Chemical loss processes of isocyanic acid, HNCO, in the atmosphere

Abstract

Abstract. The impact of chemical loss processes of isocyanic acid was studied by a combined theoretical and modeling study. The potential energy surfaces of the reactions of HNCO with OH and NO3 radicals, Cl atoms, and ozone, were studied using high-level CCSD(T)/CBS(DTQ)//M06-2X/aug-cc-pVTZ quantum chemical methodologies, followed by TST theoretical kinetic predictions of the rate coefficients at temperatures of 200–3000 K. It was found that the reactions are all slow in atmospheric conditions, with k(300 K) ≤ 7 × 10−16 cm3 molecule−1 s−1; the predictions are in good agreement with earlier experimental work, where available. The reverse reactions of NCO radicals, of importance mostly in combustion, were also examined briefly. The global model confirms that gas phase chemical loss of HNCO is a negligible process, contributing less than 1 %. Removal of HNCO by clouds and precipitation is a larger sink, contributing for about 10 % of the total loss, while globally dry deposition is the main sink, accounting for ~ 90 %. The global simulation also shows that due to its long chemical lifetime in the free troposphere, HNCO can be efficiently transported into the UTLS by deep convection events. Average daily concentrations of HNCO are found to rarely exceed levels considered potentially toxic, though locally instantaneous toxic levels are expected.the free troposphere, HNCO can be efficiently transported into the UTLS by deep convection events. Average daily concentrations of HNCO are found to rarely exceed levels considered potentially toxic, though locally instantaneous toxic levels are expected.