Secondary organic aerosol formation from 3C⁎-initiated oxidation of 4-ethylguaiacol in atmospheric aqueous-phase

Chen, Yantong; Li, Nanwang; Li, Xudong; Tao, Ye; Luo, Shipeng; Zhao, Zi-Long; Ma, Shuaishuai; Huang, Hongying; Chen, Yanfang; Ye, Zhaolian; Ge, Xinlei

doi:10.1016/j.scitotenv.2020.137953

Cited by 27 publications

(87 citation statements)

References 41 publications

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“…2,3 Very recently, the potential importance of triplet state chemistry has been unraveled for the atmospheric aqueous phase by novel ambient measurements of triplet state concentrations in fog and aerosol water, and by reactivity measurements under atmospheric conditions of various photosensitizers known to be present in the particulate matter. [3][4][5][6][7][8][9][10][11] For instance, triplet excited states of aromatic ketones have been shown to oxidize phenols commonly found in biomass burning aerosol, 12,13 and halide ions commonly found in sea spray aerosol. 14 In the latter case, the halide ion oxidation induces the formation of halogen atoms (Xc) or radical anions (X 2 c À ), 10 which are important reactive species for the oxidation of organic and inorganic compounds throughout the troposphere.…”

Section: Introductionmentioning

confidence: 99%

Quenching of ketone triplet excited states by atmospheric halides

Gemayel

Emmelin

Perrier

et al. 2021

Environ. Sci.: Atmos.

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Section: Introductionmentioning

confidence: 99%

Quenching of ketone triplet excited states by atmospheric halides

Gemayel

Emmelin

Perrier

et al. 2021

Environ. Sci.: Atmos.

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“…CC BY 4.0 License. air-and N2-saturated conditions, respectively, and the bubbling was continued throughout the reactions (Du et al, 2011;Chen et al, 2020). The aim of the air-saturated experiments was to enable the generation of secondary oxidants ( 1 O2, O2 •-/ • HO2, • OH) from 3 VL* as O2 is present.…”

Section: Aqueous Phase Photo-oxidation Experimentsmentioning

confidence: 99%

Section: Kinetics Mass Spectrometric and Absorbance Changes Analyses During Aqueous Phase Photo-oxidation Of Vanillinmentioning

confidence: 99%

“…The disproportionation of HO2 • /O2 •- (Anastasio et al, 1996) and reaction of HO2 • with O2 •- (Du et al, 2011) Chen et al, 2020). 1 O2 is also an efficient oxidant for unsaturated organic compounds and has a lifetime that is much longer than 3 C* (Chen et al, 2020). Similar to VL*, the decay rate for VL+AN under air-saturated conditions was faster (6.6 times) than N2-saturated conditions, which can be due to several reactions facilitated by nitrate photolysis products and the enhancement of N(III)-mediated photo-oxidation in the presence of O2 as reported in early works (Vione et al, 2005;Kim et al, 2014;Pang et al, 2019a).…”

Section: Kinetics Mass Spectrometric and Absorbance Changes Analyses During Aqueous Phase Photo-oxidation Of Vanillinmentioning

confidence: 99%

“…The 3 C* concentration in typical fog water has been estimated to be >25 times than that of • OH, making 3 C* the primary photooxidant for biomass burning phenolic compounds (Kaur and Anastasio, 2018;Kaur et al, 2019). Recent works on tripletdriven oxidation of phenols have mainly focused on changes of physicochemical properties (e.g., light absorption) and aqSOA yield (e.g., Smith et al, 2014Smith et al, , 2015Smith et al, , 2016, with few reports on reaction mechanisms and characterization of reaction products (e.g., Yu et al, 2014;Chen et al, 2020;Jiang et al, 2021).…”

Section: Introductionmentioning

confidence: 99%

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Aqueous SOA formation from the photo-oxidation of vanillin: Direct photosensitized reactions and nitrate-mediated reactions

Mabato

Lyu

et al. 2021

Preprint

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Abstract. Vanillin (VL), a phenolic aromatic carbonyl abundant in biomass burning emissions, forms triplet excited states (3VL*) under simulated sunlight leading to aqueous secondary organic aerosol (aqSOA) formation. This direct photosensitized oxidation of VL was compared with nitrate-mediated VL photo-oxidation under atmospherically relevant cloud and fog conditions, through examining the VL decay kinetics, product compositions, and light absorbance changes. The majority of the most abundant products from both VL photo-oxidation pathways were potential Brown carbon (BrC) chromophores. In addition, both pathways generated oligomers, functionalized monomers, and oxygenated ring-opening products, but nitrate promoted functionalization and nitration, which can be ascribed to its photolysis products (•OH, •NO2, and N(III), NO2- or HONO). Moreover, a potential imidazole derivative observed from nitrate-mediated VL photo-oxidation suggested that ammonium may be involved in the reactions. The effects of secondary oxidants from 3VL*, pH, the presence of volatile organic compounds (VOCs) and inorganic anions, and reactants concentration and molar ratios on VL photo-oxidation were also explored. Our findings show that the secondary oxidants (1O2, O2•-/•HO2, •OH) from the reactions of 3VL* and O2 play an essential role in VL photo-oxidation. Enhanced oligomer formation was noted at pH < 4 and in the presence of VOCs and inorganic anions, probably due to additional generation of radicals (•HO2 and CO3•-). Also, functionalization was dominant at low VL concentration, whereas oligomerization was favored at high VL concentration. Furthermore, guaiacol oxidation by photosensitized reactions of VL was observed to be more efficient relative to nitrate-mediated photo-oxidation. Lastly, potential VL photo-oxidation pathways under different reaction conditions were proposed. This study indicates that the direct photosensitized oxidation of VL, which nitrate photolysis products can further enhance, may be an important aqSOA source in areas influenced by biomass burning emissions.

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