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Estimation of denitrification potential in a karst aquifer using the 15N and 18O isotopes of NO 3

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Abstract.

A confined aquifer in the Malm Karst of the Franconian Alb, South Germany was investigated in order to understand the role of the vadose zone in denitrifiaction processes. The concentrations of chemical tracers Sr2+ and Cl and concentrations of stable isotope 18O were measured in spring water and precipitation during storm events. Based on these measurements a conceptual model for runoff was constructed. The results indicate that pre-event water, already stored in the system at the beginning of the event, flows downslope on vertical and lateral preferential flow paths. Chemical tracers used in a mixing model for hydrograph separation have shown that the pre-event water contribution is up to 30%. Applying this information to a conceptual runoff generation model, the values of δ15N and δ18O in nitrate could be calculated. Field observations showed the occurence of significant microbial denitrification processes above the soil/bedrock interface before nitrate percolates through to the deeper horizon of the vadose zone. The source of nitrate could be determined and denitrification processes were calculated. Assuming that the nitrate reduction follows a Rayleigh process one could approximate a nitrate input concentration of about 170 mg/l and a residual nitrate concentration of only about 15%. The results of the chemical and isotopic tracers postulate fertilizers as nitrate source with some influence of atmospheric nitrate. The combined application of hydrograph separation and determination of isotope values in δ15N and δ18O of nitrate lead to an improved understanding of microbial processes (nitrification, denitrification) in dynamic systems.

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References

  • J.D. Aber K.J. Nadelhoffer P. Steudler J.M. Melillo (1989) ArticleTitleNitrogen saturation in northern forest ecosystems Bioscience 39 378–386

    Google Scholar 

  • A. Amberger H.-L. Schmidt (1996) ArticleTitleNatürliche Isotopengehalte für Nitrat als Indikatoren für dessen Herkunft Geochim. Cosmochim. Acta 51 1699–2705

    Google Scholar 

  • R. Aravena W.D. Robertson (1998) ArticleTitleUse of multiple isotope tracers to evaluate denitrification in ground water: study of nitrate from a large-flux septic system plume Ground Water 36 975–982 Occurrence Handle1:CAS:528:DyaK1cXnsVSisro%3D

    CAS  Google Scholar 

  • Buyarian water Management Agency 1996. Groundwater Recharge in Bavaria. Heft 5/96, (in German).

  • D.E. Bazemore K.N. Eshleman K.J. Hollenbeck (1994) ArticleTitleThe role of soil water in storm flow generation in a forested headwater catchment: synthesis of natural tracers and hydrometric evidence J. Hydrol. 162 47–75

    Google Scholar 

  • T. Biegert G. Fuchs J. Heider (1996) ArticleTitleEvidence that anaerobic oxidation of toluene in the denitrifying bacterium Thauera aromatica is initiated by formation of benzylsuccinate from toluene and fumarate Eur. J. Biochem. 238 661–668 Occurrence Handle1:CAS:528:DyaK28XktVaktL8%3D Occurrence Handle8706665

    CAS  PubMed  Google Scholar 

  • J. Böttcher O. Strebel S. Voerkelius H.L. Schmidt (1990) ArticleTitleUsing isotope fractionation of nitrate nitrogen and nitrate oxygen for evaluation of denitrification in a sandy aquifer J. Hydrol. 114 413–424

    Google Scholar 

  • A. Brown J.J. McDonnell D.A. Burns C. Kendall (1999) ArticleTitleThe role of event watera rapid shallow flow componentand catchment size in summer stormflow J. Hydrol. 217 IssueID3–4 171–190

    Google Scholar 

  • J.M. Buttle (1994) ArticleTitleIsotope hydrograph separations and rapid delivery of preevent water from drainage basins Prog. Phys. Geogr. 18 16–41

    Google Scholar 

  • Buttle J.M. and McDonald D.J. 2002. Coupled vertical and lateral preferential flow on a forested slope. Water Resour. Res. 38(5): 10.1029/2001 WR000773.

  • J.M. Buttle D.S. Turcotte (1999) ArticleTitleRunoff processes on a forested slope on the Canadian Shield Nordic Hydrol. 30 1–20

    Google Scholar 

  • I. Clark P. Fritz (1997) Environmental Isotopes in Hydrogeology Lewis Publishers Boca Raton, USA 151

    Google Scholar 

  • T.B. Coplen J.A. Hopple J.k. Böhlke H.S. Peiser S.E. Rieder H.R. Krouse K.J.R. Rosman T. Ding R.D. Vocke K.M. Revez A. Lamberty P. Tayler P. De Bievre (2002) Compilation of Minimum and Maximum Isotope Ratios of Selected Elements in Naturally Occurring Terrestrial materials and Reagents. Water-Resources Investigations Report 01-4222 US Geological Survey Reston, Virginia

    Google Scholar 

  • W. Durka E.D. Schulze B. Gebauer S. Voerkelius (1994) ArticleTitleEffects of forest decline on uptake and leaching of deposited nitrate determined from 15N and 18O measurements Nature 372 765–768 Occurrence Handle1:CAS:528:DyaK2MXisl2qu7c%3D

    CAS  Google Scholar 

  • Einsiedl F., Stichler W. and Maloszewski P. 2002. Untersuchung hydrodynamischer Prozesse eines Karstsystems unter Verwendung natürlicher und künstlicher Tracer. In: Herbert D., Merkel B. and Wolkersdorf C.H. (eds.)Workshop “Isotope und Tracer in der Wasserforschung”. Freiberg, pp. 95–102 (in German).

  • St. Glaser (1998) Der Grundwasserhaushalt in verschiedenen Faziesbereichen des Malms der Südlichen und Mittleren Frankenalb GSF-Bericht 2/98 München

    Google Scholar 

  • T.H.E. Heaton (1986) ArticleTitleIsotope studies of nitrogen pollution in the hydrosphere and atmosphere: a review Chem. Geol. 59 87–102 Occurrence Handle1:CAS:528:DyaL28XmtlWqtbw%3D

    CAS  Google Scholar 

  • C. Hellmeier (2001) Stofftransport in der ungesättigten Zone der landwirtschaftlich genutzten Flächen in Scheyern/Oberbayern (Tertiärhügelland) GSF-Bericht 5/01 Munich

    Google Scholar 

  • A.R. Hill W.A. Kemp J.M. Buttle D. Goodyear (1999) ArticleTitleNitrogen chemistry of subsurface storm runoff on forested Canadian Shield hillslopes Water Resour. Res. 35 IssueID3 811–821 Occurrence Handle1:CAS:528:DyaK1MXitVGjsLY%3D

    CAS  Google Scholar 

  • M.J. Hinton S.L. Schiff M.C. English (1994) ArticleTitleExamining the contributions of glacial till water to storm runoff using two- and three component hydrograph seperations Water Resour. Res. 30 983–993

    Google Scholar 

  • Hötzl H 1999. Der Karst als Trinkwasserressource. In: Seiler K.-P., Grundwasserschutz im Karst der Südlichen FrankenalbGSF-Bericht 4/99. pp. 99–114 (in German).

  • Kaiser K., Guggenberg G., Kaupenjohann M. and Zech W. 2002. Refractory organic substances in aggregated forest soils – retention versus translocation. In: Frimmel F.H. Abbt-Braun G. Heumann K.G. Hock B. Lüdemann H.D. and Spiteller M.(eds.)Refractory Organic Substances in the Environment.

  • C. Kendall (1998) Tracing nitrogen sources and cycling in catchments C. Kendall J.J. McDonnell (Eds) Isotope Tracers in Catchment Hydrology Elsevier Amsterdam

    Google Scholar 

  • Kendall C., Silva S.R., Chang C.C.Y., Burns D.A., Cambell D.H. and Shanley J.B. 1996. Use of the δ18O and δ15N of nitrate in earlier spring runoff in forested chatchments. Isotopes in Water Resources ManagementInternational Atomic Energy Agency, Vol. 1. Viennapp. 167–176.

  • Kreitler C.W. 1975. Determining the source of nitrate in groundwater by nitrogen isotope studies. Bureau of Economic Geology, Report of Investigation No. 83. University of Texas, Austin, Texas, Austin, p. 57.

  • M. Langdsmand K.G. Villholth M. Ullum K.H. Jensen (1999) ArticleTitleProcesses of colloid mobilization and transport in macropours soil monoliths Geoderma 93 33–59

    Google Scholar 

  • E.S. Lee N.C. Krothe (2001) ArticleTitleA four-component mixing model for water in a karst terrain in south-central IndianaUSA. Using solute concentration and stable isotopes as tracers Chem. Geol. 179 129–143 Occurrence Handle1:CAS:528:DC%2BD3MXltlGgtbY%3D

    CAS  Google Scholar 

  • E.S. Lee N.C. Krothe (2003) ArticleTitleDelineating the karstic flow system in the upper Lost River drainage basin, south central Indiana: using sulphate and δ34 S \(_{{\rm S}-34({\rm SO}_{4})}\) as tracers Appl. Geochem. 18 145–153 Occurrence Handle1:CAS:528:DC%2BD38XoslKru7k%3D

    CAS  Google Scholar 

  • P. Maloszewski W. Stichler A. Zuber D. Rank (2002) ArticleTitleIdentifying the flow systems in a karstic-porous aquiferthe SchneealpeAustriaby modelling of environmental 18O und 3H isotopes J. Hydrol. 256 48–59 Occurrence Handle1:CAS:528:DC%2BD38Xht1Olsrk%3D

    CAS  Google Scholar 

  • P. Maloszewski A. Zuber (1985) ArticleTitleMathematical models for interpreting tracer experimets in fissured rocks with a porous matrix J. Hydrol. 79 333–358 Occurrence Handle1:CAS:528:DyaL28Xit1ajug%3D%3D

    CAS  Google Scholar 

  • A. Mariotti A. Landreau B. Simon (1988) ArticleTitle15N isotope biogeochemistry and natural denitrification process in groundwater: application to the chalk aquifer of northern France Geochim. Cosmochim. Acta 52 1869–1878 Occurrence Handle1:CAS:528:DyaL1cXltlCmtb4%3D

    CAS  Google Scholar 

  • J.J. McDonnel I.F. Owens M.K. Stewart (1991) ArticleTitleA case study of shallow flow paths in a steep zero-order basin Water Resour. Bull. 27 679–685

    Google Scholar 

  • R.U. Meckenstock (1999) ArticleTitleFermenative toluene degradation in anaerobic defined syntrophic cocultures FEMS Microbiol. Lett. 177 67–73 Occurrence Handle1:CAS:528:DyaK1MXls1Smsbo%3D Occurrence Handle10436924

    CAS  PubMed  Google Scholar 

  • M. Mengis U. Walther S. Berasconi B. Wehrli (2001) ArticleTitleLimitations of using δ18O for the source identification of nitrate in Agricultural soils Environ. Sci. Technol. 35 1840–1844 Occurrence Handle1:CAS:528:DC%2BD3MXitFGmu70%3D Occurrence Handle11355201

    CAS  PubMed  Google Scholar 

  • Michel U. 1999. Gesteinsphysikalische Eigenschaften und fazielle Ausbildung der oberjurassischen Massenfazies (Kimmeridge) der Südlichen Frankenalb. In: Seiler K.-P.(eds)Trinkwasserschutz im Karst der Südlichen FrankenalbGSF-Bericht 4/99, München, pp. 48–57 (in German).

  • K.J. Nattelhofer B. Fry (1988) ArticleTitleControls on natural nitrogen-15 and carbon-13 abundances in forest soil organic matter Soil Sci. Soc. Am. J. 52 1633–1640

    Google Scholar 

  • S.V. Panno K.C. Hackley H.H. Hwang W.R. Kell (2001) ArticleTitleDetermination of the sources of nitrate contamination in karst springs using isotopic and chemical data Chem. Geol. 179 113–128 Occurrence Handle1:CAS:528:DC%2BD3MXltlGgtbk%3D

    CAS  Google Scholar 

  • Pfaff T. 1987. Grundwasserumsatzräume im Karst der Frankenalb. Ph.D. thesis, LMU, München, GSF-Bericht 3/87 (in German).

  • Rau I. 1999. Untersuchungen zur langfristigen Speicherung von persistenten Schadstoffen in heterogenen porösen Medien mit Umweltracermethoden. Ph.D. thesis, LMU, Munich (in German).

  • K.C. Rice G.M. Hornberger (1998) ArticleTitleComparison of hydrochemical tracers to estimate source contributions to peak flow in a small, forested headwater catchment Water Resour. Res. 34 1755–1766

    Google Scholar 

  • Schmidt-Kaler H. 1989. Geologische Karte 1.25000, Erläuterungen zum Blatt Nr. 7136 Neustadt a. d. Donau.-167 S., München, (Geol. Survey) (in German).

  • R.A. Schroeder J.G. Setmire J.N. Densmore (1991) Use of stabile isotopes, tritiumsoluble salts and redox-sensitive elements to distinguish groundwater from irrigation water in the Salton Sea basin W.F. Ritter (Eds) Irrigation and Drainage American Society of Civil Engineers New York 524–530

    Google Scholar 

  • K.P. Seiler P. Maloszewski H. Behrens (1989) ArticleTitleHydrodynamic dispersion in karstified limestones and dolomites in the Upper Jurassic of the Franconian Alb F.R.G. J. Hydrol. 108 235–247

    Google Scholar 

  • Stichler W. and Herrmann A. 1983. Application of environmental isotope techniques in water balance studies of small basins. New Approaches in Water Balance Computations IAHS Publication no. 148, pp. 93–112.

  • N. Sun M. Elimelech Ne-Zheng. Sun J. Ryan (2001) ArticleTitleA novel two-dimensional model for colloid transport in a physically and geochemically heterogeneous porous media J. Contam. Hydrol. 49 173–199 Occurrence Handle1:CAS:528:DC%2BD3MXjsFWmurw%3D Occurrence Handle11411396

    CAS  PubMed  Google Scholar 

  • B.R. Swistock D.R. DeWalle W.E. Sharpe (1989) ArticleTitleSources of acidic storm flow in an Appalachian headwater stream Water Resour. Res. 25 IssueID10 2139–2147 Occurrence Handle1:CAS:528:DyaK3cXktFWksLw%3D

    CAS  Google Scholar 

  • J.V. Turner D.K. MacPherson R.A. Stokes (1987) ArticleTitleThe mechanisms of chatchment flow processes using natural variations in deuterium and oxygen-18 J. Hydrol. 94 143–162 Occurrence Handle1:CAS:528:DyaL2sXmsVaitrc%3D

    CAS  Google Scholar 

  • S. Uhlenbrook M. Frey Ch Leibundgut P. Maloszewski (2002) ArticleTitleHydrograph separations in a meso-scale mountainous basin at event and seasonal time scales Water Resour. Res. 38 IssueID6 31.1–31.14

    Google Scholar 

  • Voerkelius S. 1990 Isotopendiskriminierungen bei der Nitrifikation und Denitrifikation; Grundlagen und Anwendungen der Herkunfts-Zuordnung von Nitrat und Distickstoffmonoxid. Ph.D. thesis, Tech. Univ., MunichGermany (in German).

  • L.I. Wassenaar (1995) ArticleTitleEvaluation of the origin and fate of nitrate in the Abbotsford Aquifer using the isotopes of 15N and 18O in NO3 Appl. Geochem. 10 391–405 Occurrence Handle1:CAS:528:DyaK2MXptVCmtb0%3D

    CAS  Google Scholar 

  • F. Wendland H. Albert M. Bach R. Schmidt (1993) Atlas zum Nitratstrom in der Bundesrepublik Deutschland Springer Berlin, Heidelberg

    Google Scholar 

  • Williard K.W.J., DeWalle D.R., Edwards P.J. and Sharpe W.E. 2001. 18O isotopic separation of stream nitrate sources in mid-Appalachian forested watersheds. J. Hydrol. 174–188.

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Einsiedl, F., Maloszewski, P. & Stichler, W. Estimation of denitrification potential in a karst aquifer using the 15N and 18O isotopes of NO 3 . Biogeochemistry 72, 67–86 (2005). https://doi.org/10.1007/s10533-004-0375-8

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