Processes of ammonia air–surface exchange in a fertilized Zea mays canopy
Abstract. Recent incorporation of coupled soil biogeochemical and bi-directional NH3 air–surface exchange algorithms into regional air quality models holds promise for further reducing uncertainty in estimates of NH3 emissions from fertilized soils. While this represents a significant advancement over previous approaches, the evaluation and improvement of such modeling systems for fertilized crops requires process-level field measurements over extended periods of time that capture the range of soil, vegetation, and atmospheric conditions that drive short-term (i.e., post-fertilization) and total growing season NH3 fluxes. This study examines the processes of NH3 air–surface exchange in a fertilized corn (Zea mays) canopy over the majority of a growing season to characterize soil emissions after fertilization and investigate soil–canopy interactions. Micrometeorological flux measurements above the canopy, measurements of soil, leaf apoplast and dew/guttation chemistry, and a combination of in-canopy measurements, inverse source/sink, and resistance modeling were employed. Over a period of approximately 10 weeks following fertilization, daily mean and median net canopy-scale fluxes yielded cumulative total N losses of 8.4% and 6.1%, respectively, of the 134 kg N ha−1 surface applied to the soil as urea ammonium nitrate (UAN). During the first month after fertilization, daily mean emission fluxes were positively correlated with soil temperature and soil volumetric water. Diurnally, maximum hourly average fluxes of ≈ 700 ng N m−2 s−1 occurred near mid-day, coincident with the daily maximum in friction velocity. Net emission was still observed 5 to 10 weeks after fertilization, although mid-day peak fluxes had declined to ≈ 125 ng N m−2 s−1. A key finding of the surface chemistry measurements was the observation of high pH (7.0–8.5) in leaf dew/guttation, which reduced the ability of the canopy to recapture soil emissions during wet periods. In-canopy measurements near peak leaf area index (LAI) indicated that the concentration of NH3 just above the soil surface was highly positively correlated with soil volumetric water, which likely reflects the influence of soil moisture on resistance to gaseous diffusion through the soil profile and hydrolysis of remaining urea. Inverse source/sink and resistance modeling indicated that the canopy recaptured ≈ 76% of soil emissions near peak LAI. Stomatal uptake may account for 12–34% of total uptake by foliage during the day compared to 66–88% deposited to the cuticle. Future process-level NH3 studies in fertilized cropping systems should focus on the temporal dynamics of net emission to the atmosphere from fertilization to peak LAI and improvement of soil and cuticular resistance parameterizations.