Reduction and Photoreduction of NO2 in Humic Acid Films as a Source of HONO, ClNO, N2O, NOX, and Organic Nitrogen

Abstract

Atmospheric nitrous acid (HONO), a trace atmospheric gas, is often underestimated in global atmospheric models due to the poor understanding of its daytime sources and sinks. HONO is known to accumulate during nighttime and undergo rapid photodissociation during the day to form NO and highly reactive OH radical, making it important to have accurate atmospheric HONO estimations. Despite its rapid photolysis, recent field observations have found quasi-steady-state concentrations of HONO at midday, suggesting photolytic HONO formation pathways to replenish daytime atmospheric HONO. Recent studies suggest that the presence of complex organic photosensitizers in atmospheric aerosols converts atmospheric NO2 into HONO. To better understand the effect of environmental photosensitizers in daytime mechanisms of HONO formation, we present here laboratory studies on the heterogeneous photolytic reduction of NO2 by humic acid films, a proxy for organic chromophoric compounds. The effect of pH and Cl- in the photosensitized formation of HONO and other nitrogen-containing gases is also investigated. A dual Fourier transform infrared (FTIR) system is utilized to simultaneously perform in situ analysis of condensed-phase reactants and gas-phase products. We find that the rate of HONO formation is faster at lower pHs. Nitrogen incorporation in the complex organic chromophore is observed, suggesting a competing pathway that results in suppressed daytime formation of nitrogenous gases. Significantly, the presence of chloride ions also leads to the organic-mediated photolytic formation of nitrosyl chloride (ClNO), a known precursor of HONO. Overall, this work shows that organic acid photosensitizers can reduce adsorbed NO2 to form HONO, ClNO, and NO while simultaneously incorporating nitrogen into the organic chromophores present in aerosol.