Please use this identifier to cite or link to this item: http://hdl.handle.net/10397/79990
Title: Chlorine oxidation of VOCs at a semi-rural site in Beijing : significant chlorine liberation from ClNO2 and subsequent gas- A nd particle-phase Cl-VOC production
Authors: Le Breton, M
Hallquist, ÅM
Kant, Pathak R
Simpson, D
Wang, Y
Johansson, J
Zheng, J
Yang, Y
Shang, D
Wang, H
Liu, Q
Chan, C
Wang, T 
Bannan, TJ
Priestley, M
Percival, CJ
Shallcross, DE
Lu, K
Gu,o S
Hu, M
Hallquist, M
Issue Date: 2018
Publisher: Copernicus GmbH
Source: Atmospheric chemistry and physics, 2018, v. 18, no. 17, p. 13013-13030 How to cite?
Journal: Atmospheric chemistry and physics 
Abstract: Nitryl chloride (ClNO2) accumulation at night 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 and a suite of inorganic halogens including ClNO2 and reactions of chloride with volatile organic compounds (Cl-VOCs) in the gas and particle phases utilising the Filter Inlet for Gas and AEROsols time-of-flight chemical ionisation mass spectrometer (FIGAERO-ToF-CIMS) during an intensive measurement campaign 40km northwest of Beijing in May and June 2016. A maximum mixing ratio of 2900ppt of ClNO2 was observed with a mean campaign nighttime mixing ratio of 487ppt, 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 mixing ratios persisting after numerous e-folding times of the photolytic lifetime enabling the chlorine atom production to reach 2.3 × 105moleculescm-3 from ClNO2 alone, peaking at 09:30LT and up to 8.4 × 105moleculescm-3 when including the supporting inorganic halogen measurements. Cl-VOCs were observed in the particle and gas phases 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 secondary organic aerosol (SOA) formation.
URI: http://hdl.handle.net/10397/79990
ISSN: 1680-7316
EISSN: 1680-7324
DOI: 10.5194/acp-18-13013-2018
Rights: © Author(s) 2018. This work is distributed under the Creative Commons Attribution 4.0 License (https://creativecommons.org/licenses/by/4.0/).
The following publication 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. (2018). 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., 18, 13013-13030 is available at https://doi.org/10.5194/acp-18-13013-2018
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