Abstract
The Sava River and its tributaries in Slovenia represent waters strongly influenced by chemical weathering of limestone and dolomite. The carbon isotopic compositions of dissolved inorganic carbon (DIC) and suspended organic carbon (POC) fractions as well as major solute concentrations yielded insights into the origin and fluxes of carbon in the upper Sava River system. The major solute composition was dominated by carbonic acid dissolution of calcite and dolomite. Waters were generally supersaturated with respect to calcite, and dissolved CO2 was about fivefold supersaturated relative to the atmosphere. The δ13C of DIC ranged from −13.5 to −3.3‰. Mass balances for riverine inorganic carbon suggest that carbonate dissolution contributes up to 26%, degradation of organic matter ∼17% and exchange with atmospheric CO2 up to 5%. The concentration and stable isotope diffusion models indicated that atmospheric exchange of CO2 predominates in streams draining impermeable shales and clays while in the carbonate-dominated watersheds dissolution of the Mesozoic carbonates predominates.
Similar content being viewed by others
References
Agency of Republic of Slovenia for the Environment (2004–2005) Monthly bulletin, No. 1–12 (in Slovene)
Amiotte Suchet P, Probst JL (1993) Modelling of atmospheric CO2 consumption by chemical weathering of rocks: application to the Garonne, Congo and Amazon basins. Chem Geol 107:205–210
Atekwana EA, Krishnamurthy RV (1998) Seasonal variations of dissolved inorganic carbon and δ13C of surface waters: application of a modified gas evaluation technique. J Hydrol 205:260–278
Atkins PW (1994) Physical chemistry. Oxford University press, Oxford
Aucour AM, Sheppard SMF, Guyomar O, Wattelet J (1999) Use of 13C to trace the origin and cycling of inorganic carbon in the Rhône river system. Chem Geol 159:87–105
Aumont O, Orr JC, Monfray W, Ludwig P, Amiotte-Suchet P, Probst JL (2001) Riverine-driven interhemispheric transport of carbon. Global Biogeochem Cycles 15:393–406
Barth JAC, Veizer J (1999) Carbon cycle in St. Lawrence aquatic ecosystems at Cornwall (Ontario), Canada: seasonal and spatial variations. Chem Geol 159:107–128
Barth JAC, Cronin AA, Dunlop J, Kalin RM (2003) Influence of carbonates on the riverine carbon cycle in an anthropogenically dominated catchment basin: evidence from major elements and stable carbon isotopes in the Lagan River (N. Ireland). Chem Geol 200:203–216
Broecker WS (1974) Chemical oceanography. Harcourt Brace Jovanovich, New York
Broecker HC, Peterman J, Siems W (1978) The influence of wind on CO2-exchange in a wind-wave tunnel, including the effects of monolayers. J Mar Res 36:595–610
Buhl D, Neuser RD., Richter DK, Riedel D, Roberts B, Strauss H, Veizer J (1991) Nature and nurture: environmental isotope story of the river Rhine. Naturwissenshaften 78:337–346
Buser S (1987) Geological map of Slovenia. In: Encyclopedia of Slovenia No. 8. Mladinska knjiga, Ljubljana (in Slovene)
Chen J, Wang F, Xia X, Zhang L (2002) Major element chemistry of the Changjiang (Yangtze River). Chem Geol 187:231–255
Dever L, Durand R, Fontes J Ch, Vaicher P (1983) Etude pédogénétique et isotopique des néoformations de calcite dans un sol sur craie. Caractéristiques et origines. Geochim Cosmochim Acta 47:2079–2090
Devol AH, Hedges JI (2001) Organic matter and nutrients in the mainstem Amazon River. In: McClain ME, Victoria RL, Richey JE (eds) The biogeochemistry of the Amazon Basin. Oxford Univ. Press, New York, p 365
EIONET (2005) European Environment Information and Observation Network http://www.eionet-en.arso.gov.si Cited 11 Nov 2005
Flintrop C, Hohlmann B, Jasper T, Korte C, Podlaha O, Scheele SM, Veizer J (1996) Anatomy of pollution: rivers of North – Rhine – Westphalia, Germany. Am J Sci 296:59–98
Gaillardet J, Dupre B, Allegre CJ (1999a) Geochemistry of large river suspended sediments: silicate weathering or recycling tracer? Geochim Cosmochim Acta 63:4037–4051
Gaillardet J, Dupre B, Louvat P, Allegre CJ (1999b) Global silicate weathering and CO2 consumption rates deduced from the chemistry of large rivers. Chem Geol 159:3–30
Gao W, Kempe S (1987) The Changjiang: its long-term changes in pCO2 and carbonate mineral saturation. In Degens ET et al (eds) Transport of carbon and minerals in major world rivers, vol 1. Mitt. Geol.-Paläont. Inst. Univ., Hamburg, pp 207–216
Gieskes JM (1974) The alkalinity-total carbon dioxide system in seawater. In: Goldberg ED (ed) Marine chemistry of the sea, vol 5. Wiley, New York, pp 123–151
Grosbois C, Négrel P, Fouillac C, Grimaud D (2000) Dissolved load of the Loire River: chemical and isotopic characterization. Chem Geol 170:179–201
Haskoning (1994) Danube integrated environmental study, report phase 1, Haskoning, Royal Dutch Consulting Engineers and Architects, EPDRB report
Hedges JI (1992) Global biogeochemical cycle: progress and problem. Mar Chem 39:67–93
Hedges JI, Clark WA, Quay PD, Richey JE, Devol AH, Santos UM (1986) Compositions and fluxes of particulate organic material in the Amazon River. Limnol Oceanogr 31:717–738
Hellings L, Dehairs F, Tackx M, Keppens E, Baeyens W (1999) Origin and fate of organic carbon in the freshwater part of the Scheldt Estuary as traced by stable carbon isotope composition. Biogeochemistry 47:167–186
Hélie JF, Hillaire-Marcel C, Rondeau B (2002) Seasonal changes in the sources and fluxes of dissolved inorganic carbon through the St. Lawrence River – isotopic and chemical constraint. Chem Geol 186:117–138
Holley EH (1977) Oxygen transfer at the air–water interface. In: Gibbs RJ (ed) Transport processes in lakes and oceans. Proceedings of the symposium on transport processes in the ocean held at the 82nd Nat. Meet Of the AICE, Atlantic City, N.J. Aug. 29–Sep. 1, 1976, Plenum Press, pp 117–150
Hrvatin M (1998) Discharge regimes in Slovenia. Geografski zbornik XXXVIII:60–87
Ittekkot V (1988) Global trends in the nature of organic matter in the river suspensions. Nature 332:436–438
Jähne B, Heinz G, Dietrich W (1987) Measurments of the diffision coefficients of sparingly soluble gases in water. J Geophys Res 92:10767–10776
Kanduč T (2006) Hydrogeochemical characteristics and carbon cycling in the Sava River watershed in Slovenia, Dissertation. University of Ljubljana
Karim A, Veizer J (2000) Weathering processes in the Indus River Basin: implications from riverine carbon, sulfur, oxygen and strontium isotopes. Chem Geol 170:153–177
Kempe S (1982) Long-term record of CO2 pressure fluctuations in fresh waters: In: Degens ET (ed) Transport of carbon and minerals in major world rivers, part 1, vol 52. Mitt. Geol.-Paläont. Inst. Univ. Hamburg, Hamburg, pp 91–332
Kempe S, Pettine M, Cauwet G (1991) Biogeochemistry of European rivers. In: Kempe S, Degens ET, Richey JE (eds) Biogeochemistry of major world rivers. Wiley, New York, SCOPE/UNEP 42, pp 169–211
Kendall C, Silva SR, Kelly VJ (2001) Carbon and nitrogen isotopic composition of particulate organic matter in four large river systems across the United States. Hydrol Process 15:1301–1346
Levin I, Kromer B, Wagenback D, Minnich KO (1987) Carbon isotope measurements of atmospheric CO2 at a coastal station in Antarctica. Tellus 39B:89–95
Livingstone DA (1963) Chemical composition of rivers and lakes. U.S. Geol. Survey Prof Paper, p 44-G
Mayorga E, Aufdenkampe AK, Masiello CA, Krusche AV, Hedges JI, Quay PD, Richey JE, Brown TA (2005) Young organic matter as a source of carbon dioxide outgassing from Amazonian rivers. Nature 436:538–541
Meybeck M (1982) Carbon, nitrogen and phosphorus transport by world rivers. Am J Sci 282:401–450
Meybeck M (1993) Natural sources of C, N, P and S. NATO ASI Series, vol. 14. Interactions of C, N, P and S, biogeochemical cycles and global change. Springer Verlag, Berlin, pp 163–193
Miyajima T, Yamada Y, Hanba YT (1995) Determining the stable isotope ratio of total dissolved inorganic carbon in lake water by GC/C/IRMS. Limnol Oceanogr 40(5):994–1000
Mook WG (1970) Stable carbon and oxygen isotopes of natural water in the Netherlands. In Isotopic Hydrology, IAEA, pp 163–190
Mook WG, Bommerson JC, Staverman WH (1974) Carbon isotope fractionation between dissolved bicarbonate and gaseous carbon dioxide. Earth Planet Sci Lett 22:169–176
Neal C, Harrow M, Williams RJ (1998) Dissolved carbon dioxide and oxygen in the River Thames: Spring-summer 1997. Sci Total Environ 210:205–217
Parkhurst DL, Appelo CAJ (1999) User’s guide to PHREEQC (version 2) – a computer program for speciation, batch-reaction, one-dimensional transport, and inverse geochemical calculations. Water Resources Investigations Report 99-4259
Pawellek F, Veizer J (1994) Carbon cycle in the upper Danube and its tributaries: δ13CDIC constraints. Isr J Earth Sci 43:187–194
Pawellek F, Frauenstein F, Veizer J (2002) Hydrochemistry and isotope geochemistry of the upper Danube River. Geochim Cosmochim Acta 66(21):3839–3854
Picouet C, Dupré B, Orange D, Valladon M (2002) Major and trace element geochemistry in the upper Niger river (Mali): physical and chemical weathering rates and CO2 consumption. Chem Geol 185:93–124
Raymond PA, Cole JJ (2003) Increase in the export of alkalinity from North America’s largest river. Science 301:88–91
Reardon EJ, Allison GB, Fritz P (1979) Seasonal chemical and isotopic variations of soil CO2 at Trout Creek, Ontario. J Hydrol 43:355–371
Richey JE, Hedges JI, Devol AH, Quay PD (1990) Biogeochemistry of carbon in the Amazon River. Limnol Oceanogr 35(2):352–371
Roy S, Gaillardet J, Allègre CJ (1999) Geochemistry of dissolved and suspended loads of the Seine River, France: anthropogenic impact, carbonate and silicate weathering. Geochim Cosmochim Acta 63:1277–1292
Sarmiento JL, Sundquist ET (1992) Revised budget for the oceanic uptake of anthropogenic carbon-dioxide. Nature 356(6370):589–593
Spötl C (2005) A robust and fast method of sampling and analysis of δ13C of dissolved inorganic carbon in ground waters. Isotopes Environ Health Stud 41:217–221
Stallard RF (1980) Major element geochemistry of the Amazon River system. Ph.D MIT/WHO
Szramek K (2006) Carbonate mineral weathering in mid-latitude watersheds: importance of calcite and dolomite dissolution on dissolved inorganic carbon acquisition and transport. Dissertation, University of Michigan
Szramek K, McIntosh JC, Williams EL, Kanduč T, Ogrinc N, Walter LM (2007) Relative weathering intensity of calcite versus dolomite in carbonate-bearing temperate zone watersheds: carbonate geochemistry and fluxes from catchments within the St. Lawrence and Danube river basins. Geochem Geophy Geosys (G3) 8:1–26
Tao S (1998) Spatial and temporal variation in DOC in the Yichun River, China. Water Res 32:2205–2210
Taylor CB, Fox VJ (1996) An isotopic study of dissolved inorganic carbon in the catchment of the Waimakariri River and deep ground water of the North Canterbury plains, New Zealand. J Hydrol 186:161–190
Telmer K, Veizer J (1999) Carbon fluxes, pCO2 and substrate weathering in a large northern river basin, Canada: carbon isotope perspectives. Chem Geol 159:61–86
Urbanc–Berčič O (1999) Aquatic macrophytes in the rivers Sava, Kolpa and Krka. Ichthyos 1:23–34
Van Breenan N, Protz R (1988) Rates of calcium carbonate removal from soils. Can J Soil Sci 68:449–454
Wachniew P (2006) Isotopic composition of dissolved inorganic carbon in a large polluted river: The Vistula, Poland. Chem Geol 233:293–308
Weiguo L, Zisheng AN, Weijian Z, Head MJ, Delin C (2003) Carbon isotope and C/N ratios of suspended matter in rivers: as indicator of seasonal change in C4/C3 vegetation. Appl Geochem 18:1241–1249
Wu Y, Zhang J, Liu SM, Zhang ZF, Yao QZ, Hong GH, Cooper L (2007) Sources and distribution of carbon within the Yangtze River system. Estuar Coast Shelf Sci 71:13–25
Zhang J, Quay PD, Wilbur DO (1995) Carbon isotope fractionation during gas–water exchange and dissolution of CO2. Geochim Cosmochim Acta 59(1):107–1146
Yang C, Telmer K, Veizer J (1996) Chemical dynamics of the ‘St. Lawrance’ riverine system: δDH2O, δ18OH2O, δ13CDIC, δ34Ssulfate, and dissolved 87Sr/86Sr. Geochim Cosmochim Acta 60:851–866
Acknowledgements
The authors are grateful to Mr. Stojan Žigon for technical support and assistance to Dale Austin for help with the graphic presentation in this manuscript. This research was conducted in the framework of the project L2-6458-792 funded by the Slovenian Research Agency (ARRS) and within the EU 6th Framework Specific Targeted Research Project—SARIB (Sava River Basin: Sustainable Use, Management and Protection of Resources), Contract No. INCO-CT-2004-509160. The project was also financially supported by the National Science Foundation, USA (NSF-EAR#0208182). Special thanks are given to Stephen K. Hamilton for linguistic corrections.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Kanduč, T., Szramek, K., Ogrinc, N. et al. Origin and cycling of riverine inorganic carbon in the Sava River watershed (Slovenia) inferred from major solutes and stable carbon isotopes. Biogeochemistry 86, 137–154 (2007). https://doi.org/10.1007/s10533-007-9149-4
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10533-007-9149-4