Heterogeneous conversion of NO₂ and NO on HNO₃ treated soot surfaces: atmospheric implications

Abstract

Abstract. In the present study, the heterogeneous conversion of nitrogen oxide (NO) and nitrogen dioxide (NO2) was studied at atmospheric humidity levels on flame soot surfaces treated with gaseous nitric acid (HNO3). In addition, the heterogeneous reaction of HNO3 on soot was investigated at atmospheric humidity. For the treatment of soot by pure HNO3 only reversible uptake with a surface coverage of ~1-2x1014 HNO3 cm-2 was observed for HNO3 mixing ratios in the range 250-800ppbv. Only for higher HNO3 mixing ratios of >800ppbv the formation of NO and NO2 was observed. The results were not affected by the addition of NO. In none of the experiments with HNO3 the formation of nitrous acid (HONO) was observed. For HNO3 mixing ratios <600ppbv the upper limit yields for HONO, NO2 and NO were found to be <0.2%, <0.5% and <1%, respectively. Compared to untreated soot, the product formation of the reaction of NO2 with soot was not significantly affected when the soot surface was treated with gaseous HNO3 prior to the experiment. Only for high surface coverage of HNO3 the formation of HONO was suppressed in the initial phase of the reaction, probably caused by the blocking of active sites by adsorbed HNO3. Under the assumption that the experimental findings for the used model flame soot can be extrapolated to atmospheric soot particles, the results show that the reactions of HNO3 and HNO3+NO on soot surfaces are unimportant for a "renoxification" of the atmosphere and do not represent an atmospheric HONO source. In addition, the integrated HONO yield of ca. 1014cm-2 in the reaction of NO2 with soot is not significantly influenced by simulated atmospheric processing of the soot surface by HNO3, and is still too small to explain HONO formation in the atmosphere.