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Sulphate Sources in the Sava and Ljubljanica Rivers, Slovenia, Inferred from Sulphur and Oxygen Isotope Compositions

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Abstract

Measurements were made of sulphur and oxygen isotope ratios of sulphate in some Slovenian rivers, lakes and tap waters. δ34S ranged from −0.2 to + 13.3‰, δ18O ranged from +4.9 to + 13.6‰, and the sulphate content varied from 0.8 to 41.4 mg/L. Rivers flowing from the Julian Alps contain a very low amount of sulphate that is leached from a thin horizon of soil by rain. As confirmed by their low δ18O values, these sulphates do not enter the rivers directly in rain, but arise from biochemical cycling in the soil. The low δ34S of this sulphate indicates that it originates from the oxidation of sedimentary sulphides. The evolution of sulphates along the river course was investigated for the Sava and Ljubljanica rivers. The variations observed in sulphate from the waters studied result from variations in the contribution of sulphates of different origin. Downstream the Sava River sulphate is depleted in the heavy isotopes of both sulphur and oxygen, with δ-values gradually tending toward the δ-values of groundwater sulphates in the watershed. In contrast, the δ-values of sulphate in the Ljubljanica River are almost constant and similar to those of sulphate in local groundwater. Introduction of water from Italian and Slovenian mines was recorded in the Soča River, where the lowest δ34S value of sulphate sulphur (−0.2‰) was observed. In addition, the influence of sulphate from the oxidation of sedimentary sulphides was recorded in the Sotla River. No evidence was found for introduction of sulphate from factories.

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References

  • M. E. Böttcher B. Thamdrup (2001) ArticleTitleAnaerobic sulfide oxidation and stable isotope fractionation associated with bacterial sulfur disproportionation in the presence of MnO2 Geochimica et Cosmochimica Acta 65 1573–1581 Occurrence Handle10.1016/S0016-7037(00)00622-0

    Article  Google Scholar 

  • M. E. Böttcher B. Thamdrup T. W. Vennemann (2001) ArticleTitleOxygen and sulfur isotope fractionation during anaerobic bacterial disproportionation of elemental sulfur Geochimica et Cosmochimica Acta 65 1601–1609 Occurrence Handle10.1016/S0016-7037(00)00628-1

    Article  Google Scholar 

  • S. H. Bottrell N. Webber J. Gunn S. R. H. Worthington (2000) ArticleTitleThe geochemistry of sulphur in a mixed allogenic-autogenic karst catchment, Castleton, Derbyshire, UK Earth Surface Processes and Landforms 25 155–165 Occurrence Handle10.1002/(SICI)1096-9837(200002)25:2<155::AID-ESP55>3.0.CO;2-P

    Article  Google Scholar 

  • D. E. Canfield (2001) ArticleTitleIsotope fractionation by natural populations of sulfate-reducing bacteria Geochimica et Cosmochimica Acta 65 1117–1124 Occurrence Handle10.1016/S0016-7037(00)00584-6

    Article  Google Scholar 

  • Chukhrov F. V., Churikov V. S., Yermilova L. P. and Nosik L. P. (1975) On the variation of sulfur isotopic composition in some natural waters. Geochem Int. 12(2) 20–33 (Translation from Geokhimiya, 1975, 3, 343–356)

    Google Scholar 

  • G. E. Claypool W. T. Holser I. R. Kaplan H. Sakai I. Zak (1980) ArticleTitleThe age curve of sulfur and oxygen isotopes in marine sulfate and their mutual interpretation Chemical Geology 28 199–260 Occurrence Handle10.1016/0009-2541(80)90047-9

    Article  Google Scholar 

  • T. Ding S. Valkiers H. Kipphardt P. Bievre ParticleDe P. D. P. Taylor R. Gonfiantini H. R. Krouse (2001) ArticleTitleCalibrated sulfur isotope abundance ratios of three IAEA sulfur isotope reference materials and V-CDT with a reassessment of the atomic weight of sulfur Geochimica et Cosmochimica Acta 65 2433–2437 Occurrence Handle10.1016/S0016-7037(01)00611-1

    Article  Google Scholar 

  • B. Dold J. E. Spangenberg (2005) ArticleTitleSulfur speciation and stable isotope trends of water-soluble sulfates in mine tailings profiles Environmental Science & Technology 39 5650–5656 Occurrence Handle10.1021/es040093a

    Article  Google Scholar 

  • T. Dolenec J. Pezdič U. Herlec D. Kušcar G. Mitrevski (1989) ArticleTitleDetermining of origin of waters in collieries with natural isotopes and other geochemical parameters Mining and Metallurgy Quaterly 36 IssueID3 521–546

    Google Scholar 

  • M. Drovenik J. Duhovnik J. Pezdic (1976) ArticleTitleIsotopska sestava zvelpa v sulfidih rudnih nahajalisc v Sloveniji Rudarkso-metalurski zbornik 2–3 193–246

    Google Scholar 

  • S. Halas (1979) ArticleTitleAn automatic inlet system with pneumatic changeover valves for isotope ratio mass spectrometer Journal of Physics E.: Science Instruments 18 417–420

    Google Scholar 

  • S. Halas J. Szaran (2001) ArticleTitleImproved thermal decomposition of sulfates to SO2 and mass spectrometric determination of δ34S of IAEA SO-5, IAEA SO-6 and NBS-127 sulfate standards Rapid Communication Mass Spectrometry 15 1618–1620 Occurrence Handle10.1002/rcm.416

    Article  Google Scholar 

  • S. Halas J. Szaran (2004) ArticleTitleUse of Cu2O–NaPO3 mixtures for SO2 extraction from BaSO4 for sulfur isotope analysis Isotopes in Environmental and Health Studies 40 IssueID3 229–231 Occurrence Handle10.1080/10256010410001675001

    Article  Google Scholar 

  • F. Haubrich M. Tichomirowa (2002) ArticleTitleSulfur and oxygen isotope geochemistry of acid mine drainage – the polymetallic sulfide deposit “Himmelfahrt Fundgrube” in Freiberg (Germany) Isotopes in Environmental and Health Studies 38 121–138 Occurrence Handle10.1080/10256010212985

    Article  Google Scholar 

  • B. Hitchon H. R. Krouse (1972) ArticleTitleHydrogeochemistry of the surface waters of the Mackenzie River drainage basin, Canada, III. Stable isotopes of oxygen, carbon and sulfur Geochimica et Cosmochimica Acta 36 1337–1357 Occurrence Handle10.1016/0016-7037(72)90066-X

    Article  Google Scholar 

  • Hunt C. D., West D. E. and Peven C. S. (1995) Deer Island effluent characterization and pilot treatment plant studies: June 1993–November 1994. MWRA Technical Report No. 95-7

  • H. R. Krouse (1980) Sulphur isotopes in our environment P. Fritz J. Ch. Fontes (Eds) Handbook of Environmental Isotope Geochemistry vol. I, The Terrestrial Environment, A Elsevier Amsterdam 435–471

    Google Scholar 

  • Krouse H. R. and Grinenko V. A. (eds.) In SCOPE 43, Stable isotopes: Natural and Anthropogenic Sulphur in the Environment. John Wiley & Sons, Chichester, New York, Brisbane, Toronto, Singapore

  • Krouse H. R. and Mayer B. (2000) Sulphur and oxygen isotopes in sulphate. In P. Cook and A. L. Herczeg (eds), Environmental Tracers in Subsurface Hydrology Chap. 7, pp. 195–231, Kluwer Academic Publishers

  • J. V. Lavrič J. E. Spangenberg (2003) ArticleTitleStable isotope (C, O, S) systematics of the mercury mineralization at Idrija, Slovenia: constraints on fluid source and alteration processes Mineralium Deposita 38 886–899 Occurrence Handle10.1007/s00126-003-0377-9

    Article  Google Scholar 

  • R. M. Lloyd (1968) ArticleTitleOxygen isotope behavior in the sulfate-water system Journal of Geophysical Research 73 6099–6110 Occurrence Handle10.1029/JB073i018p06099

    Article  Google Scholar 

  • A. Longinelli G. Cortecci (1970) ArticleTitleIsotope abundance of oxygen and sulfur in sulfate ions from river water Earth and Planetary Science Letters 7 376–380 Occurrence Handle10.1016/0012-821X(69)90053-3

    Article  Google Scholar 

  • Mayer B. (1998) Potential and limitations of using sulfur isotope abundance ratios as an indicator for natural and anthropogenic environmental change. In Isotope Techniques in the Study of Environmental Change, pp. 423–435. International Atomic Energy Agency, Vienna

  • Y. Mizutani (1971) ArticleTitleAn improvement in the carbon-reduction method for the oxygen isotopic analysis of sulphates Geochemical Journal 5 69–77

    Google Scholar 

  • Y. Mitzutani T. A. Rafter (1969) ArticleTitleOxygen isotopic composition of sulfates: Part 5, Isotopic value of sulfate in rain water, Gracefield, New Zealand NewZealand Journal of Science 12 69–80

    Google Scholar 

  • S. J. Moncaster S. H. Bottrell J. H. Tellam J. W. Lloyd K. O. Konhauser (2000) ArticleTitleMigration and attenuation of agrochemical pollutants: insights from isotopic analysis of ground water sulfate Journal of Contaminant Hydrology 43 147–163 Occurrence Handle10.1016/S0169-7722(99)00104-7

    Article  Google Scholar 

  • Morrison J., France-Lanord C. and Pierson-Wickmann A. C. (1999) Oxygen-sulphur-isotopic measurement in continuous flow mode: Application to the origin of dissolved sulphates in Himalayan rivers using elemental analyzer stable isotope ratio mass spectrometry. Ninth Annual V. M. Goldschmidt Conference, August 22–27, 1999, Cambridge, Massachusetts, abstract no. 7620

  • M. Novák J. W. Kirchner H. Groscheová M. Havel J. Černý R. Krejčí F. Buzek (2000) ArticleTitleSulfur isotope dynamics in two Central European watersheds affected by high atmospheric deposition of SOx Geochimica et Cosmochimica Acta 64 367–383 Occurrence Handle10.1016/S0016-7037(99)00298-7

    Article  Google Scholar 

  • N. Otero A. Soler (2002) ArticleTitleSulfur isotopes as tracers of the influence of potash mining in groundwater salinisation in the Llobregat Basin (NE Spain) Water Research 36 3989–4000 Occurrence Handle10.1016/S0043-1354(02)00125-2

    Article  Google Scholar 

  • J. Pezdič (1998) ArticleTitleStable isotopes as natural tracers of the karst recharge to the Tertiary clastic aquifers. A case study of the southern part of Ljubljana marsh (Ljubljansko barje, Slovenia) Acta Carsologica XXVII/1 20 349–360

    Google Scholar 

  • Pleničar M. (1956) The development of Pliocene in Slovenia. 1st. Geological Congress of FNR Yugoslavia, Bled 1954, pp. 55–58

  • H. P. Schwarcz G. Cortecci (1974) ArticleTitleIsotopic analysis of spring and stream water from Italian Alps and Apennines Chemical Geology 13 285–294 Occurrence Handle10.1016/0009-2541(74)90135-1

    Article  Google Scholar 

  • Soler A., Ginebreda A., Otero N., Canals A., Cardellach E., Antich N., Vitoria L., Godé L. I. and Piniella J. F. (1999) Environmental applications of sulphur isotopic geochemistry to the study of water pollution problems. 9as Jordanas de Analisis Instrumental, MAP1-55, p. 187

  • A. Soler A. Canals S. L. Goldstein N. Otero N. Anrtich J. Spangenberg (2002) ArticleTitleSulfur and strontium isotope composition of the Llobregat River (NE Spain): tracers of natural and anthropogenic chemicals in stream waters Water, Air and Soil Pollution 136 207–224 Occurrence Handle10.1023/A:1015231810548

    Article  Google Scholar 

  • Spangenberg J. E., Lavrič J. V. and Herlec U. (2001) Sulfur-isotope study of the Mežica Mississippi Valley-type lead–zinc ore deposits, Slovenia: Mineral deposits at the beginning of the 21st century. Proceedings of joint 6th Biennial SGA-SEG Meeting, 26–29 August 2001, Kraków, Poland, pp. 181–184

  • B. E. Taylor M. C. Wheeler D. K. Nordstrom (1984) ArticleTitleStable isotope geochemistry of acid mine drainage: Experimental oxidation of pyrite Geochimica et Cosmochimica Acta 48 2669–2678 Occurrence Handle10.1016/0016-7037(84)90315-6

    Article  Google Scholar 

  • L. Toran R. F. Harris (1989) ArticleTitleInterpretation of sulfur and oxygen isotopes in biological and abiological sulfide oxidation Geochimica et Cosmochimica Acta 53 2341–2348 Occurrence Handle10.1016/0016-7037(89)90356-6

    Article  Google Scholar 

  • A. Trembaczowski (1991) ArticleTitleSulphur and oxygen isotopes behaviour in sulphates of atmospheric groundwater system, observation and model Nordic Hydrology 22 49–66

    Google Scholar 

  • A. Trembaczowski S. Ha\las (1993) ArticleTitleSulphur and oxygen isotopes in sulphates in natural waters (1). Surface waters of relatively unpolluted terrains Isotopenpraxis 28 215–228

    Google Scholar 

  • A. Trembaczowski J. Szaran H. Niezgoda (2004) ArticleTitleInvestigating the provenance and seasonal variations in the sulphate sulphur and oxygen isotopes of Central Roztocze river water, SE Poland Water, Air and Soil Pollution 157 65–84 Occurrence Handle10.1023/B:WATE.0000038873.25798.6b

    Article  Google Scholar 

  • S. M. Turner G. Malin P. S. Liss D. S. Harbour P. M. Holligan (1988) ArticleTitleThe seasonal variation of dimethylsulfide and dimethylsufonio-propionate concentration in near shore waters Limnology and Oceanography 33 364–375 Occurrence Handle10.4319/lo.1988.33.3.0364

    Article  Google Scholar 

  • D. R. Stempvoort ParticleVan E. J. Reardon P. Fritz (1990) ArticleTitleFractionation of sulfur and oxygen isotopes in sulfate by soil sorption Geochimica et Cosmochimica Acta 54 2817–2826 Occurrence Handle10.1016/0016-7037(90)90016-E

    Article  Google Scholar 

  • E. Wakshal H. Nielsen (1982) ArticleTitleVariations of δ34S, δ18O and Cl/SO4 rations in rainwater over northern Israel, from the Mediterranean coast to Jordan Rift Valley and Golan Heights Earth and Planetary Science Letters 61 272–282 Occurrence Handle10.1016/0012-821X(82)90058-9

    Article  Google Scholar 

  • W. Yang R. J. Spencer H. R. Krouse (1997) ArticleTitleStable isotope compositions of waters and sulfate species therein, Death Valley, California, USA; Implications for inflow and sulfate sources, and arid basin climate Earth and Planetary Science Letters 147 69–82 Occurrence Handle10.1016/S0012-821X(97)00011-3

    Article  Google Scholar 

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Authors and Affiliations

  1. Slovenian Nuclear Safety Administration, Zelezna cesta 16, 1000, Ljubljana, Slovenia

    Barbara Vokal-Nemec

  2. Institute of Physics, Maria Curie-Sklodowska University, Plac M. Curie-Sklodowskiej 1, 20-031, Lublin, Poland

    Janina Szaran, Andrzej Trembaczowski & Stanislaw Halas

  3. Department of Geology, Faculty of Natural Sciences and Engineering, Aškerčeva 12, 1000, Ljubljana, Slovenia

    Tadej Dolenec

  4. Department of Environmental Sciences, Jožef Stefan Institute, Jamova 39, 1000, Ljubljana, Slovenia

    Sonja Lojen

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  1. Barbara Vokal-Nemec
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  2. Janina Szaran
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  3. Andrzej Trembaczowski
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  4. Stanislaw Halas
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  5. Tadej Dolenec
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  6. Sonja Lojen
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Correspondence to Janina Szaran.

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Vokal-Nemec, B., Szaran, J., Trembaczowski, A. et al. Sulphate Sources in the Sava and Ljubljanica Rivers, Slovenia, Inferred from Sulphur and Oxygen Isotope Compositions. Aquat Geochem 12, 199–220 (2006). https://doi.org/10.1007/s10498-005-5792-3

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