An intercomparison of two chamber methods for the determination of emission of nitric oxide from soil

Two chamber-based methods for measurement of emission of NO from soil have been compared. One method measured NO by conversion to NO₂ with a CrO₃ converter and NO₂ detection by luminol chemiluminescence. The other technique detects NO directly via NO/ozone chemiluminescence. The techniques were tested with a glass manifold system by addition of NO and other trace gases into a flowing zero air gas stream; water vapor was also added to the carrier gas in some cases. A second set of tests involved the simultaneous determination of NO concentrations from a chamber placed over the soil. Finally, flux measurements were made independently from common plots and from different plots within the same field. The luminol system was unaffected by the presence of ammonia, methylamine, acetonitrile and nitrous oxide, but had a lower response to NO in the presence of water vapor. The decrease was 7% at a relative humidity of 50%, and about 3% at a relative humidity of 23%. The NO/ozone chemiluminescence system was not influenced by any of the species doped into the gas stream. The simultaneous chamber data also showed a decreased response from the luminol system that was consistent with the humidity effect observed in the manifold tests. The average of independently measured flux values from common plots agreed reasonably well. However, the overall site mean flux determined by the luminol system was 74% of that of the NO/ozone system due to a larger data set from the luminol system. This comparison demonstrates that flux spatial heterogeneity can overwhelm analytical uncertainties, and that large sample sizes are needed to accurately characterize field fluxes.