Modelling nitrogen and oxygen isotope fractionation during denitrification in a lacustrine redox-transition zone

The stable isotope composition (δ¹⁵N and δ¹⁸O) of nitrate was measured during Summer 1999 in the anaerobic hypolimnion of eutrophic Lake Lugano (Switzerland). Denitrification was demonstrated by a progressive nitrate depletion coupled to increasing δ¹⁵N and δ¹⁸O values for residual nitrate. Maximum δ¹⁵N and δ¹⁸O values amounted to 27.2 and 15.7‰, respectively.¹⁵N and ¹⁸O enrichment factors for denitrification (ε) were estimated using a closed-system model and a dynamic diffusion-reaction model. Using the Rayleigh equation (closed-system approach), we obtained ε values of −11.2 and −6.6‰ for nitrogen and oxygen, respectively. The average ε values derived using the diffusion-reaction model were determined to be −20.7 ± 3.8 for nitrogen and −11.0 ± 1.7 for oxygen. Both N and O isotope fractionation appeared to be lower when denitrification rates where high, possibly in association with high organic carbon availability. In addition, variations in the isotope effects may be attributed to the variable importance of sedimentary denitrification having only a small isotope effect on the water column. The combined measurement of N and O isotope ratios in nitrate revealed that coupled nitrification-denitrification in the open-water was of minor importance. This is the first study of nitrogen and oxygen isotope effects associated with microbial denitrification in a natural lake. Moreover, this study confirms the high potential of δ¹⁸O of nitrate as a valuable biogeochemical tracer in aquatic systems, complementing nitrate δ¹⁵N.