Measurement of HONO flux using the aerodynamic gradient method over an agricultural field in the Huaihe River Basin, China.

To investigate nitrous acid (HONO) levels and potential HONO sources above crop rotation fields. The HONO fluxes were measured by the aerodynamic gradient (AG) method from 14 December 2019 to 2 January 2020 over an agricultural field in the Huaihe River Basin. The ambient HONO levels were measured at two different heights (0.15 and 1.5 m), showing a typical diurnal cycle with low daytime levels and high nighttime levels. The upward HONO fluxes were mostly observed during the day, whereas deposition dominated at night. The diurnal variation of HONO flux followed solar radiation, with a noontime maximum of 0.2 nmol/(m2∙sec). The average upward HONO flux of 0.06 ± 0.17 nmol/(m2∙sec) indicated that the agricultural field was a net source for atmospheric HONO. The higher HONO/NO2 ratio and NO2-to-HONO conversion rate close to the surface suggested that nocturnal HONO was formed and released near the ground. The unknown HONO source was derived from the daytime HONO budget analysis, with an average strength of 0.31 ppbV/hr at noontime. The surface HONO flux, which was highly correlated with the photolysis frequency J(NO2) (R2 = 0.925) and the product of J(NO2) × NO2 (R2 = 0.840), accounted for ∼23% of unknown daytime HONO source. The significant correlation between HONO fluxes and J(NO2) suggests a light-driven HONO formation mechanism responsible for the surface HONO flux during daytime.

An automated dynamic chamber system for exchange flux measurement of reactive nitrogen oxides (HONO and NOX) in farmland ecosystems of the Huaihe River Basin, China.

An automated dynamic chamber system was first developed to simultaneously measure the HONO flux and NOx flux. The new dynamic chamber system was applied to field observation, and the HONO and NOX exchange flux of farmland in the Huaihe River Basin was obtained for the first time. The performance of the dynamic chamber system was verified in the field. In the field observation, the diurnal variations of the HONO fluxes and NO fluxes before and after a rainfall event exhibited two different trends. Before the rainfall and in the latter stage after the rainfall, the maxima of the HONO fluxes and NO fluxes occurred in the morning, then decreased gradually. However, during the early stage after the rainfall, the HONO fluxes and NO fluxes gradually increased in the morning and reached their maximum values in the afternoon. During the measurement period, the maximum HONO flux was 7.69 ng N m-2 s-1 and the maximum NO flux was 34.52 ng N m-2 s-1. There was no significant correlation between HONO flux and temperature before the rainfall and in the latter stage after the rainfall period, although the correlation coefficient (R) between HONO flux and temperature reached 0.78 in the early stage after the rainfall period, and the R between NO flux and HONO flux reached more than 0.6 before and after rainfall periods. The HONO flux of fresh soil samples were the same order of magnitude as that of field observations. The field results indicate that soil emissions are an important source of atmospheric HONO during the crop growth stage. Negative NO2 fluxes were found in most observation periods, and there were significant negative linear correlations between NO2 fluxes and atmospheric NO2 concentrations. The R between ambient NO2 concentration and NO2 flux was 0.79, and the compensation point of NO2 was 5 ppbv.