Articles | Volume 17, issue 20
Atmos. Chem. Phys., 17, 12797–12812, 2017
Atmos. Chem. Phys., 17, 12797–12812, 2017

Research article 27 Oct 2017

Research article | 27 Oct 2017

Hygroscopic behavior and chemical composition evolution of internally mixed aerosols composed of oxalic acid and ammonium sulfate

Xiaowei Wang1,2, Bo Jing3, Fang Tan3,4, Jiabi Ma1, Yunhong Zhang1, and Maofa Ge3,4,5 Xiaowei Wang et al.
  • 1The Institute of Chemical Physics, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081, China
  • 2School of Chemical Engineering and Pharmaceutics, Henan University of Science and Technology, Luoyang 471023, China
  • 3Beijing National Laboratory for Molecular Sciences (BNLMS), State Key Laboratory for Structural Chemistry of Unstable and Stable Species, CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China
  • 4University of Chinese Academy of Sciences, Beijing 100049, China
  • 5Center for Excellence in Regional Atmospheric Environment, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen 361021, China

Abstract. Although water uptake of aerosol particles plays an important role in the atmospheric environment, the effects of interactions between components on chemical composition and hygroscopicity of particles are still not well constrained. The hygroscopic properties and phase transformation of oxalic acid (OA) and mixed particles composed of ammonium sulfate (AS) and OA with different organic to inorganic molar ratios (OIRs) have been investigated by using confocal Raman spectroscopy. It is found that OA droplets first crystallize to form OA dihydrate at 71 % relative humidity (RH), and further lose crystalline water to convert into anhydrous OA around 5 % RH during the dehydration process. The deliquescence and efflorescence point for AS is determined to be 80.1 ± 1.5 % RH and 44.3 ± 2.5 % RH, respectively. The observed efflorescence relative humidity (ERH) for mixed OA ∕ AS droplets with OIRs of 1 : 3, 1 : 1 and 3 : 1 is 34.4 ± 2.0, 44.3 ± 2.5 and 64.4 ± 3.0 % RH, respectively, indicating the elevated OA content appears to favor the crystallization of mixed systems at higher RH. However, the deliquescence relative humidity (DRH) of AS in mixed OA ∕ AS particles with OIRs of 1 : 3 and 1 : 1 is observed to occur at 81.1 ± 1.5 and 77 ± 1.0 % RH, respectively. The Raman spectra of mixed OA ∕ AS droplets indicate the formation of ammonium hydrogen oxalate (NH4HC2O4) and ammonium hydrogen sulfate (NH4HSO4) from interactions between OA and AS in aerosols during the dehydration process on the time scale of hours, which considerably influence the subsequent deliquescence behavior of internally mixed particles with different OIRs. The mixed OA ∕ AS particles with an OIR of 3 : 1 exhibit no deliquescence transition over the RH range studied due to the considerable transformation of (NH4)2SO4 into NH4HC2O4 with a high DRH. Although the hygroscopic growth of mixed OA ∕ AS droplets is comparable to that of AS or OA at high RH during the dehydration process, Raman growth factors of mixed particles after deliquescence are substantially lower than those of mixed OA ∕ AS droplets during the efflorescence process and further decrease with elevated OA content. The discrepancies for Raman growth factors of mixed OA ∕ AS particles between the dehydration and hydration process at high RH can be attributed to the significant formation of NH4HC2O4 and residual OA, which remain solid at high RH and thus result in less water uptake of mixed particles. These findings improve the understanding of the role of reactions between dicarboxylic acid and inorganic salt in the chemical and physical properties of aerosol particles, and might have important implications for atmospheric chemistry.

Short summary
Our results reveal the formation of NH4HC2O4 and NH4HSO4 from the reaction of oxalic acid (OA) with ammonium sulfate within aerosols during the slow dehydration compared to the rapid dehydration process. The hygroscopic growth of mixed particles at high RH upon hydration is substantially lower than that of the corresponding dehydration process due to the significant formation of low hygroscopic NH4HC2O4 and residual OA. These findings have important implications for atmospheric chemistry.
Final-revised paper