Flux between soil and atmosphere, vertical concentration profiles in soil, and turnover of nitric oxide: 1. Measurements on a model soil core

A stainless steel soil corer which was filled with homogenized soil was used to measure the flux (J) of NO between soil and atmosphere and the vertical profile of the NO mixing ratios (m) in the soil atmosphere, both as function of the NO mixing ratio (mm _a ) in the atmosphere of the headspace. The NO emission flux decreased linearly with increasing NO mixing ratio and turned into a deposition flux after passage of the compensation point (m _c) at about 400 ppbv NO. Almost the same compensation point was obtained when the turnover of NO was measured in flask-incubated soil samples as function of the NO mixing ratio. The flux (J) of NO at the soil-atmosphere interface was calculated from the production rate (P) of NO and the NO uptake rate constant (k) that were measured in these flask-incubated soil samples using the diffusion model of Galbally and Johansson (1989). The calculated fluxes agreed within <15% with those actually measured. The vertical profiles of NO were fitted to an exponential function and analyzed by Fick's first law of diffusion. The shape of the profiles indicated a net production of NO in the upper 10 cm soil layer when the atmospheric NO mixing ratio was below the compensation point and in a net consumption of NO when the atmospheric NO mixing ratio was above the compensation point. In soil layers below 10 cm depth, the turnover of NO resulted in compensation of production and consumption rates. Measurement of the actual diffusion coefficient using SF₆ showed that gas transport in the soil core was not only due to molecular diffusion but in addition due to a bidirectional gas flow. The experimentally determined diffusion coefficient was smaller than that computed from soil porosities, but resulted together with the additional transport term in NO fluxes that were close (< ±15%) to those measured. This is the first comprehensive study of NO concentration profiles and turnover rates in soil providing a theoretical basis for modelling NO fluxes at the soil-atmosphere interface.     

Flux between soil and atmosphere, vertical concentration profiles in soil, and turnover of nitric oxide: 2. Experiments with naturally layered soil cores

Intact soils cores were taken with a stainless steel corer from a sandy podzol and a loamy luvisol, and used to measure the flux (J) of NO between soil and atmosphere and the vertical profile of the NO mixing ratios (m) in the soil atmosphere, both as function of the NO mixing ratio (m _a) in the atmosphere of the headspace. These measurements were repeated after stepwise excavation of the soil column from the top, e.g. by removing the upper 2 cm soil layer. The gaseous diffusion coefficients of NO in the soil cores were either computed from soil porosity or were determined from experiments using SF6. The NO fluxes (J) that were actually measured at the soil surface were compared to the fluxes which were calculated either from the vertical NO profiles (J _c ) or from the NO production and uptake rates (J _m ) determined in the excavated soil samples. In the podzol, the actually measured (J) and the calculated (J _m , J_m) NO fluxes agreed within a factor of 2. In the luvisol, the measured NO fluxes (J) and those calculated from the vertical NO profiles (J _c ) also agreed well, but in the upper 6 cm soil layer the NO fluxes (J _m ) calculated from NO production and uptake rates were up to 7 times higher than the measured NO fluxes. This poor agreement was probably due to the inhomogeneous distribution of NO production and consumption processes and the change of diffusivities within the top layers of the luvisol. Indeed, the luvisol showed a pronounced maximum of the NO mixing ratios at about 6 cm depth, whereas the podzol column exhibited a steady and exponential decrease of the NO mixing ratios with depth. The inhomogeneities in the luvisol were confirmed by incubation of the soil cores under anoxic conditions. This treatment resulted in production of NO at several depths indicating a zonation of increased potential activities within the luvisol profile which may have biased the modelling of the NO surface flux from turnover measurements in soil samples. Inhomogeneities could be achieved even in homogenized soil by fertilization with nitrate solution.     

Emission of nitrogen oxides (NO x ) from a flooded soil fertilized with urea: Relation to other nitrogen loss processes

Emissions of nitric oxide and other odd nitrogen oxides (NO _x ) from a flooded rice field were studied after urea had been broadcast into the floodwater.The NO _x flux from the fertilized area was very low (0.2×10^-9 g N m^-2 s^-1) for the first few days after application of urea and was high (0.95×10^-9 g N m^-2 s^-1) in the subsequent period when significant nitrite and nitrate were present in the floodwater. At night, little if any NO _x was exhaled but ambient NO₂ was absorbed by the floodwater. An uptake velocity for NO₂ of 3×10^-4 m s^-1 was measured during one night. Maximum NO _x losses were observed near 1300 h when temperature and solar ultraviolet light were maximum.While the amounts of nitrogen oxides emitted are of little agronomic importance (2×10^-3 per cent of the fertilizer nitrogen was lost as NO _x during the 10-day study period), they may well be of significance as a source for some gas reactions in the atmosphere and for the global nitrogen cycle.Of the fertilizer nitrogen applied (as urea) approximately 30% was lost to the atmosphere by NH₃ volatilization, 15% by denitrification, presumably as N₂, and the remainder, less minor losses of NO and N₂O, remained in the plant/soil/water system.Now at Forestry Department, Australian National University, G.P.O. Box 4, ACT 2601, Australia.