Aqueous-phase oxidation of three phenolic compounds by hydroxyl radical: Insight into secondary organic aerosol formation yields, mechanisms, products and optical properties

Ye, Zhaolian; Zhuang, Yanxin; Chen, Yantong; Zhao, Zi-Long; Ma, Shuaishuai; Huang, Hongying; Chen, Yanfang; Ge, Xinlei

doi:10.1016/j.atmosenv.2019.117240

Cited by 29 publications

(27 citation statements)

References 54 publications

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“…This suggests that initial oxidation of FF-POA to MD-OOA increases light absorption and subsequent oxidation to aq-SOA decreases light absorption. A similar behavior of initial increase in light absorption during aging, followed by a decrease, has been observed in biomass burning plumes (36,51,52). MD-OOA has the highest correlation with BC-PM 1 nitrate among all OA components (SI Appendix, Fig.…”

Section: Resultssupporting

confidence: 72%

Aqueous production of secondary organic aerosol from fossil-fuel emissions in winter Beijing haze

Wang

Zhang

et al. 2021

Proc. Natl. Acad. Sci. U.S.A.

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115

106

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Secondary organic aerosol (SOA) produced by atmospheric oxidation of primary emitted precursors is a major contributor to fine particulate matter (PM2.5) air pollution worldwide. Observations during winter haze pollution episodes in urban China show that most of this SOA originates from fossil-fuel combustion but the chemical mechanisms involved are unclear. Here we report field observations in a Beijing winter haze event that reveal fast aqueous-phase conversion of fossil-fuel primary organic aerosol (POA) to SOA at high relative humidity. Analyses of aerosol mass spectra and elemental ratios indicate that ring-breaking oxidation of POA aromatic species, leading to functionalization as carbonyls and carboxylic acids, may serve as the dominant mechanism for this SOA formation. A POA origin for SOA could explain why SOA has been decreasing over the 2013–2018 period in response to POA emission controls even as emissions of volatile organic compounds (VOCs) have remained flat.

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Section: Resultssupporting

confidence: 72%

Aqueous production of secondary organic aerosol from fossil-fuel emissions in winter Beijing haze

Wang

Zhang

et al. 2021

Proc. Natl. Acad. Sci. U.S.A.

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115

106

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“…Comparison of products at 11h and 23h showed no significant difference. Similar to results reported by our previous work (Ye et al, 2020) Overall, there are little differences between products identified in this work and those in our previous work (Ye et al, 2020), despite the different light sources and oxidants.…”

Section: Oxidation Degrees Of Aqsoasupporting

confidence: 92%

“…The aqSOA mass yields in OH-initiated oxidation of this work agree well with that reported previously for phenolic carbonyls, that is, 120% for syringaldehyde (Huang et al, 2018). Our previous study on eugenol OH oxidation illuminated by a 500 W Xe lamp reported the aqSOA mass yield of ~180% for eugenol (Ye et al, 2020), slightly higher than the value reported in this work.…”

Section: Generated Hulis Concentrationsupporting

confidence: 91%

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Optical properties and oxidative potential of aqueous-phase products from OH and <sup>3</sup>C<sup>*</sup>-initiated photolysis of eugenol

Tao

Zhu

et al. 2021

Preprint

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Abstract. In ambient air, aqueous-phase oxidation may turn precursors into more light-absorbing and toxic products, leading to air quality deterioration and adverse health effects. In this study, we investigated eugenol degradation in aqueous phase under direct photolysis, and triplet excited organic (3C*) and hydroxyl radical (OH) as oxidants. Results showed degradation rates of eugenol followed the order of 3C* > OH > direct photolysis. Relative contributions of reactive oxygen species (ROS) and 3C* were evaluated via quenching and O2-free experiments. 3C* played a dominant role in eugenol degradation for 3C*-initiated oxidation, while both O2 and O2•-generated were important for eugenol degradation for OH-initiated oxidation. Rate constants under O2, air and N2 followed the order of ko2＞kAir＞kN2 under both direct photolysis and OH oxidation, and it changed to kAir＞kN2＞ko2 in 3C*-initiated oxidation. Light absorption spectra showed absorbance at 300–400 nm increased as photolysis progressed, and there were new broad fluorescent spectra at excitation/emission (Ex/Em) = 250/(400–500) nm, suggesting the formation of new chromophores and fluorophores, such as humic-like substances (HULIS). Additionally, distinct ﬂuorescence peaks appeared at Ex/Em=(300–350)/300 nm at different stages. Concentration of generated HULIS increased gradually over time, then leveled off. Dithiothreitol (DTT) assay was applied to assess the oxidation potential of products, which was greater than pure eugenol, suggesting more harmful species were produced during oxidation. Detailed reaction pathways were elucidated via analyses of chemical characteristics of the products.

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“…In cloud water, the oxidation of precursors can be initiated by the hydrogen abstraction or electron transfer reaction driven by the OH q , resulting in the formation of organic acids and condensed compounds (McNeill, 2015). On the one hand, photolysis causes the fragmentation of high-molecular-weight organic compounds, resulting in the formation of relatively lowmolecular-weight compounds such as small acids, including oxalic, glyoxylic, and, in large quantities, formic and acetic acid (Renard et al, 2015;Schurman et al, 2018;Huang et al, 2018;Sun et al, 2010;Li et al, 2014;Löflund et al, 2002;Ye et al, 2020). These compounds are highly oxygenated owing to cloud processing (Brege et al, 2018;Sareen et al, 2016), as indicated by the fact that aqSOA has a higher O/C ratio (∼ 1) than gas-phase SOA (0.3-0.5) in the atmosphere (Ervens et al, 2011).…”

Section: Introductionmentioning

confidence: 99%

Measurement report: Molecular characteristics of cloud water in southern China and insights into aqueous-phase processes from Fourier transform ion cyclotron resonance mass spectrometry

Sun

Zhang

et al. 2021

Atmos. Chem. Phys.

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Abstract. Characterizing the molecular composition of cloud water could provide unique insights into aqueous chemistry. Field measurements were conducted at Mt. Tianjing in southern China in May, 2018. There are thousands of formulas (C5–30H4–55O1–15N0–2S0–2) identified in cloud water by Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). CHON formulas (formulas containing C, H, O, and N elements; the same is true for CHO and CHOS) represent the dominant component (43.6 %–65.3 % of relative abundance), followed by CHO (13.8 %–52.1%). S-containing formulas constitute ∼5 %–20 % of all assigned formulas. Cloud water has a relative-abundance-weighted average O/C of 0.45–0.56, and the double bond equivalent of 5.10–5.70. Most of the formulas (>85 %) are assigned as aliphatic and olefinic species. No statistical difference in the oxidation state is observed between cloud water and interstitial PM2.5. CHON with aromatic structures are abundant in cloud water, suggesting their enhanced in-cloud formation. Other organics in cloud water are mainly from biomass burning and oxidation of biogenic volatile organic compounds. The cloud water contains more abundant CHON and CHOS at night, which are primarily contributed by −N2O5 function and organosulfates, demonstrating the enhanced formation in dark aqueous or multi-phase reactions. While more abundant CHO is observed during the daytime, likely due to the photochemical oxidation and photolysis of N- or S-containing formulas. The results provide an improved understanding of the in-cloud aqueous-phase reactions.

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Aqueous-phase oxidation of three phenolic compounds by hydroxyl radical: Insight into secondary organic aerosol formation yields, mechanisms, products and optical properties

Cited by 29 publications

References 54 publications

Aqueous production of secondary organic aerosol from fossil-fuel emissions in winter Beijing haze

Aqueous production of secondary organic aerosol from fossil-fuel emissions in winter Beijing haze

Optical properties and oxidative potential of aqueous-phase products from OH and <sup>3</sup>C<sup>*</sup>-initiated photolysis of eugenol

Measurement report: Molecular characteristics of cloud water in southern China and insights into aqueous-phase processes from Fourier transform ion cyclotron resonance mass spectrometry

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Aqueous-phase oxidation of three phenolic compounds by hydroxyl radical: Insight into secondary organic aerosol formation yields, mechanisms, products and optical properties

Cited by 29 publications

References 54 publications

Aqueous production of secondary organic aerosol from fossil-fuel emissions in winter Beijing haze

Aqueous production of secondary organic aerosol from fossil-fuel emissions in winter Beijing haze

Optical properties and oxidative potential of aqueous-phase products from OH and &lt;sup&gt;3&lt;/sup&gt;C&lt;sup&gt;*&lt;/sup&gt;-initiated photolysis of eugenol

Measurement report: Molecular characteristics of cloud water in southern China and insights into aqueous-phase processes from Fourier transform ion cyclotron resonance mass spectrometry

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Optical properties and oxidative potential of aqueous-phase products from OH and <sup>3</sup>C<sup>*</sup>-initiated photolysis of eugenol