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Isotopic evidence of the origin of mineralized waters from the Central Carpathian Synclinorium, SE Poland

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Environmental Geology

Abstract

Stable isotopes of hydrogen and oxygen were determined in 45 samples of water (27 samples of oil-associated waters, 17 samples of mineral waters used by spas, 1 sample of surface river water) from the Central Carpathian Synclinorium, covering a stratigraphic range of flysch sediments from Upper Cretaceous to Oligocene. Moreover, oxygen isotope compositions of authigenic calcite (vein and cement) from core samples of four boreholes were made to evaluate isotopic equilibrium between waters and diagenetic carbonates as a function of temperature. The saline and brackish waters (TDS from≅1 g/l to 48.9 g/l) considered here, generally belong to four hydrogeochemical classes: Na-Cl, Cl-HCO3-Na, HCO3-Cl-Na and HCO3-Na. Their isotopic composition causes them to fall to the right of Global Meteoric Water Line (GMWL) showing enrichment in 18O and 2H. On the other hand, relative to Standard Mean Ocean Water (SMOW) they are depleted in 2H and both depleted and enriched in 18O. The observed isotopic composition can be explained by the three-component mixing of surface water, diagenetically modified sea water (kind of connate water) and metamorphic water. The mixing is accompanied by an exchange of oxygen isotopes between water and carbonate cements causes 18O enrichment of interstitial waters. The contribution of isotopic exchange between water and clay minerals in shales was evaluated only theoretically basing of the literature.

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References

  • Ciężkowski W, Zuber A (1995) Stable isotopes of oxygen and hydrogen in shallow groundwaters in the central part of the Polish Carpathians. In: Szczepańska J, Kulma R, Szczepański A (eds) Współczesne problemy hydrogeologii, Wydawnictwo Profil, Kraków, Vol. 7, pp 245–250 (in Polish only)

  • Chowaniec J (1991) Hydrogeologia. In: Malinowski J (ed) Budowa geologiczna Polski. Wydawnictwa Geologiczne, Warszawa, VII pp 204–214 (in Polish only)

  • Coleman ML, Shepherd TJ, Durham J J, Rouse JE, Moore GR (1982) Reduction of water with zinc for hydrogen isotope analysis. Analytical Chemistry 54:993–995

    CAS  Google Scholar 

  • Craig H (1961) Isotopic variations in meteoric waters. Science 133:1,702–1,703

    Google Scholar 

  • Dowgiałło J (1973) The results of the oxygen and hydrogen isotopic composition of groundwaters in south Poland. Biuletyn Instytutu Geologicznego 277:319–334 (in Polish, English abstract)

    Google Scholar 

  • Dowgiałło J (1976) Problems of the origin of Cl-HCO3-Na mineral waters of the Polish flysh Carpathians. In: Ćadek J, Paćes T (eds) Proceedings of the International Symposium on Water-Rock Interaction, Czechoslovakia (1974), Geological Survey, Prague, pp 12–22

  • Dowgiałło J (1980) Poligenetic model of Carpathian chloride waters and some of its consequences. In: Współczesne Problemy Hydrogeologii Regionalnej. Uniwersytet Warszawski, Warszawa, pp 275–290 (in Polish only)

  • Dowgiałło J, Sławiński A (1979) Remarks on the origin of saline ground waters at Rabka (West Carpathians). In: Słowańska B, Pakulska Z (eds) Hydrogeochemistry of mineralized waters. Proceedings of the IAH Conference of Cieplice Spa (Poland), 1978. Geological Institute, Warsaw, pp 195–203

  • Dowgiałło J, Leśniak PM (1980) The origin of chloride waters in the Polish flysch Carpathians. In: Hitchon B (ed) Proceedings of the 3rd International Symposium on Water-Rock Interaction, Canada, Edmonton pp 20–23

  • Drever JI (1997) Isotopes. In: The geochemistry of natural waters. Prentice-Hall Inc., Upper Saddle River, NJ, pp 311–326

  • Dziadzio P, Baszkiewicz A (2001) Analiza sedymentologiczna i petrograficzna w rejonie otworów Draganowa-1, Zboiska-3, Lubatówka-19 (zachodnia część fałdu Iwonicza-Zdroju). Archiwum BG Geonafta, Warszawa – Gorlice, pp 127 (in Polish only)

  • Epstein S, Mayeda T (1953) Variation of 18O content of waters from natural sources. Geochimica et Cosmochimica Acta. 4:213–224

    Google Scholar 

  • Hanor JS (1987) Origin and migration of subsurface sedimentary brines. Lecture notes for short course no. 21. Society of Economic Paleontologists and Mineralogists (SEPM), USA. 247 pp

  • Hitchon B, Friedman I (1969) Geochemistry and origin of formation waters in the western Canada sedimentary basin – I. Stable isotopes of hydrogen and oxygen. Geochimica et Cosmochimica Acta. 33:1,321–1,349

    Google Scholar 

  • Kendall C, Coplen TB (1985) Multisample conversion of water to hydrogen by zinc for stable isotope determination. Analytical Chemistry 57:1,437–1,440

    PubMed  Google Scholar 

  • Kharaka YK, Berry FAF (1973) Isotopic composition of oil-field brines from Kettleman North Dome, California, and their geologic implications. Geochimica et Cosmochimica Acta. 37:1899–1908

    Google Scholar 

  • Kyser TK (1987) Equilibrium fractionation factors for stable isotopes. In: Kyser TK (ed) Short course in stable isotope geochemistry of low temperature fluids. Mineralogical Association of Canada, Saskatoon, Vol. 13, pp 1–84

  • Leśniak PM (1980) The origin of the chloride waters at Wysowa, West Carpathians – chemical and isotopic approach. Acta Geologica Polonica 30:519–550

    Google Scholar 

  • Leśniak PM (1998) Origin of carbon dioxide and evolution of CO2-rich waters in the West Carpathians, Poland. Acta Geologica Polonica 48:342–366

    Google Scholar 

  • Longstaffe FJ (1987) Stable isotope studies of diagenetic processes. In: Kyser TK (ed) Short Course in Stable isotope geochemistry of low temperature fluids. Mineralogical Association of Canada, Saskatoon, Vol. 13, pp 187–257

  • Majorowicz J, Plewa S (1979) Study of heat flow in Poland with special regard to tectonophysical problems. In: Ćermak V, Rybach L (eds) Terrestrial heat flow in Europe. Springer, Berlin Heidelberg New York, pp 240–252

  • Matthews A, Katz A (1977) Oxygen isotope fractionation during dolomitization of calcium carbonate. Geochimica et Cosmochimica Acta 41:1,431–1,438

    Article  Google Scholar 

  • McCrea JM (1950) On the isotopic chemistry of the carbonates and paleotemperature scale. Journal of Chemical Physics 18:849–857

    CAS  Google Scholar 

  • O’Neil JR (1987) Preservation of H, C and O isotopic ratios in the low temperature environment. In: Kyser TK (ed) Short Course in Stable isotope geochemistry of low temperature fluids. Mineralogical Association of Canada, Saskatoon, Vol. 13, pp 85–128

  • O’Neil JR, Clayton RN, Mayeda TK (1969) Oxygen isotope fractionation in divalent metal carbonates. Journal of Chemical Physics 51:5,547–5,558

    Google Scholar 

  • Oszczypko N, Zuber A (2002) Geological and isotopic evidence of diagenetic waters in the Polish flysch Carpathians. Geologica Carpathica 53:257–268

    CAS  Google Scholar 

  • Porowski A (2001a) Chemical indicators of the origin of mineralized waters in the Central Carpathian Synclinorium. In: Bocheńska T, Staśko S, Wąsik M (eds) Współczesne problemy hydrogeologii, Wrocław, Vol. X, pp 397–404

  • Porowski A (2001b) Chemical composition and origin of ionic ratios in the Iwonicz Anticline mineralized groundwaters (Polish Outer Carpathians). Annales Societatis Geologorum Poloniae 71:125–134

    Google Scholar 

  • Roether W (1970) Water-CO2 exchange set-up for routine 18Oxygene assay of natural waters. International Journal of Applied Radiation and Isotopes 21:379–387

    Article  PubMed  Google Scholar 

  • Różański K, Araguas-Araguas L, Gonfiantini R (1993) Isotopic patterns in modern global precipitation. In: Climate change in continental isotopic records, Geophysical Monography 781–36, American Geophysical Union, Washington DC

  • Schimmelmann A, DeNiro MJ (1993) Preparation of organic and water hydrogen for stable isotope analysis: effects due to reaction vessels and zinc reagent. Analytical Chemistry 65:789–792

    CAS  Google Scholar 

  • Sheppard SMF (1986) Characterization and isotopic variations in natural waters. In: Valley JW, Taylor HP Jr, O’Neil JR (eds) Stable isotopes in high temperature geological processes. Reviews in Mineralogy, Vol. 16, Mineralogical Society of America. Book Crafters Inc., Chelsea. pp 165–183

  • Ślączka A (1977) Uwagi o budowie geologicznej Ziemi Krośnieńskiej. In: Ślączka A (ed) Przewodnik XLIX Zjazdu Polskiego Towarzystwa Geologicznego, Krosno 22–25 września 1977. Wydawnictwa Geologiczne, Warszawa, pp 7–23 (in Polish only)

  • Sofer Z, Gat JR (1972) Activities and concentrations of oxygen-18 in concentrated aqueous salt solutions: analytical and geophysical implications. Earth and Planetary Science Letter 15:232–238

    Article  Google Scholar 

  • Wdowiarz S (1985) Niektóre zagadnienia budowy geologicznej oraz ropo- i gazonośności centralnego synklinorium Karpat w Polsce. Biuletyn Instytutu Geologicznego 350:5-49

    Google Scholar 

  • Wdowiarz S, Zubrzycki A, Frysztak-Wołkowska A (1991) Objaśnienia do Szczegółowej Mapy Geologicznej Polski w skali 1:50,000. Arkusz Rymanów. Państwowy Instytut Geologiczny, Warszawa, 92 pp

  • Welhan JA (1987) Stable isotope hydrology. In: Kyser TK (ed) Short Course in Stable isotope geochemistry of low temperature fluids. Mineralogical Association of Canada, Vol. 13, pp 129–161

  • Yeh HW (1980) D/H ratios and late-stage dehydration of shales during burial. Geochimica et Cosmochimica Acta 44:341–352

    Article  Google Scholar 

  • Yeh HW, Savin SM (1976) The extent of oxygen isotope exchange between clay minerals and seawater. Geochimica et Cosmochimica Acta 40:743–748

    Article  Google Scholar 

  • Yeh HW, Savin SM (1977) Mechanism of burial metamorphism of argillaceous sediments: 3. O-isotope evidence. Geological Society of America Bulletin 88:1,321–1,330

    Google Scholar 

  • Yeh HW, Epstein S (1978) Hydrogen isotope exchange between clay minerals and sea water. Geochimica et Cosmochimica Acta 42:140–143

    Article  Google Scholar 

  • Zuber A, Grabczak J (1987) On the origin of waters in flysch Carpathians. Przegląd Geologiczny 7:366–372 (in Polish, English abstract)

    Google Scholar 

Download references

Acknowledgements

Prof. Jan Dowgiałło (IGS PAS) is thanked for his scientific help, advices and consultations. Dr Bożena Łącka (IGS PAS) is thanked for considerable help in isotopic analyses of carbonates. Authorities of the Centre for Environmental Research in Halle, Germany, are thanked for arranging the possibility of doing fruitful research among the Isotope Hydrology Group; special thanks to Peter Kowski for his help in isotopic measurements.

Work supported financially by Komitet Badań Naukowych (Committee for Scientific Research) grant No 6P04D 007 18.

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Porowski, A. Isotopic evidence of the origin of mineralized waters from the Central Carpathian Synclinorium, SE Poland. Env Geol 46, 661–669 (2004). https://doi.org/10.1007/s00254-004-1005-4

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