Limitations of an Eddy-Covariance System in Measuring Low Ammonia Fluxes

Green manuring of legume crops can improve soil fertility and sustainability. To evaluate its agronomic and environmental effectiveness, gaseous losses of ammonia (NH₃) in the surface layer need to be quantified by direct measurements in the field. However, the application of the eddy-covariance technique to atmospheric NH₃ is challenging: its high reactivity, water solubility, and low background concentrations all hinder the response time of closed-path sensors for fast measurements of NH₃ concentration. Ammonia emissions following green manuring were measured for 21 days using a flux system equipped with a fast-pulsed quantum-cascade tunable-infrared-laser spectrometer. The noisy cross-covariance function for this configuration indicates flux measurements are close to the limit of detection; the low signal-to-noise ratio further increases the uncertainties, introducing a mirroring effect on the fluxes, which results in the rapid alternation between emission and deposition, within the limit of detection (around 13 and 20 ng m^?2 s^?1, at the 95 and 99% confidence limits, respectively). An evaluation of the measurement errors is presented, focussing on three technical aspects of the eddy-covariance system: (1) time lag, (2) random error, and (3) limit of detection. The NH₃ fluxes measured by the spectrometer are close to its limit of detection, with a random error of the same order as the flux.