Diurnal fluxes and the isotopomer ratios of N(2)O in a temperate grassland following urine amendment

There is an urgent need to provide an accurate, up-to-date estimate of N(2)O fluxes in order that national policies can be developed to reduce emissions of N(2)O from soils. There are only limited data on temporal and diurnal patterns of N(2)O fluxes to the atmosphere, mainly due to constraints in the measurement techniques. In this paper we present the first terrestrial source values of N(2)O isotopomers and have measured and quantified the temporal and diurnal variability in N(2)O fluxes following urine addition to a grassland system in the UK. The experiment was carried out over a 2-week period on an artificially drained grassland system at the Institute of Grassland and Environmental Research (IGER), North Wyke, UK. Duplicate samples of urine, each of 2 L, were collected from dairy cows and applied to chambers (of area 0.16 m(2)). The N(2)O diurnal fluxes from urine and control (no urine) plots were measured by an automatic closed chamber technique. The isotopomers of N(2)O were obtained by analysing the gas samples collected during a peak emission phase. Soil and meteorological data were also collected. The results showed strong diurnal variations in N(2)O fluxes with minimum fluxes generally occurring between 7:00 and 14:00 hrs. The total cumulative flux of N(2)O for the whole experimental period was higher by a factor of >2 compared with estimates based on the daytime (between 10.00-16.00 hrs) measurements only. Therefore, measurements of N(2)O fluxes based on daily single exposure and expressed on a 24-h basis could impose a considerable bias and inaccuracy to the emission estimates, depending on when it was taken. The measured site preference values (difference between the centre (delta(15)Nalpha) and the end (delta(15)Nbeta) N atom of the N(2)O molecule) for soil-emitted N(2)O measured during our study were always lower than the tropospheric value. This work confirms that the enhanced tropospheric N(2)O site preference value could be the result of the back injection from the stratosphere. The intramolecular isotope ratios of nitrogen (delta(15)N) and oxygen (delta(18)O) and the site preference of the emitted N(2)O indicated that there was a shift of processes during the measurement period.