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Title: | Modeling c-1-c-4 alkyl nitrate photochemistry and their impacts on O-3 production in urban and suburban environments of Hong Kong | Authors: | Lyu, XP Guo, H Wang, N Simpson, IJ Cheng, HR Zeng, LW Saunders, SM Lam, SHM Meinardi, S Blake, DR |
Issue Date: | 16-Oct-2017 | Source: | Journal of geophysical research. Atmospheres, 16, Oct. 2017, v. 122, no. 19, p. 10539-10556 | Abstract: | As intermediate products of photochemical reactions, alkyl nitrates (RONO2) regulate ozone (O-3) formation. In this study, a photochemical box model incorporating master chemical mechanism well reproduced the observed RONO2 at an urban and a mountainous site, with index of agreement in the range of 0.66-0.73. The value 0.0003 was identified to be the most appropriate branching ratio for C-1 RONO2, with the error less than 50%. Although levels of the parent hydrocarbons and nitric oxide (NO) were significantly higher at the urban site than the mountainous site, the production of C-2-C-3 RONO2 was comparable to or even lower than at the mountainous site, due to the lower concentrations of oxidative radicals in the urban environment. Based on the profiles of air pollutants at the mountainous site, the formation of C-2-C-4 RONO2 was limited by NOx (volatile organic compounds (VOCs)) when total volatile organic compounds (TVOCs)/NOx was higher (lower) than 10.0 +/- 0.4 parts per billion by volume (ppbv)/ppbv. This dividing ratio decreased (p < 0.05) to 8.7 +/- 0.4 ppbv/ppbv at the urban site, mainly due to the different air pollutant profiles at the two sites. For the formation of C-1 RONO2, the NOx-limited regime extended the ratio of TVOCs/NOx to as low as 2.4 +/- 0.2 and 3.1 +/- 0.1 ppbv/ppbv at the mountainous and urban site, respectively. RONO2 formation led to a decrease of simulated O-3, with reduction efficiencies (O-3 reduction/RONO2 production) of 4-5 parts per trillion by volume (pptv)/pptv at the mountainous site and 3-4 pptv/pptv at the urban site. On the other hand, the variations of simulated O-3 induced by RONO2 degradation depended upon the regimes controlling O-3 formation and the relative abundances of TVOCs and NOx. | Publisher: | Wiley-Blackwell | Journal: | Journal of geophysical research. Atmospheres | ISSN: | 2169-897X | EISSN: | 2169-8996 | DOI: | 10.1002/2017JD027315 | Rights: | ©2017. American Geophysical Union. All Rights Reserved. This is the peer reviewed version of the following article: Lyu, X. P., Guo, H., Wang, N., Simpson, I. J., Cheng, H. R., Zeng, L. W., … Blake, D. R. (2017). Modeling C1–C4 alkyl nitrate photochemistry and their impacts on O3 production in urban and suburban environments of Hong Kong. Journal of Geophysical Research: Atmospheres, 122, 10,539– 10,556, which has been published in final form at https://doi.org/10.1002/2017JD027315. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions. This article may not be enhanced, enriched or otherwise transformed into a derivative work, without express permission from Wiley or by statutory rights under applicable legislation. Copyright notices must not be removed, obscured or modified. The article must be linked to Wiley’s version of record on Wiley Online Library and any embedding, framing or otherwise making available the article or pages thereof by third parties from platforms, services and websites other than Wiley Online Library must be prohibited. |
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Lyu_Modeling_C1–C4_Alkyl.pdf | Pre-Published version | 3 MB | Adobe PDF | View/Open |
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