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Recently, realistic simulation of nitrous acid (HONO) based on the HONO/NOx ratio of 0.02 was found to have a significant impact on the global budgets of HOx (OH + HO2) and gas phase oxidation products in polluted regions, especially in winter when other photolytic sources are of minor importance. It has been reported that chemistry-transport models underestimate sulphate concentrations, mostly during winter. Here we show that simulating realistic HONO levels can significantly enhance aerosol sulphate (S(VI)) due to the increased formation of H2SO4. Even though in-cloud aqueous phase oxidation of dissolved SO2 (S(IV)) is the main source of S(VI), it appears that HONO related enhancement of H2O2 does not significantly affect sulphate because of the predominantly S(IV) limited conditions, except over eastern Asia. Nitrate is also increased via enhanced gaseous HNO3 formation and N2O5 hydrolysis on aerosol particles. Ammonium nitrate is enhanced in ammonia-rich regions but not under ammonia-limited conditions. Furthermore, particle number concentrations are also higher, accompanied by the transfer from hydrophobic to hydrophilic aerosol modes. This implies a significant impact on the particle lifetime and cloud nucleating properties. The HONO induced enhancements of all species studied are relatively strong in winter though negligible in summer. Simulating realistic HONO levels is found to improve the model-measurement agreement of sulphate aerosols, most apparent over the US. Our results underscore the importance of HONO for the atmospheric oxidizing capacity and corroborate the central role of cloud chemical processing in S(IV) formation. [ABSTRACT FROM AUTHOR]

Nitrous acid (HONO) photolysis can significantly increase HOx (OH + HO2) radical formation, enhancing organic and inorganic oxidation products in polluted regions, especially during winter. It has been reported that chemistry-transport models underestimate sulphate concentrations, mostly during winter. Here we show that HONO can significantly enhance aerosol sulphate (S(VI)), mainly due to the increased formation of H2SO4. Even though in-cloud aqueous phase oxidation of dissolved SO2 (S(IV)) is the main source of S(VI), it appears that HONO related enhancement of H2O2 does not significantly affect sulphate because of the predominantly S(IV) limited conditions, except over eastern Asia. Nitrate is also increased via enhanced gaseous HNO3 formation and N2O5 hydrolysis on aerosol particles. Ammonium nitrate is enhanced in ammonia-rich regions but not under ammonia-limited conditions. Furthermore, particle number concentrations are also higher, accompanied by the transfer from hydrophobic to hydrophilic aerosol modes. This implies a significant impact on the particle lifetime and cloud nucleating properties. The HONO induced enhancements of all species studied are relatively strong in winter though negligible in summer. Simulating realistic HONO levels is found to improve the model-measurement agreement of sulphate aerosols, most apparent over the US. Our results underscore the importance of HONO for the atmospheric oxidizing capacity and the central role of cloud chemical processing in aerosol formation. [ABSTRACT FROM AUTHOR]

The photolysis of HONO is important for the atmospheric HOx (OH +HO2) radical budget and ozone formation, especially in polluted air. Nevertheless, owing to the incomplete knowledge of HONO sources, realistic HONO mechanisms have not yet been implemented in global models. We investigated measurement data sets from 15 field measurement campaigns conducted in different countries worldwide. It appears that the HONO/NOx ratio is a good proxy predictor for HONO mixing ratios under different atmospheric conditions. From the robust relationship between HONO and NOx, a representative mean HONO/NOx ratio of 0.02 has been derived. Using a global chemistry-climate model and employing this HONO/NOx ratio, realistic HONO levels are simulated, being about one order of magnitude higher than the reference calculations that only consider the reaction OH+NO→HONO. The resulting enhancement of HONO significantly impacts HOx levels and photo-oxidation products (e.g, O3, PAN), mainly in polluted regions. Furthermore, the relative enhancements in OH and secondary products are higher in winter than in summer, thus enhancing the oxidation capacity in polluted regions, especially in winter when other photolytic OH sources are of minor importance. Our results underscore the need to improve the understanding of HONO chemistry and its representation in atmospheric models. [ABSTRACT FROM AUTHOR]

The photolysis of HONO is important for the atmospheric HOx (OH+HO2) radical budget and ozone formation, especially in polluted air. Nevertheless, owing to the incomplete knowledge of HONO sources, realistic HONO mechanisms have not yet been implemented in global models. We investigated measurement data sets from 15 field 5 measurement campaigns conducted in different countries worldwide. It appears that the HONO/NOx ratio is a good proxy predictor for HONO mixing ratios under different atmospheric conditions. From the robust relationship between HONO and NOx, a representative mean HONO/NOx ratio of 0.02 has been derived. Using a global chemistry-climate model and employing this HONO/NOx ratio, realistic HONO levels are simulated, being about one order of magnitude higher than the reference calculations, which only consider the reaction OH+NO→HONO. The resulting enhancement of HONO significantly impacts HOx levels and photo-oxidation products (e.g, O3, PAN), mainly in polluted regions. Furthermore, the relative enhancements in OH and secondary products were higher in winter than in summer, thus enhancing the oxidation capacity in polluted regions, especially in winter, when the other photolytic OH sources are of minor importance. Our results underscore the need to improve the understanding of HONO chemistry and its representation in atmospheric models. [ABSTRACT FROM AUTHOR]

The oxidation capacity of the highly polluted urban area of Santiago, Chile has been evaluated during a summer measurement campaign carried out from 8-20 March 2005. The hydroxyl (OH) radical budget was evaluated employing a simple quasi-photostationary-state model (PSS) constrained with simultaneous measurements of HONO, HCHO, O3, NO, NO2, j(O¹D), j(NO2), 13 alkenes and meteorological parameters. In addition, a zero dimensional photochemical box model based on the Master Chemical Mechanism (MCMv3.1) has been used to estimate production rates and total free radical budgets, including OH, HO2 and RO2. Besides the above parameters, the MCM model has been constrained by the measured CO and volatile organic compounds (VOCs) including alkanes and aromatics. Both models simulate the same OH concentration during daytime indicating that the primary OH sources and sinks included in the simple PSS model predominate. Mixing ratios of the main OH radical precursors were found to be in the range 0.8- 7 ppbv (HONO), 0.9-11 ppbv (HCHO) and 0-125 ppbv (O3). The alkenes average mixing ratio was ∼58 ppbC accounting for ∼12% of the total identified non-methane hydrocarbons (NMHCs). During the daytime (08:00 h-19:00 h), HONO photolysis was shown to be the most important primary OH radical source comprising alone ∼55% of the total initial production rate, followed by alkene ozonolysis (∼24%) and photolysis of HCHO (∼16%) and O3 (∼5%). The calculated average and maximum daytime OH production rates from HONO photolysis was 1.7 ppbv h-1 and 3.1 ppbv h-1, respectively. Based on the experimental results a strong photochemical daytime source of HONO is proposed. A detailed analysis of the sources of OH radical precursors has also been carried out. [ABSTRACT FROM AUTHOR]