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https://doi.org/10.5194/acp-2019-944
© Author(s) 2019. This work is distributed under
the Creative Commons Attribution 4.0 License.
https://doi.org/10.5194/acp-2019-944
© Author(s) 2019. This work is distributed under
the Creative Commons Attribution 4.0 License.

Submitted as: research article 09 Dec 2019

Submitted as: research article | 09 Dec 2019

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This preprint is currently under review for the journal ACP.

Contribution of HONO to the atmospheric oxidation capacity in an industrial zone in the Yangtze River Delta region of China

Jun Zheng1, Xiaowen Shi1, Yan Ma1,2, Xinrong Ren3,4,5, Halim Jabbour1, Yiwei Diao1,6, Weiwei Wang6, Yifeng Ge1, Yuchan Zhang1, and Wenhui Zhu1 Jun Zheng et al.
  • 1Collaborative Innovation Center of Atmospheric Environment and Equipment Technology, Nanjing University of Information Science & Technology, Nanjing 210044, China
  • 2NUIST Reading Academy, Nanjing University of Information Science & Technology, Nanjing 210044, China
  • 3Air Resources Laboratory, National Oceanic and Atmospheric Administration, College Park, Maryland, USA
  • 4Department of Atmospheric and Oceanic Science, University of Maryland, College Park, Maryland, USA
  • 5Cooperative Institute for Satellite Earth System Studies, University of Maryland, College Park, Maryland, USA
  • 6Key Laboratory for Aerosol-Cloud-Precipitation of China Meteorological Administration, Department of Atmospheric Physics, Nanjing University of Information Science and Technology, Nanjing 210044, China

Abstract. A suite of instruments were deployed to simultaneously measure nitrous acid (HONO), nitrogen oxides (NOx = NO + NO2), carbon monoxide (CO), ozone (O3), volatile organic compounds (VOCs, including formaldehyde (HCHO)) and meteorological parameters near a typical industrial zone in Nanjing of the Yangtze River Delta region, China. High levels of HONO were detected using a wet chemistry-based method. HONO ranged from 0.03–7.04 ppbv with an average of 1.32 ± 0.92 ppbv. Elevated daytime HONO was frequently observed with a minimum of several hundreds of pptv on average, which cannot be explained by the homogeneous OH + NO reaction (POH+NO) alone, especially during periods with high loadings of particulate matters (PM2.5). The HONO chemistry and its impact on atmospheric oxidation capacity in the study area were further investigated using a MCM-box model. The results show that the average hydroxyl radical (OH) production rate was dominated by the photolysis of HONO (7.13×106 molecules cm−3 s−1), followed by ozonolysis of alkenes (3.94×106 molecules cm−3 s−1), photolysis of O3 (2.46×106 molecules cm−3 s−1) and photolysis of HCHO (1.60×106 molecules cm−3 s−1), especially within the plumes originated from the industrial zone. The observed similarity between HONO/NO2 and HONO in diurnal profiles strongly suggests that HONO in the study area was likely originated from NO2 heterogeneous reactions. The average nighttime NO2 to HONO conversion rate was determined to be ~ 0.9 % hr−1. Good correlation between nocturnal HONO/NO2 and the products of particle surface area density (S/V) and relative humidity (RH), S/V·RH, supports the heterogeneous NO2/H2O reaction mechanism. The other HONO source, designated as Punknonwn, was about twice as much as POH+NO on average and displayed a diurnal profile with an evidently photo-enhanced feature, i.e., photosensitized reactions of NO2 may be an important daytime HONO source. Nevertheless, our results suggest that daytime HONO formation was mostly due to the light-induced conversion of NO2 on aerosol surfaces but heterogeneous NO2 reactions on ground surface dominated nocturnal HONO production. Concurred elevated HONO and PM2.5 levels strongly indicate that high HONO may increase the atmospheric oxidation capacity and further promote the formation of secondary aerosols, which may in turn synergistically boost NO2/HONO conversion by providing more heterogeneous reaction sites.

Jun Zheng et al.

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Short summary
High level of HONO is formed from NOx emitted by industrial activities, which in turn will promote secondary air pollutants (e.g., aerosol and O3) formation within these plumes by contributing to free radical productions. Heterogeneous reactions on aerosol surfaces are found to be one of the major formation routes of HONO. Therefore, HONO is playing a synergic role in haze formation in areas populated with heavy industries.
High level of HONO is formed from NOx emitted by industrial activities, which in turn will...
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