Evaluation of laser absorption spectroscopic techniques for eddy covariance flux measurements of ammonia

An intercomparison was made between eddy covariance flux measurements of ammonia by a quantum cascade laser absorption spectrometer (QCLAS) and a lead-salt tunable diode laser absorption spectrometer (TDLAS). The measurements took place in September 2004 and again in April 2005 over a managed grassland site in Southern Scotland, U.K. These were also compared with a flux estimate derived from an Ammonia Measurement by ANnular Denuder with online Analysis (AMANDA), using the aerodynamic gradient method (AGM). The concentration and flux measurements from the QCLAS correlated well with those of the TDLAS and the AGM systems when emissions were high, following slurry application to the field. Both the QCLAS and TDLAS, however, underestimated the flux when compared with the AMANDA system, by 64%. A flux loss of 41% due to chemical reaction of ammonia in the QCLAS (and 37% in the TDLAS) sample tube walls was identified and characterized using laboratory tests but did not fully account for this difference. Recognizing these uncertainties, the agreement between the systems was nevertheless very close (R-2 = 0.95 between the QCLAS and the TDLAS; R-2 = 0.84 between the QCLAS and the AMANDA) demonstrating the suitability of the laser absorption methods for quantifying the temporal dynamics of ammonia fluxes.