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https://doi.org/10.5194/acp-2020-113
© Author(s) 2020. This work is distributed under
the Creative Commons Attribution 4.0 License.
https://doi.org/10.5194/acp-2020-113
© Author(s) 2020. This work is distributed under
the Creative Commons Attribution 4.0 License.

Submitted as: research article 13 Feb 2020

Submitted as: research article | 13 Feb 2020

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This preprint is currently under review for the journal ACP.

Contribution of hydroxymethanesulfonate (HMS) to severe winter haze in the North China Plain

Tao Ma1, Hiroshi Furutani2,3, Fengkui Duan1, Takashi Kimoto4, Jingkun Jiang1, Qiang Zhang5, Xiaobin Xu6, Ying Wang6, Jian Gao7, Guannan Geng1, Meng Li5, Shaojie Song8, Yongliang Ma1, Fei Che7, Jie Wang7, Lidan Zhu1, Tao Huang4, Michisato Toyoda3, and Kebin He1 Tao Ma et al.
  • 1State Key Joint Laboratory of Environment Simulation and Pollution Control, School of Environment, State Environmental Protection Key Laboratory of Sources and Control of Air Pollution Complex, Beijing Key Laboratory of Indoor Air Quality Evaluation and Control, Tsinghua University, Beijing 100084, China
  • 2Support Center for Scientific Instrument Renovation and Custom Fabrication, Osaka University, Osaka, 560-0043, Japan
  • 3Project Research Center for Fundamental Sciences, Graduate School of Science, Osaka University, Osaka, 560-0043, Japan
  • 4Kimoto Electric Co., Ltd, 3-1 Funahashi-cho Tennoji-ku, Osaka 543-0024, Japan
  • 5Ministry of Education Key Laboratory for Earth System Modeling, Department of Earth System Science, Tsinghua University, Beijing 100084, China
  • 6State Key Laboratory of Severe Weather & Key Laboratory for Atmospheric Chemistry of CMA, Chinese Academy of Meteorological Sciences, Beijing 100081, China
  • 7State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012, China
  • 8School of Engineering and Applied Sciences, Harvard University, Cambridge, MA 02138, USA

Abstract. Severe winter hazes accompanied by high concentrations of fine particulate matter (PM2.5) occur frequently in the North China Plain and threaten public health. Organic matter (OM) and sulfate are recognized as major components of PM2.5, while atmospheric models often fail to predict their high concentrations during severe winter hazes due to incomplete understanding of secondary aerosol formation mechanisms. By using a novel combination of single particle mass spectrometer and optimized ion chromatography measurement, here we show that hydroxymethanesulfonate (HMS), formed by the reaction between formaldehyde (HCHO) and dissolved SO2 in aerosol water, is ubiquitous in Beijing winter. The HMS concentration and the molar ratio of HMS to sulfate increased with the deterioration of winter haze. High concentrations of precursors (SO2 and HCHO) coupled with low oxidant levels, low temperature, high relative humidity, and moderately acid pH facilitate the heterogeneous formation of HMS, which could account for up to 15 % of OM in winter haze and lead to 36 % overestimates of sulfate when using traditional ion chromatography measurements. Despite the clean air actions have substantially reduced SO2 emissions, HMS concentration and molar ratio of HMS to sulfate during severe winter hazes increased from 2015 to 2016 with the growth of HCHO concentration. Our findings illustrate the significant contribution of heterogeneous HMS chemistry to severe winter hazes in Beijing, which help to improve the prediction of OM and sulfate, and suggest that the reduction in HCHO can help to mitigate haze pollution.

Tao Ma et al.

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Short summary
Formation mechanisms of organic matter and sulfate in winter hazes in the North China Plain remain unclear. We quantify the large amounts of hydroxymethanesulfonate (HMS), formed by the reaction between formaldehyde and SO2, in PM2.5 in Beijing winter hazes, and elucidate the heterogeneous HMS chemistry in favorable winter haze conditions. The HMS not only contributes a substantial mass of organic matter, but also leads to overestimation of sulfate in conventional measurements.
Formation mechanisms of organic matter and sulfate in winter hazes in the North China Plain...
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