Isotopic composition of nitrogen species in groundwater under agricultural areas: A review

Sci Total Environ. 2018 Apr 15:621:1415-1432. doi: 10.1016/j.scitotenv.2017.10.086. Epub 2017 Oct 23.

Abstract

This work reviews applications of stable isotope analysis to the studies of transport and transformation of N species in groundwater under agricultural areas. It summarizes evidence regarding factors affecting the isotopic composition of NO3-, NH4+ and N2O in subsurface, and discusses the use of 11B, 18O, 13C, 34S, 87Sr/86Sr isotopes to support the analysis of δ15N values. The isotopic composition of NO3-, NH4+ and N2O varies depending on their sources and dynamics of N cycle processes. The reported δ15N-NO3- values for sources of NO3- are: soil organic N - +3‰-+8‰, mineral fertilizers - -8‰-+7‰; manure/household waste - +5‰ to +35‰. For NH4+ sources, the isotopic signature ranges are: organic matter - +2.4-+4.1‰, rainwater - -13.4-+2.3‰, mineral fertilizers - -7.4-+5.1‰, household waste - +5-+9‰; animal manure - +8-+11‰. For N2O, isotopic composition depends on isotopic signatures of substrate pools and reaction rates. δ15N values of NO3- are influenced by fractionation effects occurring during denitrification (ɛ=5-40‰), nitrification (ɛ=5-35‰) and DNRA (ɛ not reported). The isotopic signature of NH4+ is also affected by nitrification and DNRA as well as mineralization (ɛ=1‰), sorption (ɛ=1-8‰), anammox (ɛ=4.3-7.4‰) and volatilization (ɛ=25‰). As for the N2O, production of N2O leads to its depletion in 15N, whereas consumption - to enrichment in 15N. The magnitude of fractionation effects occurring during the considered processes depends on temperature, pH, DO, C/NO3- ratio, size of the substrate pool, availability of electron donors, water content in subsoil, residence time, land use, hydrogeology. While previous studies have accumulated rich data on isotopic composition of NO3- in groundwater, evidence remains scarce in the cases of NH4+ and N2O. Further research is required to consider variability of δ15N-NH4+ and δ15N-N2O in groundwater across agricultural ecosystems.

Keywords: Agriculture; Groundwater pollution; N anthropogenic sources; N cycle processes; N isotopes; Stable isotope analysis.

Publication types

  • Review