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Title: | Re-examination of C1-C5 alkyl nitrates in Hong Kong using an observation-based model | Authors: | Lyu, XP Ling, ZH Guo, H Saunders, SM Lam, SHM Wang, N Wang, Y Liu, M Wang, T |
Issue Date: | Nov-2015 | Source: | Atmospheric environment, Nov. 2015, v. 120, p. 28-37 | Abstract: | The photochemical formation of alkyl nitrates (RONO2) and their impact on ozone (O3) formation were investigated using a Photochemical Box Model incorporating the Master Chemical Mechanism (PBM-MCM). The model was constrained with field measurement data collected on selected O3 episode days at Tai O, a rural-coastal site in southwestern Hong Kong, from August 2001-December 2002. The in-situ observations showed that the sum of C1-C5 RONO2 varied from 30.7 ± 14.8 pptv in spring to 120.7 ± 10.4 pptv in autumn, of which 2-butyl nitrate dominated with the highest average concentration of 30.8 ± 2.6 pptv. Model simulations indicated that the pathway of CH3O reacting with NO2, proposed in our previous study, made minor contributions (11.3 ± 0.7%) to methyl nitrate formation. Indeed, 51.8 ± 3.1% and 36.5 ± 6.3% of the methyl nitrate was attributed to the reaction of CH3O2+NO and to oceanic emissions/biomass burning, respectively. For the C2-C5 alkyl nitrates, the contribution of photochemical formation increased with increasing carbon number, ranging from 64.4 ± 4.0% for ethyl nitrate (EtONO2) to 72.6 ± 4.2% for 2-pentyl nitrate (2-PenONO2), while the contribution of oceanic emissions/biomass burning decreased from 35.1 ± 6.5% for EtONO2 to 26.8 ± 6.8% for 2-PenONO2. Model simulations of photochemical O3 levels influenced by RONO2 chemistry showed that the formation of methyl-, ethyl-, i-propyl-, n-propyl-, 2-butyl-, 2-pentyl-, and 3-pentyl-nitrates led to O3 reduction of 0.05 ± 0.03, 0.05 ± 0.03, 0.06 ± 0.02, 0.02 ± 0.02, 0.18 ± 0.04, 0.09 ± 0.02 and 0.06 ± 0.02 ppbv, respectively, with an average reduction rate of 11.0 ± 3.2 ppbv O3 per 1 ppbv RONO2 formation. The C1-C5 RONO2 constituted 18.6 ± 1.9% of the entire RONO2, and had a nitrogen reserve of 4.1 ± 0.2%, implying their potential influence on O3 production in downwind areas. | Keywords: | Alkyl nitrate Field observation O3 production PBM-MCM model Photochemical formation |
Publisher: | Pergamon Press | Journal: | Atmospheric environment | ISSN: | 1352-2310 | EISSN: | 1873-2844 | DOI: | 10.1016/j.atmosenv.2015.08.083 | Rights: | © 2015 Elsevier Ltd. All rights reserved. © 2015. This manuscript version is made available under the CC-BY-NC-ND 4.0 license https://creativecommons.org/licenses/by-nc-nd/4.0/ The following publication Lyu, X. P., Ling, Z. H., Guo, H., Saunders, S. M., Lam, S. H. M., Wang, N., ... & Wang, T. (2015). Re-examination of C1–C5 alkyl nitrates in Hong Kong using an observation-based model. Atmospheric Environment, 120, 28-37. is available at https://doi.org/10.1016/j.atmosenv.2015.08.083. |
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