Intercomparison of fast response commercial gas analysers for nitrous oxide flux measurements under field conditions

Abstract

Four gas analysers capable of measuring nitrous oxide (N2O) concentration at a response time necessary for eddy covariance flux measurements were operated from spring until winter 2011 over a field cultivated with reed canary grass (RCG, Phalaris arundinacea, L.), a perennial bioenergy crop in eastern Finland. The instruments were TGA100A (Campbell Scientific Inc.), CW-TILDAS-CS (Aerodyne Research Inc.), N2O / CO-23d (Los Gatos Research Inc.) and QC-TILDAS-76-CS (Aerodyne Research Inc.). The period with high emissions, lasting for about 2 weeks after fertilization in late May, was characterized by an up to 2 orders of magnitude higher emission, whereas during the rest of the campaign the N2O fluxes were small, from 0.01 to 1 nmol m−2 s−1. Two instruments, CW-TILDAS-CS and N2O / CO-23d, determined the N2O exchange with minor systematic difference throughout the campaign, when operated simultaneously. TGA100A produced the cumulatively highest N2O estimates (with 29% higher values during the period when all instruments were operational). QC-TILDAS-76-CS obtained 36% lower fluxes than CW-TILDAS-CS during the first period, including the emission episode, whereas the correspondence with other instruments during the rest of the campaign was good. The reasons for systematic differences were not identified, suggesting further need for detailed evaluation of instrument performance under field conditions with emphasis on stability, calibration and any other factors that can systematically affect the accuracy of flux measurements. The instrument CW-TILDAS-CS was characterized by the lowest noise level (with a standard deviation of around 0.12 ppb at 10 Hz sampling rate) as compared to N2O / CO-23d and QC-TILDAS-76-CS (around 0.50 ppb) and TGA100A (around 2 ppb). We identified that for all instruments except CW-TILDAS-CS the random error due to instrumental noise was an important source of uncertainty at the 30 min averaging level and the total stochastic error was frequently of the same magnitude as the fluxes when N2O exchange was small at the measurement site. Both instruments based on continuous-wave quantum cascade laser, CW-TILDAS-CS and N2O / CO-23d, were able to determine the same sample of low N2O fluxes with a high mutual coefficient of determination at the 30 min averaging level and with minor systematic difference over the observation period of several months. This enables us to conclude that the new-generation instrumentation is capable of measuring small N2O exchange with high precision and accuracy at sites with low fluxes.