Preprints
https://doi.org/10.5194/acp-2020-443
https://doi.org/10.5194/acp-2020-443

  08 Jun 2020

08 Jun 2020

Review status: this preprint was under review for the journal ACP but the revision was not accepted.

Impact of organic acids on chloride depletion of inland transported sea spray aerosols

Bojiang Su1, Zeming Zhuo1, Yuzhen Fu2,3, Wei Sun2,3, Ying Chen1, Xubing Du1, Yuxiang Yang2,3, Si Wu1, Fugui Huang4, Duohong Chen5, Lei Li1, Guohua Zhang2,6, Xinhui Bi2,6, and Zhen Zhou1 Bojiang Su et al.
  • 1Guangdong Provincial Engineering Research Center for Online Source Apportionment System of Air Pollution, Institute of Mass Spectrometry and Atmospheric Environment, Jinan University, Guangzhou 510632, PR China
  • 2State Key Laboratory of Organic Geochemistry and Guangdong Key Laboratory of Environmental Protection and Resources Utilization, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640, PR China
  • 3University of Chinese Academy of Sciences, Beijing 100039, PR China
  • 4Guangzhou Hexin Analytical Instrument Limited Company, Guangzhou 510530, PR China
  • 5State Environmental Protection Key Laboratory of Regional Air Quality Monitoring, Guangdong Environmental Monitoring Center, Guangzhou 510308, PR China
  • 6Guangdong-Hong Kong-Macao Joint Laboratory for Environmental Pollution and Control, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640, PR China

Abstract. Heterogeneous reactions on sea spray aerosols (SSA) are the main pathway to drive the circulation of chlorine, nitrogen, and sulfur in the atmosphere. The release of Cl will significantly affect the physicochemical properties of SSA. However, the impact of organic acids and mixing state on chloride depletion of SSA is still unclear. Hence, the size and chemical composition of individual SSA particles during the East Asian summer monsoon were investigated by a single particle aerosol mass spectrometer (SPAMS). According to the chemical composition, SSA particles were classified into SSA-Aged, SSA-Bio and SSA-Ca. In comparison to the aged Na-rich SSA particles (SSA-Aged), some additional organic species related to biological origin were observed in SSA-Bio, and each of two types accounts for approximately 50 % of total SSA particles. SSA-Ca may associated with organic shell of Na-rich SSA particles, which only accounts for ~ 3 %. Strongly positive correlations between Na and organic acids (including formate, acetate, propionate, pyruvate, oxalate, malonate, succinate, and glutarate) were observed for the SSA-Aged (r2 = 0.52, p < 0.01) and SSA-Bio (r2 = 0.61, p < 0.01), indicating the significance of organic acids in the chloride depletion during inland transport. The contribution of these organic acids to the chloride depletion is estimated to be up to 34 %. Interestingly, the degree of chloride depletion is distinctly different between SSA-Aged and SSA-Bio. It is most probably attributed to the associated organic coating in the SSA-Bio particles, which inhibit the displacement reactions between acids and chloride. As revealed from the mixing state of SSA-Bio, Cl / Na ratio increases with increasing phosphate and organic nitrogen, which is known to originate from biological activities. This finding provides some basis for the improvement of modeling simulations in chlorine circulation and a comprehensive understanding of the effects of organics on chloride depletion of SSA particles.

Bojiang Su et al.

 
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Bojiang Su et al.

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Short summary
In this study, chemical composition, mixing state and aging degree of individual sea spray aerosol (SSA) were measured by single particle aerosol mass spectrometer (SPAMS) during summer monsoon in southern China. Our results show that organic acids has significant contribution to chloride depletion of SSA. A class of biological SSA underwent relative weak chloride depletion compare to other SSA types, which may attribute to organic species (i.e. organic nitrogen and biological phosphate).
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