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Atmospheric Chemistry and Physics An interactive open-access journal of the European Geosciences Union
https://doi.org/10.5194/acp-2018-9
© Author(s) 2018. This work is distributed under
the Creative Commons Attribution 4.0 License.
Research article
16 Jan 2018
Review status
This discussion paper is a preprint. It is a manuscript under review for the journal Atmospheric Chemistry and Physics (ACP).
Chlorine oxidation of VOCs at a semi-rural site in Beijing: Significant chlorine liberation from ClNO2 and subsequent gas and particle phase Cl-VOC production
Michael Le Breton1, Åsa M. Hallquist2, Ravi Kant Pathak1, David Simpson3,4, Yujue Wang5, John Johansson3, Jing Zheng5, Yudong Yang5, Dongjie Shang5, Haichao Wang5, Qianyun Liu6, Chak Chan7, Tao Wang8, Thomas J. Bannan9, Michael Priestley9, Carl J. Percival9,a, Dudley E. Shallcross10, Keding Lu5, Song Guo5, Min Hu5, and Mattias Hallquist1 1Department of Chemistry and Molecular Biology, University of Gothenburg, Gothenburg, Sweden
2IVL Swedish Environmental Research Institute, Gothenburg, Sweden
3Earth and Space Sciences, Chalmers University of Technology, Gothenburg, Sweden
4Norwegian Meteorological Institute, Oslo, Norway
5State Key Joint Laboratory of Environmental Simulation and Pollution Control, College of Environmental Sciences and Engineering, Peking University, Beijing, China
6Division of Environment and Sustainability, The Hong Kong University of Science and Technology, Clearwater Bay, Kowloon, Hong Kong
7School of Energy and Environment, City University of Hong Kong, Hong Kong
8Department of Civil and Environmental Engineering, The Hong Kong Polytechnic University, Hong Kong, China
9Centre for Atmospheric Science, School of Earth, Atmospheric and Environmental Science, University of Manchester, Manchester, UK
10School of Chemistry, University of Bristol, Cantock's Close, Bristol, BS8 1TS, UK
anow at: Jet Propulsion laboratory, Pasadena, California, USA
Abstract. Nitryl Chloride (ClNO2) accumulation at night-time acts as a significant reservoir for active chlorine and impacts the following day's photochemistry when the chlorine atom is liberated at sunrise. Here, we report simultaneous measurements of N2O5, a suite of inorganic halogens including ClNO2 and Cl-VOCs in the gas and particle phase utilizing the FIGAERO-ToF-CIMS during an intensive measurement campaign 40 km Northwest of Beijing in May and June 2016. A maximum concentration of 2900 ppt of ClNO2 was observed with a mean campaign night-time concentration of 487 ppt, appearing to have an anthropogenic source supported by correlation with SO2, CO and benzene, which often persisted at high levels after sunrise until midday. This was attributed to such high concentrations persisting after numerous e-folding times of the photolytic lifetime enabling the chlorine atom production to reach 2.3 × 105 molecules cm−3 from ClNO2 alone, peaking at 9:30 am and up to 8.4 × 105 molecules cm−3 when including the supporting inorganic halogen measurements.

Cl-VOCs were measured in the particle and gas phase for the first time at high time resolution and illustrate how the iodide ToF-CIMS can detect unique markers of chlorine atom chemistry in ambient air from both biogenic and anthropogenic sources. Their presence and abundance can be explained via time series of their measured and steady state calculated precursors, enabling the assessment of competing OH and chlorine atom oxidation via measurements of products from both of these mechanisms and their relative contribution to SOA formation.

Citation: Le Breton, M., Hallquist, Å. M., Pathak, R. K., Simpson, D., Wang, Y., Johansson, J., Zheng, J., Yang, Y., Shang, D., Wang, H., Liu, Q., Chan, C., Wang, T., Bannan, T. J., Priestley, M., Percival, C. J., Shallcross, D. E., Lu, K., Guo, S., Hu, M., and Hallquist, M.: Chlorine oxidation of VOCs at a semi-rural site in Beijing: Significant chlorine liberation from ClNO2 and subsequent gas and particle phase Cl-VOC production, Atmos. Chem. Phys. Discuss., https://doi.org/10.5194/acp-2018-9, in review, 2018.
Michael Le Breton et al.
Michael Le Breton et al.
Michael Le Breton et al.

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Short summary
We apply state of the art chemical characterization to determine the chloride radical production in Beijing via measurement of inorganic halogens at a semi rural site. The high concentration of inorganic halogens, namely nitryl chloride, enables the production of a chlorinated volatile organic compounds which are measured in both the gas and particle phase simultaneously. This enables the secondary production of aerosols via chlorine oxidation to be directly observed in ambient air.
We apply state of the art chemical characterization to determine the chloride radical production...
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