4380

170

190

750

247

15957

2574

-9

-7

er I w

ell

5700

200

201

480

734

17364

2223

-7.

-63

er IV

ell

6425

265

221

495

870

112

19600

2240

-8.

-55

er I

II w

ell

7000

325

208

378

1136

19965

2061

-6.

-56

White et al

. (

1973

);

hler

(

199

; c)

data a

fter

ocka (

1976)

; d)

ope data af

ter

ięż

kows

et al

. (

pub

lis

hed

);

& Z

uber

(

95)

;

ube

r et al

. (

1997

);

) Dow

ałł

o (

80)

;

uber

& G

rab

czak (

1991

);

, no

t r

264 OSZCZYPKO and ZUBER

DIAGENETIC WATERS IN THE POLISH FLYSCH CARPATHIANS 265

All the non-meteoric end members are free of tritium even

in the cases of shallow occurrences (e.g. in Wysowa, Szcza-
wnica,  Szczawa  and  Rabka),  whereas  waters  situated  along
the  mixing  line(s)  with  meteoric  infiltration  (Figs. 7  and  8)
usually contain tritium above the detection limit of about 0.5
T.U. That mixing between ascending dehydration waters and
modern  meteoric  waters  is  a  local  effect,  and  usually  takes
place close to the ground surface.

The dehydration origin of waters cannot be deduced only on

the basis of their isotopic composition but the geology of the
area  and  the  hydrochemistry  must  also  be  considered.  Other
waters  with  their  end  members  falling  within  the  ranges  of
metamorphic waters shown in Fig. 7 are also quite common in
different regions of the world. Their discussion is beyond the
scope  of  the  present  work  because  they  are  often  associated
with oil fields or thermal waters, and their origin is either more
complex than just dehydration, or they were subject to second-
ary changes.

Mineral waters of the Krynica Spa

The mineral waters of meteoric origin in Krynica are of the

HCO

—Ca, HCO

—Ca—Mg and HCO

—Mg—Ca types. Waters

discharging from several springs and withdrawn from wells up
to about 200 m deep contain tritium. Waters withdrawn from
wells deeper than about 200 m are tritium free and in some cases
have

O and

H values distinctly more negative than the av-

erage values of waters rich in tritium, that is

≅

—10.5 ‰

and

≅

—75 ‰. These distinctly more negative delta values

are characteristic for waters in wells about 400 m deep. They do
not result from the local altitude effect, because their

O and

H values are more negative than the values found in springs

and dug wells at high altitudes (Zuber et al. 1999). Therefore,
waters with the most negative delta values are most probably of
glacial age, or contain a significant glacial component. Radio-
carbon dating and noble gas temperatures cannot support that
finding due to high contents of dead CO

Therapeutic waters withdrawn from the four deepest wells

with flow rates of 0.8—3.5 m

/day distinctly differ chemically

and isotopically from other waters in Krynica, and, as men-
tioned, they are called the Zuber waters. Their isotope data
neither indicate a common origin, nor fit to a typical mixing
line of dehydration waters as seen in Fig. 9. However, a con-
sistent picture is obtained when the relationship between the
two most conservative water components is considered, that is
between Cl

—

and

H, as shown in Fig. 10. In such a case it is

possible to draw a straight mixing line which fits the data for
the Zuber waters reasonably well. The dehydration end mem-
ber of that line is assumed to correspond to the highest Cl

—

content in the Krynica area, which was measured in water tak-
en from the B-1 well during drilling (Świdziński 1972). The
isotopic composition of water from that well was not mea-
sured, but under the above assumption the mixing line shows
the

H value of about —30 %, which is equal to the value of

the end member in nearby Wysowa. The mixing line shown in
Fig. 10 can serve for determining the contributions of the de-
hydration and meteoric components to the Zuber waters in
each well. Chloride contents yield the following fractions of

the dehydration water: 0.09, 0.26, 0.34 and 0.41, for Z-II, Z-I,
Z-IV and Z-III wells, respectively. The fractions of the dehy-
dration water determined from the

H values are 0.08, 0.27,

0.43, and 0.41, respectively. Both methods yield practically
the same results except for Z-IV well, as discussed below.

The initial point of the Cl

—

H mixing line corresponds to

the  mean  isotopic  composition  of  hydrogen  in  local  Ho-
locene  waters,  that  is  about  —75  ‰.  However,  due  to  very
low  outflow  rates,  high  mineralization,  and  depths  larger
than the depths of glacial waters, the meteoric member of the
Zuber  waters  cannot  be  of  the  Holocene  age.  As  a  conse-
quence,  an  interglacial  age  can  be  supposed  for  that  water.
Water from the Zuber IV well does not fit the mixing line of
three  other  wells  very  well  and  seems  to  have  a  meteoric
component  with  somewhat  heavier  isotopic  composition,
that  is

≅

—65 ‰ (see Fig. 10). That value suggests an

even greater age of the meteoric component because it corre-
sponds to recharge in a pre-Quaternary warm climate. Such
pre-Quaternary meteoric waters of the last hydrologic cycle
have been found in several regions of Poland (Ciężkowski et

Fig. 10. Cl

—

H relations for the Zuber waters and water from

abandoned B-1 well for which the Cl

—

content is assumed to repre-

sent  the  dehydration  end  member.  The  isotopic  composition  was
not  measured,  but  the  mixing  line  of  the  Zuber  waters  suggests  a
value  close  to  that  of  Alexandra  well  in  nearby  Wysowa.  Boxes
represent the scatter of data obtained in different years.

Fig. 9. Isotopic composition of waters exploited in Zuber wells in
comparison with the non-chloride CO

-rich waters of Krynica Spa.

266 OSZCZYPKO and ZUBER

al. 1989; Zuber & Grabczak 1985b; Zuber et al. 1997). If a
separate mixing line is assumed for the Z-IV well, the frac-
tion of dehydration water is about 0.34.

The shifts of the Zuber waters from the mixing line of dehy-

dration and meteoric waters seen in Fig. 9 can be explained by
isotopic exchange of oxygen between large amounts of CO

and small volumes of water. Carbon dioxide released from car-
bonate rocks of marine origin is characterized by

O values

of about 0 ‰ in the PDB notation, which corresponds to about
+30 ‰ in the SMOW notation (Gat & Gonfiantini 1981). For

O, the fractionation enrichment between CO

and water at

the temperature of about 10

°C is —43.5 ‰ (Friedman &

O’Neil 1977). Therefore, a small quantity of water affected by
a continuous flow of CO

will have a tendency to change the

isotopic composition of oxygen to be in equilibrium with CO

that is to —13.5 ‰. The process of exchange is very fast and
takes only several hours (Gat & Gonfiantini 1981). A large
amount of CO

is indicated by high pressures of CO

, which

are from about 2.1 to 3.2 MPa at closed well heads. Therefore,
in the case of the Zuber waters, the masses of through-flowing
CO

and water are probably comparable, and the isotopic shift

of oxygen in water is observed.

The origin of CO

in Krynica was also a subject of controver-

sies. In the past, the most common opinion related its origin to
volcanic processes (Świdziński 1972). A similar opinion was
expressed by Cornides & Kecskés (1982) on the basis of

C(CO

) measurements for CO

-rich waters in Slovakia. In

general, the distinction between the mantle (volcanic) and crust-
al (metamorphic) CO

is difficult due to overlapping ranges of

C values (e.g. Deines 1980), and the evolution of the isotopic

composition of CO

during its migration through groundwater

reservoirs (Leśniak 1998). However, as

C(CO

) in the Zuber

wells is about —1 ‰ (Leśniak 1985, 1988), the origin of CO

can be related to the thermal decomposition of carbonate miner-
als in the presence of SiO

(Maxwell & Sofer 1982). The carbon

dioxide is probably derived from the Mesozoic and Paleozoic
rocks of the platform basement and partly from the Paleogene
and Lower Miocene autochthonous clastic deposits (Oszczypko
1998). The small amount of mantle helium found in all the in-
vestigated CO

-rich waters of the POC (Leśniak et al. 1997) in-

dicates that some contribution of the mantle CO

is perhaps pos-

sible. However, that contribution, if any, cannot be regarded as
significant.

The Zuber waters are chemically unique as indicated by data

given in Table 1. Unusually high molar ratios of Na

to Cl

—

compensated by high concentrations of HCO

ions, are char-

acteristic for the Zuber waters. For these waters, the Na/Cl ra-
tio is evidently independent of the fraction of diagenetic water
(see Table 1 and Fig. 10). Therefore, high concentrations of
Na

probably result from a secondary process related to both

components. The decomposition of albite can be supposed as
the process responsible for increased Na

concentration,

though the albite presence is not reported from the Paleocene
deposits of the Krynica Subunit, whereas the amount of K-
feldspars accounts for 9.5 % (Bromowicz 1986). However,
that hypothesis is weak because the deepest non-chloride wa-
ters in Krynica, with T.D.S. values reaching about 10 g/l, are
of the HCO

-Ca-Mg type, without an indication of unusually

high Na

contents. Therefore, the origin of very high Na

con-

tents in the Zuber waters remains unclear.

Conclusions

In the Polish Outer Carpathians there are common occur-

rences of CO

-rich and CO

-free chloride waters of non-mete-

oric  origin  as  deduced  from  their  isotopic  composition.  In  a
number  of  areas  these  waters  migrate  to  the  surface  due  to
pressures higher than hydrostatic, and mix with local meteoric
waters  yielding  similar  mixing  lines  on

O-

H diagrams.

The mixing lines start at the mean isotopic composition of lo-
cal meteoric waters, that is

≅

—10.2 ‰ and

≅

—72 ‰,

and end at the values characteristic for dehydration waters,
that is

≅

+6.5 ‰ and

≅

—25 ‰ (Fig. 7). Mixing lines

on Cl

—

O (Fig. 8) and Cl

—

H diagrams usually distinctly

differ; they are characteristic only for small areas (a spa or vil-
lage). According to numerous authors (White et al. 1973; Tay-
lor 1974; Leśniak 1980; Sheppard 1986; Kerrich 1987), such
waters can be regarded as being released from clay minerals
during metamorphism, with high Cl

—

contents related to the

remnants of marine water. However, it is difficult to explain
the same isotopic composition and highly different Cl

—

con-

tents for assumed mixing with marine water. It is more reason-
able to follow Yeh & Savin (1976, 1977), Yeh (1980), and Su-
chocki  &  Land  (1983),  who  investigated  two  active  burial
basins  in  the  USA,  and  whose  results  were  summarized  by
Longstaffe  (1987).  These  authors  showed  that  the  release  of
bound  water  and  buffering  effects  during  smectite  to  illite
transformation  during  the  burial  diagenesis  lead  to

O and

H values similar to those regarded as being of metamorphic

origin. The POC geology and the reconstructed burial history
show the possibility of a common existence of diagenetic wa-
ters and rather exclude the existence of metamorphic waters.
Similarly, chloride waters in the Tertiary Molasse Basin of
South Germany, isotopically described by Stichler (1997) can
be related to the burial diagenesis.

Smectite illitization is not necessarily an important process in

burial diagenesis. The study of pore fluid evolution in the Kim-
meridge Clay Formation (mudstone sequence deposited by epi-
continetal sea across north-west Europe during the end of Juras-
sic) showed that other pore waters can also be expected than
those presented within the present work (Scotchman 1993).

The origin of chloride waters of the Na-HCO

type in

Krynica is particularly difficult to determine because their iso-
tope data do not fall on a typical

O-

H mixing line of de-

hydration and meteoric waters in the POC. However, the Cl

—

H relationship is typical for dehydration waters, which

suggests that the Zuber waters can be regarded as those result-
ing from mixing between meteoric and diagenetic waters, with

O shifted to more negative values by isotopic exchange be-

tween large quantities of CO

and small volumes of water. In

Krynica, contrary to other regions, mixing between meteoric
and diagenetic waters takes place at relatively large depths
(500—1000 m) where slowly penetrating meteoric waters of
great ages (interglacial) meet with ascending dehydration wa-
ters. That mixing and the long-lasting action of large quantities
of CO

supposedly lead to the unique chemical composition of

the Zuber water and high T.D.S. contents of about 30 g/l.

It is demonstrated that high Na/Cl and B/Cl ratios are char-

acteristic for waters supposed to be released from clay miner-
als during burial diagenesis. These ratios can be helpful in the
identification of diagenetic waters.

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