Surface/atmosphere exchange and chemical interactions of reactive nitrogen compounds above a manured grassland

Manure application to managed grassland is a common agricultural practice. There are, however, limited studies looking at the fluxes and interactions of reactive N compounds and aerosols following fertilisation with manure. In this study, state-of-the-art chemical analysers (GRAEGOR, QCLAS, PTRMS) were used to investigate concentrations, fluxes and chemical interactions of reactive nitrogen containing trace gases (NH3, HNO3, HONO) and aerosols (NO3−) above a grassland fertilised with 164 kg N ha−1 of cattle slurry. Emissions of NH3 peaked at >67 μg m−2 s−1, based on a 30 min average. The estimated overall loss of total ammoniacal nitrogen (TAN) from the applied slurry through NH3 emissions in the first 5 days was 33.5%. The average trimethylamine flux in the first 31 h following the first slurry application was 40 ng m−2 s−1 and amounted to 0.38% of the NH3-N emissions. Apparent nitrate aerosol emissions were observed following the slurry application peaking at 13.0 ng m−2 s−1. This suggests formation of NH4NO3 from reaction of the emitted NH3 with atmospheric HNO3, consistent with the observation of gaseous concentration products exceeding the dissociation constants of ammonium nitrate. Fluxes of total nitrate (HNO3 + NO3−) were bi-directional and positive during the mid-day period after fertilisation, suggesting that the slurry acted as a net source for these compounds. There is evidence of small HONO emission following fertilisation (up to 1 ng m−2 s−1), although the production process is currently not identified. By contrast, all compounds showed deposition to the adjacent unfertilised grassland.