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Photooxidation of Methacrolein in Fe(III)-Oxalate Aqueous System and Its Atmospheric Implication


Iron and oxalic acids are widely distributed in the atmosphere and easily form ferric oxalate complex (Fe(III)-Ox). The tropospheric aqueous-phase could provide a medium to enable the photo-Fenton reaction with Fe(III)-Ox under solar irradiation. Although the photolysis mechanisms of Fe(III)-Ox have been investigated extensively, information about the oxidation of volatile organic compounds (VOC), specifically the potential for Secondary Organic Aerosol (SOA) formation in the Fe(III)-Ox system, is lacking. In this study, a ubiquitous VOC methacrolein (MACR) is chosen as a model VOC, and the oxidation of MACR with Fe(III)-Ox is investigated under typical atmospheric water conditions. The effects of oxalate concentration, Fe(III) concentration, MACR concentration, and pH on the oxidation of MACR are studied in detail. Results show that the oxidation rate of MACR greatly accelerates in the presence of oxalate when compared with only Fe(III). The oxidation rate of MACR also accelerates with increasing concentration of oxalate. The effect of Fe(III) is found to be more complicated. The oxidation rate of MACR first increases and then decreases with increasing Fe(III) concentration. The oxidation rate of MACR increases monotonically with decreasing pH in the common atmospheric water pH range or with decreasing MACR concentration. The production of ferrous and hydrogen peroxide, pH, and aqueous absorbance are monitored throughout the reaction process. The quenching experiments verify that ·OH and \(O_2^{\bar .}\) are both responsible for the oxidation of MACR. MACR is found to rapidly oxidize into small organic acids with higher boiling points and oligomers with higher molecular weight, which contributes to the yield of SOA. These results suggest that Fe(III)-Ox plays an important role in atmospheric oxidation.

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The authors gratefully acknowledge financial support from the Ministry of Science and Technology of the People’s Republic of China (Grant Nos. 2017YFC0210005 and 2016YFE0112200).

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Correspondence to Wenbo Dong.

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Article Highlights

• The oxidation mechanism of methacrolein is investigated in the Fe(III)-Ox system in atmospheric water, indicating that \(O_2^{\bar .}\) can directly oxidize MACR.

• The Fe(III)-Ox Fenton-like reaction in the atmosphere increases the absorbance of aerosols and has implications for radiative forcing.

• Methacrolein is rapidly oxidized into small organic acids with higher boiling points and oligomers with higher molecular weight in the Fe(III)-Ox Fenton-like system, which contributes to the yield of SOA.

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Wang, Y., Zhao, J., Liu, H. et al. Photooxidation of Methacrolein in Fe(III)-Oxalate Aqueous System and Its Atmospheric Implication. Adv. Atmos. Sci. 38, 1252–1263 (2021).

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Key words

  • Fe(III)-Ox
  • OH radical
  • atmospheric oxidation
  • SOA
  • methacrolein


  • 草酸铁
  • 羟基自由基
  • 大气氧化性
  • 二次气溶胶
  • 甲基丙烯醛